Cement and concrete – benefits and

barriers in coal ash utilisation

Irene M Smith
CCC/94

January 2005

Copyright © IEA Clean Coal Centre

ISBN 92-9029-409-4

Abstract
The coal combustion products industry is facing major challenges despite decades of beneficial utilisation of coal ash in a wide
variety of applications. Fly ash is especially affected by recent trends towards greater implementation of NOx control systems
which may increase the carbon and ammonia in ash. Cocombustion with greater proportions of secondary fuels, such as biomass,
also results in more varied ash. Fly ash is often produced to tight specifications for applications in the cement and concrete
industries. The requirements need to be broadened to include all potential markets for a wider range of fly ash specifications. Fly
ash utilisation is hindered where it is regarded as a waste or by-product.

This report summarises recent trends in coal ash utilisation in different countries. It then focuses on two major sectors of fly ash
utilisation: cement and concrete. Requirements for many different uses of fly ash are compared. The engineering and
environmental benefits of using fly ash are investigated for each sector. These include greater long term strength and durability,
CO2 emissions reduction, and saving primary aggregates. Barriers to utilisation occur in marketing, handling, transport and
storage, through increased carbon or ammonia in ash, the effects of cofiring with secondary fuels and through the potential for
mercury release from fly ash. These are being overcome by various means in the utilisation sectors or are under investigation.
Continued use of fly ash in traditional markets is helped by draining and drying stockpiled fly ash, classification, separation and
burnout processes. Total use of fly ash is the aim of new combined processes to produce high-grade and expensive materials for
various specialised applications.
 Acronyms and abbreviations
ACAA American Coal Ash Association
ADAA Ash Development Association of Australia Inc
AMC ash modified clinker
ASR alkali silicate reaction
ASTM American Society for Testing Materials
BVK Bundesverband Kraftwerksnebenprodukte (German Association of Coal Combustion Products)
C2P2 Coal combustion products partnership (USA)
C3A tricalcium aluminate cement
CBO carbon burnout process
CBRC Combustion Byproducts Recycling Consortium (USA)
CCP coal combustion products
CCUJ Centre for Coal Utilisation Japan
DTI Department of Trade and Industry (UK)
ECOBA European Coal Combustion Products Association
EERC Energy & Environmental Research Center (USA)
EPA Environment Protection Authorities (Australia)
EPRI Electric Power Research Institute (USA)
ESP electrostatic precipitator
EU European Union
FBC fluidised bed combustion
FGD flue gas desulphurisation
FBA furnace bottom ash
IGCC integrated gasification combined cycle
LOI loss-on-ignition
MCB microwave carbon burnout
MOEF Ministry of Environment & Forests (India)
NAS National Academy of Sciences (USA)
NETL National Energy Technology Laboratory (USA)
NEPC National Environment Protection Council (Australia)
PF pulverised fuel
PFA pulverised fuel ash
PPC Portland pozzolanic cements
PROGRES Production of Novel Products from Glassy Combustion Residues
RCRA Resource Conservation and Recovery Act (USA)
SCR selective catalytic reduction
SNCR selective non-catalytic reduction
SMCRA Surface Mining Control and Reclamation Act (USA)
STI Separation Technologies Inc
th% percentage by energy input
TFS Tribo Flow Separations
US DOE US Department of Energy
US EPA United States Environmental Protection Agency
UKQAA United Kingdom Quality Ash Association
WML Waste Management Licensing (UK)
wt% percentage by weight

2 IEA CLEAN COAL CENTRE

 Contents
Acronyms and abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2 Production and utilisation of coal residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

2.1 Production and use in different countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 Increasing ash utilisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

3 Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.1 Cement raw material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2 Blended cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3 Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

4 Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.1 Requirements for use of fly ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2 Engineering benefits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.2.1 Strength and workability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.2.2 Durability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.3 Environmental benefits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3.1 CO2 reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3.2 Saving primary aggregates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.4 Overcoming barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.4.1 Marketing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.4.2 Handling, transport and storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.4.3 Carbon in ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.4.4 Ammonia in ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.4.5 Cofiring issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.4.6 Mercury in ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.5 Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

5 Treatments and beneficiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

5.1 Carbon in ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.1.1 Classification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.1.2 Grinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.1.3 Blending processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.1.4 Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.1.5 Combined classification and separation processes. . . . . . . . . . . . . . . . . . . . . . . 52
5.1.6 Burnout, fusing and oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.1.7 Chemical neutralisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.2 Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.3 Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

Cement and concrete – benefits and barriers in coal ash utilisation 3

4 IEA CLEAN COAL CENTRE
 1 Introduction
Residues from coal-fired power stations are referred to in
many different ways. In general the terms coal combustion
products, coal ash and fly ash are preferred in this report but
the terms adopted in the information cited are also retained.
Coal combustion products is the term favoured both by the
American Coal Ash Association (ACAA) and the European
Coal Combustion Products Association (ECOBA) because
the products are actually manufactured to meet certain
requirements set in standards or regulations (vom Berg,
2000). These products broadly include fly ash from the
electrostatic precipitator (ESP) or baghouse of pulverised
coal-fired boilers, bottom ash at the bottom of the furnace,
residues from flue gas desulphurisation (FGD), fluidised bed
combustors and from gasifiers used for power generation. By
the mid 1970s fly ash became known as pulverised fuel ash
(PFA) in the UK to differentiate it from fly ashes derived
from other processes such as municipal waste incineration
(Sear, 2001). The coarser bottom ash from dry bottom,
pulverised coal-fired boilers is termed furnace bottom ash
(FBA) in the UK. It is classified as clinker ash in Japan
(Sakai and Hara, 2003). Boiler slag is a granular material that
settles to the bottom of wet bottom pulverised coal-fired
where the operating temperature in the boiler exceeds the ash
fusion temperature. Dry bottom boilers produce only 20%
bottom ash and 80% fly ash, while wet bottom boilers
produce equal quantities of both slag and fly ash (Walker and
others, 2002).
Residues from FGD include FGD gypsum, spray dry
absorption product, and more specialised products such as
sulphuric acid from less commonly used systems. This topic
is not included here but may be reviewed by the Clean Coal
Centre in a future report. Residue issues form part of the
decision when choosing alternative technologies to pulverised
fuel (PF) combustion. The actual and potential applications
for circulating fluidised bed combustion and for integrated
gasification combined cycle residues are examined in greater
detail in a separate report by IEA CCC (see Adams, 2004).
Despite successful use of fly ash for many decades, and
current emphasis on minimising waste materials to avoid
landfill, environmental legislation is being applied in a way
which hinders rather than furthers deployment of fly ash in
traditional applications. Designation of fly ash as a waste
material rather than a product furthers use of primary,
naturally occurring materials. This is overall detrimental to
the environment (Sear, 2003a). Fly ash is included in the
European Waste Catalogue, which lists about 800 waste
materials, as non-hazardous as determined by the EC
Hazardous Waste List. The ash results from burning coal at
temperatures of between 1250°C and 1400°C. Hence, it is a
glassy material and its principal constituents are oxides of
silica, alumina, iron and some calcium which are chemically,
or pozzolanically, active (combines with free lime). The pH
of the leachate is typically 8 to 11 or 12 although it could
initially have a low pH if sufficient sulphate, deposited on the
surface, is brought into solution as sulphuric acid. Some
Australian coals produce ashes giving leachate with a pH of
Cement and concrete – benefits and barriers in coal ash utilisation
4.5–5.5 (Riley, 2004). Lagoon ash or pond ash also has a
lower pH as most of the water soluble material has been
washed out. About 2–5% of PFA is water soluble and the
solution is generally alkaline although it initially has a low
pH as the sulphate deposited on the surface of the particles is
brought into solution as sulphuric acid. After a short time the
pH rises rapidly as calcium is leached into solution. Other
properties which are important for PFA becoming one of the
main raw materials for the building and construction industry
are that it is a fine, lightweight powder with predominantly
rounded particles, and it can take up water (DTI, 2002; Sear,
2002; Sear and others, 2003):
Marketing of fly ash is more successful where ash
associations are promoting co-operation between the relevant
industries, and are involved with the development of
standards and environmental legislation (see Brennan, 2003;
Brennan and others, 2003; Kumar and others, 2003a,b and
Chapter 2). Networks to promote transfer of knowledge from
utilities to ash users also play a major role (Janssen, 2003).
Storage may be an issue for dry fly ash, used in high value
applications. In many cases, the highest production of fly ash
does not occur at the time of greatest demand from the
construction industry. Hence storage capacity in the silos may
limit the chances of a utility delivering its fly ash to the
market (Backer van Ommeren, 2003). Wet fly ash may be
stored easily but is mostly used in landfill. This practice is
becoming less acceptable in many countries. In the USA, the
low cost of landfilling coal combustion products and
variations in material properties have been a barrier to
utilisation (Walker and others, 2002). Reclamation of ash
from lagoons is in progress in some countries. There is an
incentive to utilise the lower quality fly ashes which may
require some treatment for use in cement and concrete. The
market study by the Cooperative Research Centre for Coal in
Sustainable Development in Australia strongly emphasised
that there is merit in pursuit of applications which will result
in very large volumes of ash being removed. It is critical to
reduce the effect of transport costs by finding uses that have a
high value to the user (Heeley, 2003).
Recent trends towards tighter air pollution control and wider
use of cocombustion with secondary fuels has resulted in
more varied ashes, stimulating research and development of
applications for particular types of ash. Concerns that
mercury and other trace elements may be increased in ashes
from cofiring at high substitution rates have been addressed
for example in the Netherlands (Meij and te Winkel, 2003;
Meij and others, 2001a,b, 2002, 2003). In future, if mercury
control technologies are implemented in the USA, the
potential release of mercury from coal combustion
by-products becomes an issue. This is now under
investigation (CATM, 2003).
This report surveys recent information giving trends in
production and use of coal ash in different countries in
Chapter 2. After this it focuses on utilisation of fly ash,
5
Introduction

reviewing benefits and how current barriers to its wider

deployment are being overcome. The focus here is on the
traditional major utilisation sectors: cement (Chapter 3) and
concrete (Chapter 4). Soil stabilisation, use as backfill with
no binder, and agricultural applications are also major
utilisation sectors in many countries and will form the subject
of a separate report (Smith, 2005). There are commercially
available treatments and some under development to improve
the use of fly ash which has high carbon and or ammonia
content, resulting from adoption of NOx control technology
(see Chapter 5).

The preparation, and especially the focus, of this report have

benefited greatly from consultation with many experts from
countries with differing practices and priorities.

6 IEA CLEAN COAL CENTRE

 2 Production and utilisation of coal residues
Worldwide the production of coal combustion products will FBC - ash other
increase with the increase in coal use for electric power 1.6% 0.3%
generation. The effective management of these by-products SDA - product
boiler slag
will be a significant factor in determining the environmental 3.3% 0.8%
acceptability and the economics of future coal-fired power
generation. Maximising by-product utilisation will FGD - gypsum
bottom ash 16.5%
increasingly be the preferred management option for both 9.5%
economic and environmental reasons. It may become
mandatory since disposal will no longer be a permitted
option in many countries. The efforts of the European Coal
Combustion Products Association (ECOBA) in Europe and
the American Coal Ash Association (ACAA) in the USA to
increase by-product utilisation over the past 10 years have
been relatively successful (Hall and Livingston, 2001).
However, barriers to increased utilisation still exist and new
practices pose new challenges (see Chapters 3 and 4).

Coal ash production worldwide (fly ash, bottom ash and

boiler slag) was estimated at 460 Mt/y by Manz (1997, 1998,
1999) using data of the early 1990s. The overall utilisation
rate was then around 33% with great variations between
different countries. Many of the highest utilisation rates were
in the fifteen states of the European Union (EU15) where
coal ash production amounted to about 59 Mt/y, similar to
that in the USA, and much less than that in China fly ash
68.0%
(>90 Mt/y). No further studies have attempted to update this
on a global scale so it is useful to look first at recent data for Total production: 63 Mt
Europe before individual countries.
Figure 1 Production of coal residues in Europe
The production of coal combustion products for the fifteen (EU15) in 2002 (vom Berg, 2004)
Members of the European Union (EU15) in 2002 is shown in
Figure 1. Several European countries use 100% or more of as cocombustion of biomass with coal is forced and
their fly ash production although the overall utilisation rate supported by governments. Fossil fuels and their by-products
averaged 47% (20 Mt) in 2002 for applications of fly ash in which cannot be used are taxed. One third of the installed
the construction industry. If reclamation and restoration are power plant capacity has to be replaced in the next 10 to
included, the utilisation rate amounted to 89%. Temporary 20 years, due to aging of the plants (Vale and others, 2003).
stockpiles accounted for 7% of production (3 Mt) and 0.6 Mt
of this was reused. Disposal amounted to only 4% (1.6 Mt). ECOBA was set up in 1990 to deal with the issues resulting
The largest utilisation sectors for the 43 Mt of fly ash from legislation (see Brennan and others, 2003; vom Berg,
produced in 2002 are (vom Berg, 2004): 2000; vom Berg and others, 2001). For example, the
European Standard EN 450 ‘Fly ash for concrete’, introduced
% in 1994, is currently being revised and will include three
Cement raw material 12 categories for loss-on-ignition (LOI), cocombustion of
Blended cement 6 biomass and waste, as well as processed fly ash. New
Various concretes 16 standards for fly ash in bound and unbound mixtures for road
General engineering 7 construction are also under preparation (Vale and others,
and structural fill 2003).

Other uses include lightweight aggregates, bricks, ceramics,
grouting, asphalt filler, road base and subgrade, infill, soil
amendment, blasting grit, and fertiliser (vom Berg, 2004). Fly
ashes with higher lime content are used successfully for soil
beneficiation where they can replace pure lime (ECOBA,
2004).
The utilisation of coal combustion products in Europe is
being influenced by the liberalisation of the electricity
market. Competition from renewable energy sources as well
A special problem is caused by the combustion by-products
from power stations being designated initially as waste under
European legislation. It is not clear at what point these wastes
become valuable commodities and a requirement to designate
the products as hazardous waste would exclude any
utilisation option. Such a view does not take into account the
fact that coal combustion products are produced deliberately
with guaranteed properties; also that they are marketed for
applications according to given rules similar to other products
where such procedures are taken for granted. The marketing

Cement and concrete – benefits and barriers in coal ash utilisation 7

Production and utilisation of coal residues
of coal combustion products solved the former disposal
problem and even led to supply problems because of the high
demand for hard coal fly ash in some European countries
(vom Berg, 2000).
In the near future the production of coal combustion products
in Europe is expected to remain at current levels. More
stringent air pollutant emission standards, reflecting advances
in the control of SO2, NOx and particulate emissions from
coal-fired power stations, will affect the characteristics of the
residues. The amounts of flue gas desulphurisation (FGD)
residues will increase, including both FGD gypsum and spray
dry absorption product (Vale and others, 2003).
Meeting the challenges of bringing together varied
by-products with diverse markets is the aim of the
international network on the Production of Novel Products
from Glassy Combustion Residues (PROGRES), launched in
1998. Its main objectives are to:
● identify novel applications;
● communicate between producers of residues and end
users;
● disseminate information on novel products to a wide
audience.
PROGRES is preparing a book describing novel technologies
for products based on coal fly ash and the new generation of
coal residues (Blondin, 2002; Janssen, 2003).
2.1 Production and use in different
countries
A summary of the latest data on production and utilisation of
fly ash for selected countries where information has recently
been published is given in Table 1. The largest amounts of
fly ash are produced in China, India, the USA, and
substantial amounts, in Australia, Canada, and Japan where
there is also an increasing trend. All other major producers
of fly ash have shown decreasing production rates over
recent years. The highest proportion used is generally in
Europe but also in Japan, Korea and Israel. The reasons for
the differences vary from country to country and are
summarised in the following sections for some of the
individual countries:
Australasia
The utilisation rate for around one third of production in
2002 (see Table 1) for Australia and New Zealand concerns
fly ash and bottom ash. The main applications for the high
value, large volume part of the market (1.2 Mt) are pre-mixed
concrete, road stabilisation, blended cement products, and
controlled low strength fills. Fly ash is the major component
in use for these sectors, as replacement for part of the
Portland cement. The non-cementitious product areas
(0.4 Mt) include fly ash used as a filler in asphaltic concrete
as well as applications for furnace bottom ash which is
widely used as a sand replacement material in building
construction, underground mining and agriculture. Just over
half the coal ash used (2.1 Mt) is for mine backfill in which
an open cut mine can be restored to its original land form by
beneficial use of coal ash (Heeley, 2003).
8 IEA CLEAN COAL CENTRE
Barriers to ash utilisation are identified by Heidrich (2003) as
regulations and the economics of ash production, processing,
and logistics. The effective utilisation of coal ash has become
a high priority and major challenge in the face of
deregulating electricity market places. The privatisation of
power stations is associated with the transfer of a number of
wide ranging environmental obligations to the new private
business. This change is a threat to operators once
governments are free of their financial, operational
involvement in these assets. The economics of ash production
and utilisation is detailed by Heeley (2003).
Interpretations of the current legislation across Australia
suggest that ash will still be considered a waste, regardless of
any recycling process it may undergo. This can mean that ash
is subject to environmental controls beyond those of
equivalent virgin materials which may have equal potential
for environmental impact. This position is considered to be
inequitable from a market perspective and clearly results in
virgin materials being used in preference to alternative
materials. It is considered unlikely that governments would
introduce any form of positive discrimination to encourage
recycling of coal ash. Classification of coal ash can vary
widely with one state regulating it as inert waste while it
becomes a prescribed waste in another state. The lack of state
based regulations from key agencies such as the Environment
Protection Authorities (EPA) and various State Road
Authorities is a significant hindrance to coal ash utilisation.
This inconsistency contrasts with the acceptance of the
material properties of coal ash for purposes of practical use
under Australian Standards building classification. Since ash
materials regularly move intrastate for commercial use,
greater co-ordination between state agencies is required to
remove state bias. The National Environment Protection
Council (NEPC) affords an excellent model where
representatives of various state agencies meet to ensure that
legislation is adopted across borders in a unilateral fashion.
Further information on legislative requirements for use of ash
in Australia is available from http://www.adaa.asn.au (Heeley,
2003; Heidrich, 2003).
Transport is an issue which is commonly cited as a difficulty
in the large volume utilisation of ash. In future, cocombustion
of biomass which is being encouraged by the Australian
Government, with its mandated renewable energy targets,
may affect the ability of fly ashes to comply with Australian
Standards. The impact of this must be assessed and similar
policy related issues are likely to arise in the future (Heeley,
2003).
Producers and marketers of coal ash formed the Ash
Development Association of Australia Inc (ADAA) in 1991.
The primary objectives are to conduct research and
technology transfer on behalf of members and to assist in
developing market opportunities in the use of ash materials.
The challenge for the membership ahead is to identify
potential for growth in the use of ash. Some possibilities
include production of lightweight aggregates, lightweight
bricks, and fly ash soil amendments (Heidrich, 2003).
However, lightweight aggregates would have to displace
quarried products which are integrated into the concrete
industry. Brick manufacture is very competitive and fly ash
 Production and utilisation of coal residues

Table 1 Fly ash production and use in different countries

Trends*
Amount Proportion
Country Year Reference
produced, kt used, %
Production Utilisation Since year

Australia 2002 12,500† 32 increase increase 1997 (Heidrich, 2003)

Austria 2001 128 91‡ decrease increase 1998 (Ladenhaufen, 2004)

Canada 2002 4,744 21 decrease increase 1999 (Weir, 2004)

China 2002 150,000† 66 increase increase 1995 (Barnes and Sear, 2004)
Czech
2001 4,300 9‡ decrease 1993 (Ladenhaufen, 2004)
Republic
Denmark 2002 729 98 decrease increase 1998 (Hansen, 2004)

EU15 2002 43,047 89 decrease 1997 (vom Berg, 2004)

Germany 2002 4,070 hard coal 99 decrease decrease 1996 (vom Berg, 2004)

2002 8,180 brown coal 100 decrease increase 1997 (Miskiewicz and others, 2003)

India 2001/2 100,000 23 increase increase 1997 (Kumar and others, 2003)

Israel 2000 1300† 98 increase increase 1995 (Naik and Chun, 2003a)

Japan 2002 9,300† 83 increase increase 1996 (Harada, 2004)

Korea 2001 4,900† 63 decrease decrease 1992 (Park and others, 2003)
(Vliegasunie bv, 2004)
Netherlands 2003 996 >100 decrease no change 1998
includes stored fly ash
(Szczygielski and Myszkowska,
Poland 2001 5,010 79 decrease increase 1997
2003)
Romania 2001 2,600 0‡ decrease 1989 (Ladenhaufen, 2004)

Russia 2001 3,000 7‡ decrease 1992 (Ladenhaufen, 2004)

Slovakia 2001 480 0‡ decrease 1992 (Ladenhaufen, 2004)

Slovenia 2001 17 0‡ decrease 1992 (Ladenhaufen, 2004)

Sweden 2003 38§ 88 decrease increase 1996 (Ribbing, 2004)

South Africa 2002 22,000 30 decrease 1992 (Kruger, 2003, 2005)

Turkey 2001 5,620 9‡ decrease 1992 (Ladenhaufen, 2004)

UK 2002 ~5,500 55 decrease increase 1998 (Sear, 2003)

USA 2002 76,500 35 increase increase 1997 (ACAA, 2003)

* trends are calculated against data published in previous reviews (Manz, 1997; Sloss 1999)
† includes all ash from large hard coal combustion sources
‡ utilisation rate is only for cement industry
§ includes fly ash from cofiring coal with other fuels

bricks have not necessarily proved to incur lower costs than
conventional products. Fly ash would be suitable to amend
sandy soils, for example in Western Australia. Fly ash would
improve water retention and reduce irrigation costs, while
also contributing valuable trace elements which are lacking in
such soils. Uptake of trace elements into plants and
subsequently animals requires close study and the onus
remains with the ash marketer to demonstrate that the use is
safe. However, accepted fertilisers may also contain trace
elements which are not part of the desired mix for the
specific application. The side effects could be worse than
those which may arise with ash. Furnace bottom ash would
improve clay soils which typically need sandy material to
improve their structure and this would be useful in New
South Wales (Heeley, 2003).
The need for industries to reduce CO2 production may be the
best driver to increased use of fly ash. If governments
determine that this is essential, then the cement industry in
particular is likely to continue to increase its rate of use of fly
ash (Heeley, 2003)
Canada
The utilisation of coal ash has increased from 19.2% in 1999
to 24.7% in 2002. Fly ash utilisation was 21% in 2002
(see Table 1). The increase in utilisation since 1999 has been

Cement and concrete – benefits and barriers in coal ash utilisation 9

Production and utilisation of coal residues
mainly in cement, concrete, and wallboard applications. The
mining and road base/subbase uses have declined over the
period (Weir, 2004). In 2001, utilisation of fly ash included 9%
(449 kt) of the total production in concrete applications as a
separate ingredient, 0.2% (10 kt) in blended hydraulic cements,
and 1.3% (64 kt) in other applications such as mining, and oil
well cement. A further 46% (2200 kt) could potentially be used
as supplementary cementing materials in concrete without any
major processing, such as grinding or removal of carbon. This
would increase the overall utilisation rate to 57%. However,
this would still be a lot less than the proportion of the
production of ground granulated blast furnace slag and silica
fume which are used as supplementary cementing materials.
Fly ash is therefore underused compared to other by-products.
The detailed investigation by Bouzoubaâ and Fournier (2004),
prepared for the Government of Canada Action Plan 2000 on
Climate Change, has shown that there are policy, technical and
economic barriers to the increased use of these materials.
These need to be overcome in order to decrease the CO2
emissions related to the use of Portland cement.
Producers and marketers of coal ash formed the Association
of Canadian Industries Recycling Coal Ash (CIRCA) in
2002. CIRCA is working with Natural Resources Canada, the
Cement Association of Canada and the Canadian Ready Mix
Concrete Association, among others, to educate engineers,
specifiers, architects, producers, students and the general
public on the benefits of using coal ash. Among many
benefits to its members, it monitors and co-ordinates work
with regulatory bodies, and maintains reciprocal agreements
with national and international coal ash associations. It
provides a forum for producers and marketers of coal ash in
Canada to develop consistent and effective policies and
conducts, promotes and supports collaborative demonstration
programmes (see also http://www.circainfo.ca). Canadian
industry is working with Natural Resources Canada to
increase the rate of use of coal ash across the country.
CIRCA is working with the Canadian Standards Association
to increase limits for coal ash and other supplementary
cementing materials in concrete and blended cements in
Canadian standards (Weir, 2004).
Despite successful use of high volumes of fly ash in many
projects, including high-profile projects, there are still
municipalities and provincial agencies that ban or limit its
use to a certain percentage of replacement for some
applications. Such bans could actually be detrimental to the
long-term durability of concrete for reasons such as alkali
aggregate (silica) reaction which is depressed by using fly
ash (see Section 4.1). Technical and economic barriers
include (Bouzoubaâ and Fournier, 2004):
● the slower setting times and strength development of
concrete incorporating fly ash which limits its use in
applications requiring fast form-work removal;
● reduced resistance of fly ash concrete mixtures to
freeze/thaw cycles in the presence of de-icing chemicals;
● lower quality fly ash in the Eastern part of the country due
to the type of coal and increased petroleum coke used;
● the costs of transport and silo storage.
Solutions to overcome these barriers are proposed
(Bouzoubaâ and Fournier, 2004):
10
● clear specifications and national guidelines to be
developed and agreed upon by all interested parties for
issue under the Canadian Standards Association to
replace those currently in use;
● workshops in cities throughout the country to bring
together all the specifying authorities, concrete suppliers,
users and engineering inspection and testing companies
in order to adopt the guidelines (with modifications if
necessary);
● meetings to discuss ways of resolving technical issues,
including developing a more rational and consistent
approach to the use of supplementary cementing
materials under different exposure conditions;
● support R&D programmes to resolve technical barriers;
● the cement industry should be encouraged to produce
more blended hydraulic cements to overcome the issue
related to the quality control of fly ash and also the
economic barriers due to transport and storage costs.
The biggest challenge for increased use of fly ash remains the
transport and beneficiation costs. Greater usage of fly ash
would reduce the transport costs. The greatest market for the
cement and concrete industry is in Eastern Canada where
there is a lack of quality ash. On the other hand, quality ash
is abundant in Western Canada where the concrete industry
represents only 25% of that of Canada (Bouzoubaâ and
Fournier, 2004). Many of these solutions are being addressed
through the collaborative efforts of government and industry,
with revised specifications, national guidelines and cross
country workshops to increase the responsible utilisation of
coal ash in concrete. A web-based learning module and a
cross-country series of seminars will be delivered in 2005.
Research and commercial demonstrations of ash beneficiation
processes to improve high carbon ashes are in construction
and under way in Canada (Weir, 2004).
China
The ash utilisation rate remained low at around 10% until the
1980s but then grew rapidly during the 1990s. It reached
about 66% of an ash production rate of 150 Mt in 2002
(Barnes and Sear, 2004) which represents a considerable
increase over 1995 data (see Sloss, 1999) when it was 42%.
The production of coal fly ash is predicted to increase to
250–260 Mt in 2005, 320–380 Mt in 2010 and 570–610 Mt
in 2020 (Barnes and Sear, 2004).
According to the World Bank (2001) assessment of clean
coal technologies for China, the utilisation potential is
generally not limited by technological barriers or
unawareness of the options. It is due to the low disposal
costs, wide availability of natural materials, and long
distances from the point of production to the point of use
which entail high transport costs. Use of larger percentages
of low-calcium fly ash (up to 60%) as replacement for
Portland cement in the manufacture of concrete would offer
substantial advantages over the current practice of #20%
replacement.
On the other hand, Heeley (2003) considers that the high
population density and the need for arable land mean that
natural quarries are recognised as a limited resource and
alternatives are keenly sought. Major highway projects have
IEA CLEAN COAL CENTRE

used several million cubic metres of stockpiled ash to
construct elevated embankments over long distances. Fly ash
bricks are common and are produced cheaply on a local basis
near the power stations.
In 2002, the main utilisation sector was in the construction
industries, followed by roads and then backfill, with a small
proportion in agriculture (Barnes and Sear, 2004).
Applications of fly ash in agriculture may have considerable
potential. A study of the effects of using coal ash on farmland
(525 t/ha) showed that rice, maize and wheat crops had no
difference in radioactivity (226Ra and 228Ra) from those
grown on ordinary soil, despite greater activities in the coal
ash compared to soil (Shi and Xu, 2002).
The problem of ash utilisation will increase with rapid
growth in coal-fired generating capacity in the coming years.
The government regards this as a serious problem and is
offering tax incentives for ash utilisation projects. As of June
2004, 170 cities were to ban the use of solid clay bricks as
wall material, substituting them with bricks containing coal
ash. This policy is to be extended nationally in 2005
(Barnes and Sear, 2004).
Germany
The production rate of all coal combustion residues in 2002
was 7% less than in 2001 according to VGB (2003). Fly ash
production from hard coal decreased since 1996 and 99%
was used (see Table 1). Out of the 3.7 Mt of fly ash suitable
for the construction industry, 2.6 Mt met the European
EN 450 standard for use in concrete. Fly ash was imported
(150 kt), mainly from eastern Europe. Uptake in Germany
was reduced due to the continued recession in the building
industry and 450 kt of fly ash was exported to western
countries. Production of bottom ash amounted to 1.3 Mt,
boiler slag 1.3 Mt, and fluidised bed combustion (FBC)
residues less than 0.2 Mt in 2002 (VGB, 2003). Modern
coal-fired power stations must not only generate electricity
and thermal energy but also produce by-products such as fly
ash, bottom ash and gypsum which have to meet certain
quality criteria. Non-utilisation of these materials can have
serious consequences for plant viability. The utilisation or
non-utilisation of residues from coal combustion can affect
power generation costs by as much as 15% (STEAG, 2002).
The use of SCR with less reliance on low NOx burners
means that the fly ash is of excellent quality. Around 90% of
the production is certified as suitable for the building industry
and over 95% of this is from dry bottom boilers and has
comparable quality. Hence no treatment is necessary to
satisfy EN 450 for concrete (LOI <5%) and concretes are
produced with different qualities to suit other markets too.
German regulations are a little different from the European
Waste Catalogue and fly ash should be designated as
hazardous waste in Germany on account of its chromium
content. This gives fly ash a bad image and increases costs.
The ministry is reviewing the matter but fly ash suffered from
a lack of acceptance in the cement industry during the 1970s,
despite the issue of permits by building authorities. This led
to the cement industry attempting to meet increasing demand
by using ground granulated blast furnace cement instead. Fly
ash then filled market opportunities directly in the concrete
Cement and concrete – benefits and barriers in coal ash utilisation
Production and utilisation of coal residues
industry, following research to demonstrate the benefits of
using fly ash. The amount of fly ash used in concrete has
increased from 3 Mt/y to 25 Mt/y now while there is less
demand for fly ash in cement for several reasons (Hugot,
2004; vom Berg, 2004).
Ash from cofiring coal with other fuels is seldom used in
Germany, except in wet bottom boilers. This is a disincentive
to cofiring with biomass but Germany has the advantage of
meeting its Kyoto targets by improvements in East Germany.
Location of most power stations in the Ruhr is a barrier to
using fly ash for cement needs throughout the country.
Security of supply of fly ash is a difficult issue due to
seasonal production which is not in phase with demand.
Despite a total storage of around 5% of production, this is
still not enough and some ash has to be stored temporarily
(Hugot, 2004; vom Berg, 2004).
As can be seen from Table 1, far more fly ash is produced
from brown coal than hard coal in Germany. Bottom ash
amounted to 1.9 Mt and FBC residues 0.2 Mt in 2002. The
fly ash is calcareous, meeting the standard EN 197-1. About
94 wt% of the fly ash was used for filling depleted surface
mines. The rest was deployed as a fill in asphalt and in
underground mining, for surface recultivation, soil
stabilisation, fertiliser and as a component in concrete. Most
of the bottom ash (96%) and 67% of the FBC residues were
used for reclamation/restoration of surface mines. Other uses
include filler in asphalt, in underground mining, for surface
recultivation, soil beneficiation, fertiliser and as a component
in concrete (Miskiewicz and others, 2003).
Apart from its active membership of ECOBA, ash utilisation
in Germany is promoted by the national association for
power station by-products, the Bundesverband
Kraftwerksnebenprodukte (BVK see www.bvk-online.com).
The most promising market is the utilisation of fly ash in
concrete, replacing cement, where there is nearly 40 years of
experience (Thamm, 2003). STEAG by-product management
includes research projects on the effects of fly ash on
important concrete attributes. These include resistance to
sulphate and de-icing salt as well as the contribution to the
prevention of the alkali silicate reaction that damages
concrete (see Section 4.1). Processes to produce
self-compacting concrete with fly ash are under investigation
(STEAG, 2003).
India
The use of coal with a high ash content (30–50%) contributes
to the large production of ash (see Table 1). India will
continue to depend on coal for energy and is expected to
produce 175 Mt/y of ash by 2012 (Kumar and others, 2003b).
Although ash utilisation has improved considerably
(see Figure 2), it needs to increase at a greater rate in future.
The quality is low calcium class F fly ash which is
successfully used to a greater extent in Europe. Khadilkar
and others (2003) consider that fly ash utilisation in cement
and concrete could be increased by various treatments
(see Chapter 5) to improve its pozzalinicity, deployment of
ash modified clinker (AMC) technology to increase the
calcium oxide content of the ash, and use in pavements which
is a high priority application in India. Choice of an
11
Production and utilisation of coal residues

120

100
100 95 production
90
85
80
80
70
Fly ash, Mt

60
60
50

40
40

23
19 utilisation
20 15 16
9.5
7
2.5 4.2
1.2
0
1993-94 94-95 95-96 96-97 97-98 98-99 99-00 00-01 2001-02
Year

Figure 2 Trends in the production and utilisation of fly ash in India (Kumar and others, 2003b)

appropriate option depends on the location of the power The current standard IS 3812 Part 1 (draft) in India was
station, whether near a city, coal mine, cement plant or revised to include improvement of fly ash through
elsewhere. If utilities regard fly ash as an important beneficiation/segregation/processing (Jha and others, 2003).
by-product rather than waste requiring disposal, efforts could More dry fly ash is now available in India but fineness is not
be directed towards optimising and improving the quality of sufficiently specified. IS 3812 specifies two grades of fly ash
fly ash instead of only increasing power generating for use in cement manufacture and as a component in
efficiency. concrete. It is suggested that two additional new grades are
considered to correspond with the British BS 3892 Part 1 and
During 1997-98, fly ash was used in the following Japanese class 1 of JIS 6201-1999 (Kumar, 2003). Codes for
proportions (%) as follows in India (Mukherjee and other applications of fly ash, for lime pozzolana mixtures,
Zevenhoven, 2004): sintered, geotechnical and agricultural applications are also
under formulation. The code of practice, IS:456, for plain and
Landfill 51 reinforced concrete has been updated with use of fly ash. The
Cement 26 minimum and maximum percentages of fly ash in Portland
Ash dykes 9 pozzolanic cements (PPC) were enhanced to 15% and 35%
Mines 5 respectively in 2000 (Jha and others, 2003; Kumar and
Bricks 5 others, 2003b).
Road work 2
Agriculture 2 Ash utilisation has been promoted by several initiatives over
many years. The Fly Ash Mission was set up in 1994 as a
Prasd and Mishra (2003) point out that the main emphasis joint activity with government, academia, and industry,
has been on the utilisation of fly ash for low and medium focusing on ten areas: fly ash characterisation, hydraulic
value applications such as bricks, partial replacement of structures, handling and transportation, ash ponds and dams,
cement and in mass concrete for dams. These have not applications in agriculture, reclamation of ash ponds for
achieved a sufficiently high utilisation rate. Future efforts human settlement, roads and embankments, underground
should be directed towards higher value applications, yielding mine fills, research and development, building components.
sales revenues for fly ash vendors. These include metal Use of fly ash is being promoted by other Government
extraction and use of fly ash as raw material for specialist initiatives through the Ministry of Environment & Forests
products such as tiles, zeolites and ultra light hollow spheres (MOEF) and the Ministry of Power (Kumar and others,
for arid zone cultivation. On the other hand, the International 2003b; Prasd and Mishra, 2003). For example, the salient
Coal Report (2003) has announced the adoption of roller features of the Government Notification of 1999 on fly ash
compacted concrete technology for building a dam for a utilisation/disposal are listed by Prasd and Mishra (2003),
hydro-power project in Maharashtra state. This technology including:
has helped to use more fly ash in cement in the west since the ● enforcing clay bricks, tiles or blocks for construction to
early 1990s. Narayanasamy (2003) notes the benefits of using be made with at least 25 wt% fly ash, bottom ash or
lignite and hard coal fly ashes in agriculture, including use as pond ash within a 50 km radius of a coal-fired power
a pesticide. station;

12 IEA CLEAN COAL CENTRE

 Production and utilisation of coal residues

● power stations to record and make ash freely available to
manufacture cement, concrete, bricks, and other
construction materials for at least 10 years from the
notification;
● every power station to submit an action plan to achieve
100% utilisation of fly ash, phasing out disposal on land
within five years of the notification;
● joint government/industries to facilitate setting up of
manufacturing activities using ash near to power stations;
● reports on compliance to be submitted annually;
● all local authorities to specify use of ash in building
materials, roads, embankments and so on within four
months of the notification.
In a draft notification in 2002, the MOEF proposed that
100% fly ash bricks are used in construction projects within a
100 km radius of a power station by the end of the year 2005.
It has also been proposed that 25 wt% fly ash should be used
in construction work for a 100 km rather than 50 km radius
of a power station (Jha and others, 2003). The TERI
Information Digest on Energy and Environment notes that
use of fly ash will soon be made mandatory in various
infrastructure development activities. These include
construction, laying of roads and reclamation of low-lying
areas. The necessary changes in Fly Ash Rules will soon be
notified (TIDEE, 2003).
Japan
Over the last 10 years of increasing ash production, the
utilisation rate has continued to increase while the disposal
rate has decreased. Approximately 90% of the coal ash is
from PF, 8% from FBC and 2% from stoker boilers. The high
utilisation rate of 81% (see Table 1) for coal ash in 2001 is
double that in 1990. The main sector is 74% use in the
cement industry (see Figure 3), most of this as a substitute
for clay in cement raw material rather than as a cement
8 utilisation in the 21st century. The focus is on hardened
7 artificial aggregate or other materials in order to use large
6 addition research is in progress to increase the quality of coal
Ash utilisation, Mt
extender. Coal consumption is expected to escalate in future
(Ando, 2003) and ten new coal-fired power stations are
starting commercial operation by 2005. Hence coal ash
production is predicted to reach about 11 Mt in 2005. This
continues to put pressure on developments in coal ash
utilisation, especially since cement production has stopped
increasing. It is important to expand utilisation in other fields.
There is a high potential for large-scale coal ash utilisation as
material for public works which includes road base materials
and soil stabilisation (Sakai and Hara, 2003; Sakai and
others, 2003).
Use of fly ash as a component in concrete started in the
1950s and standards for fly ash cement were established in
1958 and 1960. Use of fly ash as a substitute for clay in
cement raw material started in 1978. However, coal ash is
classified as industrial waste and has to meet restrictions
under the law concerning disposal and cleaning of waste. It is
also designated a by-product under the 1991 law for
promotion of effective utilisation of resources, which applies
to utilities supplying 120 million kWh/y or more. This
requires the industries to submit reports on ash utilisation,
plans to promote it and information on quality and
composition of coal ash to users. For use in the public works
sector, coal ash is subject to the environmental pollution
prevention act which applies leaching tests for hazardous
substances. The criteria are more severe than those applied to
landfills of controlled industrial waste. Use of fly ash in
cement and concrete was promoted in 1999 by classifying the
standard, JIS 6201 into classes I, II, III, and IV, according to
maximum LOI of 3–8%, fineness and other physical and
chemical properties. The current status of technology
development for effective use of coal ash is shown in Table 2
(Sakai and Hara, 2003; Sakai and others, 2003).
In 2003, the Centre for Coal Utilisation Japan (CCUJ)
formulated a new strategy for the development of coal
materials for public works, and civil engineering uses for
amounts of unused coal ash as primary raw material. In
ash by reducing the unburnt carbon content and producing

5 artificial zeolites for many marketable applications (Sakai

and Hara, 2003). Agricultural applications may also be
4 considered attractive alternatives to coal ash disposal. Here
possible trace element contamination must be avoided.
3 Demonstrations have shown that fly ash is beneficial
(Yokoyama, 2003):
2 ● as a soil improver, for soil structure, pH, electric
conductivity, soil nutrients (for example P, K, Ca, Mg,
1 Si, S, Fe, Cl, Mn, B, Mo, Co, Zn, Cu), as well as for
micro-organisms;
0 ● in compost, with soils or with organic waste products;
1993 94 95 96 97 98 1999 ● as fertiliser, mixed with nutrients such as phosphate,
Year nitrate, potassium;
cement raw material agriculture ● in land reclamation for agricultural development by
cement additive others covering the soil with a layer of coal ash.
civil engineering field landfill
construction field total production The Netherlands
Figure 3 Trends in the utilisation of coal ash in The utilisation rate of fly ash for 2003 continues to exceed
Japan (Harada, 2004) 100% due to use of stored fly ash (see Table 1). The

Cement and concrete – benefits and barriers in coal ash utilisation 13

Production and utilisation of coal residues

Table 2 Current status of technology development for effective use of coal ash (Sakai and Hara, 2003)

JIS fly ash JIS A 6201 revision (grade 4)

Portland cement (<5% fly ash content)
JIS cement Fly ash cement (classified into 3 types depending on the mixed ratio of fly ash)
Type A: 5% to <10%; Type B: 10% to <20%; Type C: 20% to <30%

Reduction in heat of hydration, appearance of

Dam (Type C)
Cement and concrete

long-term strength, water-tightness

Appearance of long-lasting strength, water

Bridge and building foundations (Type B)
Examples of use of fly tightness
ash cement
Water and sewage construction of seaport (Types A to B) Water-tightness, etc
Grout method, pre-packed method (Type C) Fluidity, etc
Concrete products (Types A to C) Improvements in finishing, etc
Alternative to clay in cement raw materials
3-constituent type cement
*Fly ash type super-plasticised concrete
Fine ash (finely powdered fly ash)
FA light (specific gravity: 1.30–1.38): currently on the market
Artificial aggregates *Ultra light-weight artificial aggregate (specific gravity: <1.25)
Construction

*High-strength artificial aggregate (specific gravity 1.8±0.1): under development

Internal and external wall

FA board, FA siding board: currently on the market
material for construction

Pavement brick, roof tile

Embankments, land *Technology for using ‘Pozzotech’

preparation *Mixed use with surplus soil generated from construction: (under development)
Asphalt filler Adopted in ‘Asphalt pavement guideline’
*Road base and road bed materials around seaport and airport facilities
*Technology for using ‘Pozzotech’
Road materials Technology for manufacturing and using ‘Ashroban’
*Technology for manufacturing ash by fluidised bed combustion (Narlton) and its usage

*Technology for manufacturing and using solidifying material for constructions made from ash generated by
Public works

combustion of pulverised coal: (under development)

Already put into practical use at the Sakata

*Revetment back-filler
seaport

*Stabiliser for soft ground

*FGC deep mixing method of soil stabilisation
Material for ground *Technology for manufacturing and using FAC
improvement, etc
*Technology for improving soft soil with high water content
*Underground filling method
Applicaton to SCP method (solidified particles)
Foundation of underwater bridge legs: CAP and PC methods
forestry and

Fertiliser
Agriculture,

fisheries

*Kelp and fish reefs

Block materials for preparing upwelling artificial fish bank

Flue gas desulphurising materials using coal ash
Others
*Artificial zeolite
* Project was executed by CCUJ

utilisation rates of the other residues from PF combustion through continued efforts by the Vliegasunie (Dutch Fly Ash
also exceed the production (154 kt bottom ash and 295 kt Corporation) which was founded by the Dutch power
FGD gypsum) (Vliegasunie, 2004). This record is maintained generating companies in 1982 in order to combine marketing

14 IEA CLEAN COAL CENTRE


and handling of the construction raw materials produced by
the coal-fired power stations. These are produced to meet the
needs of the customers for a fly ash of constant quality and
quantity. The large fly ash processing plant in Rotterdam,
completed in 1995, upgrades 250 kt/y to maintain quality in
spite of the negative effects of introducing low NOx
technologies on fly ash quality. The storage facility allows
improved matching of a supply of fly ash with demand which
is highest in summer when production is low (Moret, 1995).
Now that secondary fuels are cofired at rates >10 wt%, the
fly ash has to be checked to ensure that it is physically the
same as fly ash without secondary fuels. Ponded ash from
past operations cannot be dug out but there is a prospect of
using it in embankments from September 2004. Possible
leaching of molybdenum currently prevents use of fly ash in
road construction although furnace bottom ash can be used in
this application with a leaching certificate (Moret, 2004).
Poland
The high utilisation rate (79%) for fly ash shown in Table 1,
represents a great improvement since 1972 when Poland was
using only 32% of its total output of coal ash, but this is
mainly due to decreased production of fly ash. In addition to
fly ash, 5426 kt bottom ash, 1121 kt boiler slag, and 413 kt
FBC residues were produced in 2001. The utilisation rate was
61%, for both bottom ash and boiler slag and 67% for FBC
residues. However, the largest coal ash utilisation sector was
infill at 35%, cement and concrete accounting for only about
12% (Szczygielski and Myszkowska, 2003).
Barriers to ash utilisation are identified as a general
unawareness of environmental matters in society and low
public acceptance for serious utilisation. The latter is because
ash is perceived as a dangerous waste. Extraction of natural
aggregates for land reclamation projects is widespread and
uncontrolled, despite the degradation of further huge land
areas (Szczygielski and Myszkowska, 2003).
Progress has recently been made to promote ash utilisation
by forming the Polish Union of CCPs Companies in 1998
and the group became a member of ECOBA in 1999. An
internet platform (www.popiol.pl) was created to enhance
commercial use of coal ash in a technically advanced,
economic and environmentally sound way. A Polish Ash
Award Competition has three categories to reward people
contributing to advancing ash utilisation, producers who
achieve the best conditions for production of high quality
by-products, and companies which excel in practical
utilisation of coal ash (Szczygielski and Myszkowska, 2003).
South Africa
Use of fly ash as cement extender was investigated during the
1950s and 1960s but with disappointing results. This was
attributed to the coarseness of the fly ash. From 1979
considerable research was carried out. With the installation of
air classification plants at two power stations during the
1980s, the capacity of fly ash selection plants increased and
fly ash was used increasingly in cement and concrete
applications (Krüger, 2003). Most of the higher quality coal
is exported so that the power generating industry has to rely
on lower quality, high ash coal (up to 45% compared to the
Cement and concrete – benefits and barriers in coal ash utilisation
Production and utilisation of coal residues
average ash content of 29%). The amount of fly ash sold on
the commercial market is currently 5% but sales have grown
significantly from only 20 kt/y in the late 1980s to over
1200 kt/y in 2002. South Africa is in a phase of economic
expansion. In 2004, 1600 kt of fly ash will be used. However,
this does not include responsible filling of opencast mines. A
more realistic utilisation of around 30% in Table 1 reflects
this broader definition of fly ash utilisation (Kruger, 2003,
2005).
The South African Coal Ash Association was set up during
the late 1980s and has focused research in national and
international symposia. Two products are marketed as cement
extender. Fly ash with a nominal particle size <45 µm is
marketed under the trade name Dura-Pozz®. Fly ash with a
nominal particle size <15 µm is marketed as Super-Pozz®
(Krüger, 2003).
The ash utilisation industry is being developed with a view to
maximising exploitation. The approach adopted is to segment
potential uses according to the level of technology and the
degree of processing needed to provide a product that
consistently meets the required technical performance
(Kruger, 2003):
High technology applications:
● fillers for plastics;
● high-performance concrete;
● fillers for rubber.
Medium technology applications:
● cement extension;
● polymer concrete;
● refractories;
● sewage treatment.
Low technology applications:
● landfill;
● sand for bricks;
● raw feed for cement kilns.
Processed fly ash used in high technology applications is
more expensive and volumes are lower than for unprocessed
fly ash used directly from the power station in low
technology markets. The potential for use of fly ash in
cement is limited by several factors. Realistically only about
30% of the amount of cement produced can be substituted by
fly ash. For a cement production of 7.5 Mt in South Africa,
only up to 2.3 Mt fly ash could be used. The market size is
further decreased by transport costs and logistics. The further
the distance between the power stations, cement factories and
the market, the smaller the potential market. In South Africa
these distances are more than 500 km. Hence the ash market
in remote regions is confined to applications where
high-durability concrete is specified. In such cases, the
cost/performance ratio is favourable and the fly ash is used
solely through its ability to enhance the quality of the
concrete (Kruger, 2003).
The most important factor in establishing a viable fly ash
industry in South Africa was the paradigm shift to regard ash
as a resource rather than a waste. As a result the ash tends to
15
Production and utilisation of coal residues
be beneficiated and processed to find higher technology
markets in many industries such as building and construction,
agriculture, plastics, refractories and waste treatment
(Kruger, 2003).
UK
Fly ash was used to replace cement in structural concrete in
the 1950s and this practice had become widespread by the
mid-1970s. By the mid 1970s fly ash was regularly being
used in concrete for large construction projects in the UK. As
noted in Chapter 1, it became known as pulverised fuel ash
(PFA) to differentiate it from fly ashes derived from other
processes (Sear, 2001). The variability in quality and supply
was a handicap to the uptake of fly ash in concrete
production. The solution was to supply a tightly controlled
fineness and, since 1975, classified fly ash according to the
British standard BS3892 Part 1 has been accepted
increasingly within the UK ready-mixed and precast concrete
industries (Sear, 2002). Currently some 500 kt/y of classified
PFA are used in ready-mixed and precast concrete (Barnes
and Sear, 2004). The current standard provides for complete
beneficiation of fly ash rather than just simple mechanical
classification. Test work during the 1990s showed that fly ash
which has been wet for many years did not lose its
pozzolanic activity (Smalley, 2004). Although the utilisation
rate has increased, 45% of the fly ash produced enters long-
term storage (see Table 1) and there are many hundred
millions of tonnes of fly ash in stockpiles which could be
used (Sear, 2002).
The United Kingdom Quality Ash Association (UKQAA)
represents the interests of the producers and users of coal ash
from coal-fired power stations in the UK. The UKQAA was
set up in 1997, replacing and extending the scope of the
previous association which only supported the use of
classified fly ash in concrete (see www.ukqaa.org.uk). Now
marketable coal ash comes under the following categories
(DTI, 2002):
● cenospheres;
● furnace bottom ash (FBA);
● PFA;
● classified PFA;
● conditioned PFA;
● lagoon ash (PFA or PFA mixed with FBA).
In 2001, applications for coal ash (fly ash, bottom ash) used
the following proportions of the total ash produced (Sear,
2003a):
% technologies for the utilisation of ash from coal-fired power
Concrete blocks 55
Concrete addition (EN 450) 19
Cement raw material 6
Blended cement 3 USA
Grouting mines etc 8 The Chicago Fly Ash Company, formed in 1946, was the first
Fill and ground remediation 7 to market fly ash as a construction material for manufacturing
Cenospheres 1 concrete pipe and fly ash was used on a large scale in the
Other 1 construction of dams during the 1950s. Initial markets for fly
The standard for classified fly ash in the UK (BS3892 Part 1)
permits a limited range of fineness but classified fly ash from
many sources is similar. The 1995 European standard,
EN 450, allows a wider range of fineness for use in concrete
16
because no other European countries routinely classify fly
ash for use in concrete. The European standard also has no
requirement for water reduction. To keep the large market for
fly ash meeting BS3892 Part 1, exceeding £10 million per
year, it is important to allow co-existence of the British
standard with the European one. Alternatively, a further
European standard, or part to EN 450 should be prepared to
detail the requirements for classified ash (Sear, 2001) and this
appears to be in progress (see Vale and others, 2003). Further
standards include BS3892 Part 2 and EN 206 for inert
additions in concrete (see UKQAA, 2001b).
Another conflict with European legislation concerns the
recent categorisation of coal ash as a waste. The power
industry does not consider that PFA offered for sale is a
waste because the intent is to use it as a product. The
Environment Agency has decided that various European
Court rulings had changed the definition of waste and now
consider PFA as a waste until it is finally utilised, for
example mixed with cement. Many applications have been
exempt from Waste Management Licensing (WML) and this
has promoted the use of by-products and recycled materials
which have a good environmental record. If a by-product is
classified as a waste, many more regulations apply to obtain a
WML. There are at least 38 European standards relating to
characterising waste materials under preparation and many of
these can be called upon by the Environment Agency to form
part of an Environmental Risk Assessment (ERA). Approvals
are given on an individual basis with no national guidelines
and a full programme of environmental testing could take a
considerable amount of time and expense. These changes
have led to contractors substituting natural aggregates for
100 kt of PFA in the last two years. If the use of PFA
becomes too difficult, an additional 200 kt/y of natural
aggregates may be deployed with all the inherent
disadvantages, including the environment (Sear, 2003a,b;
UKQAA, 2003c). Further information on this issue is
available on the website: www.ukqaa.org.uk.
There is a gradual increase in use of PFA in road sub-base
construction and non-aggregate use in cementitious
applications while grouting and block manufacture remains
stable. In future a long term decline in ash production is
likely but the volume of stockpiled material compared to
aggregate and non-aggregate annual usage is large and
presents a good opportunity for use of increasing quantities
of PFA (WRAP, 2003). The DTI commissioned a study to
carry out a detailed, worldwide review of the status of
stations and to assess the market potential for exploiting these
technologies (see Barnes and Sear, 2004).
ash were as a Portland cement extender and as an enhancer of
the qualities of concrete to meet new postwar requirements
(Kalyoncu, 2002). The amount of coal combustion products
produced in the USA in 2002 ranks third after crushed stone,
sand and gravel and is greater than production of cement and
IEA CLEAN COAL CENTRE

iron ore. Both production and utilisation rates of fly ash have
increased in recent years (see Table 1). The consumption of
dry and stored fly ash is approximately 41% of the total
production but this decreases to 34% if ponded ashes are
included (Misra and others, 2003). About 11.5 Mt of fly ash
are used in concrete, generally as a replacement for cement
and around 20 Mt in lower value applications such as
backfilling or as a replacement for various fillers (Deju,
2003). However, most of the ash currently enters landfills and
surface impoundments, despite great potential for utilisation
(Walker and others, 2002; Goss, 2003).
There are two types of fly ash according to ASTM C 618:
class C and F. Class C fly ashes are rich in lime, containing
typically 10–40% CaO. Class F fly ashes are low in lime,
generally <10% CaO. Class C fly ashes participate in both
cementitious and pozzolanic reactions whereas class F fly
ashes predominately participate only in pozzolanic reactions
during the hydration process. Hence class C fly ashes are
classified as cementitious and pozzolanic components or
additives while class F fly ashes are normal pozzolans for use
in concrete (Naik and Chun, 2003a).
Naik and others (2003a,b) note that utilisation of class C ash
is lower than for low lime class F ash. Class F fly ash is often
preferred to limit the effects of alkali silica reaction in
concrete (see Section 4.1) (Hoffman, 2002). The quantity of
class C type ash will increase as will the deployment of new
FGD systems. Hence several research studies are directed
towards use of these ashes in high volume applications such
as concrete, cement and stabilised road base materials.
Similarly, as NOx emissions are reduced by more widespread
deployment of low NOx burner technologies and selective
catalytic and non-catalytic reduction (SCR and SNCR)
systems, the ash may become unsuitable for the cement
industry and require treatment (Zhang and others, 2003).
However, proper combustion management can negate the
effect of low NOx burners. In addition the fly ash can be
used in cement clinker production (Goss, 2004b).
Production and use of bottom ash also increased during 2002.
The overall utilisation rate achieved 35.4% in 2002. Bottom
ash and boiler slag are used as aggregates. Typical
applications for bottom ash are as a substitute for sand and
gravel in roadwork, embankments and structural fills. Boiler
slag was mainly used in roofing and blasting applications as
well as for snow and ice control (ACAA, 2003; Naik and
Chun, 2003a). FBC ash is chemically similar to class C fly
ash except for the SO3 and SiO2 contents. The SO3 content is
higher in FBC ash and the SiO2 content lower relative to
conventional class C fly ash. Residues from integrated
gasification combined cycle plant (IGCC) are also high in
calcium (Naik and Chun, 2003a). The potential uses of
gasification ash include cement raw material. Utilisation may
be enhanced by separating a higher carbon product from a
lower carbon product or by making the carbon less active.
The higher carbon product may be used as activated carbon
or as fuel for the gasifier or cement kiln. The remaining
residue may possibly be used in cement, ready-mix concrete,
structural fills, embankments and soil stabilisation (Larrimore
and Morton, 2003). Further information on FBC and IGCC
residues is given by Adams (2004).
Cement and concrete – benefits and barriers in coal ash utilisation
Production and utilisation of coal residues
The American Coal Ash Association (ACAA) is a trade
association to advance the safe and economic utilisation of
coal residues. It recommended the term coal combustion
products (CCP) to emphasise the role of coal residues as a
commodity. The ACAA (2003) attribute the growth in use of
fly ash to local material/mineral shortages, improved fly ash
quality, higher volumes of fly ash used in concrete, increased
use in soil projects and waste stabilisation or a combination
of several factors.
A regulatory determination was issued by the US EPA in
April 2000 that CCP did not warrant treatment as hazardous
wastes but rather should be managed as solid waste with
enforcement authority passing to the various States and local
authorities. Use in mine reclamation is controlled by the
Surface Mining Control and Reclamation Act (SMCRA). The
Resource Conservation and Recovery Act (RCRA), enacted
in 1976, legislates on solid wastes, including cradle-to-grave
regulation of hazardous waste practices (subtitle C) and
non-hazardous waste (subtitle D) (Degeare, 2002). The US
EPA did not have sufficient data on mine fill to pass
judgement on the benefits of mine fill using CCP but began
to collect information in 2001. Rules are being developed to
help prevent unwise disposal while enabling reclamation of
many polluted old mine sites using CCP (Wittner, 2003). The
US EPA is developing proposed guidance to cover the
placement of coal ash in mine reclamation activities (see also
http://www.epa.gov/epaoswer/other/fossil/).
Placement of CCP in mines has to be a genuinely beneficial
use rather than an inexpensive disposal practice since, when
not done properly, it has the potential to contaminate
groundwater which could damage human health and the
environment (Evans, 2002). The industry considers that any
additional Federal regulation of CCP placement at SMCRA
mine sites should only be based on sound scientific evidence
that the existing framework is not adequate. The final rule
from the US EPA was expected by August 2004 (Roewer,
2002; Vories, 2002a,b) but the National Academy of Sciences
(NAS) is now under contract to produce an independent study
of mine placement of CCP which is not likely to be issued
before early 2006. Unfortunately, it appears that the US EPA
has decided to suspend its work on mine placement and await
the results of the NAS study (Roewer, 2004). The
classification of CCP as a waste or a product is a central
issue to the industries concerned; classification as a waste
creates a stigma which hinders marketing (Thacker, 2003).
Indeed, if the US EPA were to agree to the petition from
environmental special interest groups of February 2004 to
halt further CCP disposal in ash ponds or mine placement
until the US EPA has reached a decision, a large percentage
of the industry’s CCP disposal capacity would be unavailable
and 40% of the US coal-fired generating capacity would be
shut down (Roewer, 2004).
A number of states have adopted laws and regulations or
issued policies and/or guidance specifically pertaining to
CCB use and these vary widely. The greatest concern relates
to applications involving land, such as in agriculture,
structural fills, mine use and embankments. A detailed review
of state regulatory requirements is provided by Ziemkiewicz
and Dube (2003).
17
Production and utilisation of coal residues
Economic barriers to increased use of CCP include the high
cost of transporting low value CCP and competition from
locally available natural materials (Kalyoncu, 2002).
In 2003 the United States Environmental Protection Agency
(US EPA) initiated a programme, with the CCP industry,
known as the ‘Coal combustion products partnership
(C2P2)’. Cosponsors of this programme include the US
Department of Energy (US DOE), the Federal Highway
Administration, the ACAA and the Utility Solid Waste
Activities Group. The 109 charter members include electric
utilities, universities, research organisations, ash marketers,
end-users, and trade associations. The programme is
designed to help identify actual or perceived barriers to
increasing CCP utilisation. The initial focus is to promote
increased use of fly ash in concrete. Four workshops were
held in 2004 across the USA and two more are to take place
in 2005. New regulations on mercury control may pose
economic challenges although they are not expected to have
a significant effect on CCP applications (Goss, 2003). To
address concerns about mercury, the National Energy
Technology Laboratory (NETL) of the US DOE is
sponsoring a number of projects to evaluate potential
leaching and volatilisation of mercury and other trace
metals from coal utilisation by-products and products
manufactured from them. Preliminary results indicate that a
minimal amount of mercury is leached from coal
combustion residues (Clean Coal Today, 2004).
Organisational partnerships between CCP stakeholders,
researchers, associations, trade groups and regulators are
another key to increasing utilisation of CCP in the future. The
US DOE set up the Combustion By-products Recycling
Consortium (CBRC) to solicit proposals for DOE funded
research related to CCP utilisation. Priorities are identified in
three areas (western, midwestern and eastern) and set against
national priorities and recommendations in order to review
the proposals. The aim is to reach 50% utilisation by 2010
through this research funding. Detailed information on the
projects is provided on the CBRC website
(http://cbrc.nrcce.wvu.edu). There are also many research
projects in progress at Universities and partnerships through
States, communities, and industries as well as international
collaboration to further coal ash utilisation (see Goss, 2003,
2004a; Feeley and others, 2004). Recent work at the Electric
Power Research Institute (EPRI) has focused on three key
applications for fly ash: horticulture, flowable fills, and
mitigation of alkali-silica reactivity (ASR) related to damage
in concrete (Power Engineering, 2004).
The future trend towards much more use of FGD is expected
to triple the quantity of FGD residues to about 75 Mt/y. This,
coupled with the potential effect of US EPA regulations,
presents a formidable challenge to electric utilities and the
CCP user industries (Kalyoncu, 2002).
2.2 Increasing ash utilisation
Actual and potential uses are summarised in this section for
coal ashes. Applications for coal residues may usefully be
divided into high, medium and low technology. The
18
suitability of high volume applications varies according to
priorities and ash markets in different countries.
Fly ash is used mainly in the construction industry in Europe,
as a component in concrete and in concrete blocks, as cement
raw material, in blended cement, in road construction, and to
a minor extent as infill (Vale and others, 2003). The German
calcareous brown coal fly ashes are mainly used for filling
depleted surface mines and to a minor extent as a fill in
asphalt and in underground mining, for surface recultivation,
soil stabilisation, fertiliser and as a component in concrete
(Miskiewicz and others, 2003). Indian lignite fly ashes may
find greater use in agriculture, including pest control
(Narayanasamy, 2003).
High value applications for fly ash cenospheres include the
development of metallic foams, for example aluminium foam
for motor vehicles (Singh and others, 2003). As noted in
Section 2.1, class C fly ash is not used as extensively as low
lime class F fly ash in the USA. Potential uses for class C ash
are graded in Table 3 and appear to offer the greatest scope
for utilisation in medium and low technology applications
(Naik and others, 2003b) as in Europe.
Bottom ash is used in concrete blocks, cement, bricks, tiles,
aggregates, road construction, embankments, structural fill
and in surface mine reclamation. Boiler slag applications are
medium/low technology road construction, mainly as
substitution for sand and gravel, for example, blasting grit, in
concrete and grouting material, aggregates, snow and ice
control.
It is generally easier to find applications for the smaller
quantities of bottom ash and boiler slag produced than for fly
ash. Hence the rest of this report will concentrate on high
volume markets for fly ash in cement (Chapter 3) and in
concrete (Chapter 4).
Both these markets deploy different benefits and have to
overcome different barriers in fly ash utilisation. Fly ash
closely resembles volcanic ashes used in production of the
earliest known hydraulic cements about 2300 years ago.
Those cements were made near the small Italian town of
Pozzuoli which later gave its name to the term ‘pozzolan’. A
pozzolan is a siliceous of siliceous/aluminous material, that,
when mixed with lime and water, forms a cementitious
compound. Fly ash is one of the most commonly used
pozzolans in the world. It is a fine, glass powder consisting
primarily of silica, alumina and iron. The features which
make fly ash an attractive material in concrete are
summarised in Table 4 (STEAG, nd).
Issues which may constitute barriers to the utilisation of fly
ash include marketing, storage, the effects of pollution
control equipment leading to increased carbon or ammonia
in ash, cofiring of coal with other fuels, and the potential
for release of mercury or other trace emissions. Legislation
may frequently also be viewed as a barrier to utilisation,
but, when seen as part of the drive to ensure use of all by-
products and to reduce the consumption of raw materials,
regulations can provide the necessary certificate to promote
utilisation.
IEA CLEAN COAL CENTRE
 Production and utilisation of coal residues

Table 3 Potential uses of Class C fly ashes (Naik and others, 2003b)
Application Potential

a High technology applications

Recovery of materials medium

Filler for polymer matrix (plastic) medium
Filler for metal matrix composites medium

Other filler applications: asphalt roofing shingles low

wallboard high
joint filler compounds medium
carpet backing medium
vinyl flooring medium
industrial coatings medium

Super pozzolanic material (beneficiated ash) very high

b Medium technology applications

Blended cement very high

Lightweight aggregates: fired very high
unfired high

Concrete products: low-strength concrete very high

medium strength concrete very high
high strength concrete very high
lightweight concrete very high
prestressed/precast concrete products very high
roller compacted concrete very high
cellular concrete very high

Filler in asphalt mix high

Bricks: unfired bricks high
fired bricks very high
clay bricks very high
Blocks: building blocks very high
decorative blocks very high

Reefs for fish habitats very high

Paving stones very high
Stabilisation of municipal sewage sludge high
Hazardous waste stabilisation: inorganic wastes high
organic wastes medium
combined complex wastes low
Ceramic products medium

c Low technology applications:

Backfills: bridge abutments, buildings etc very high

trench and excavation backfills very high
Embankments very high
Site development fills very high
Stabilisation of landslides – grouting very high
Landfill cover (substitute for soil) very high

Pavement base and subbase courses: combined with lime or cement and coarse aggregate very high
combined with cement or lime very high
combined with on-site soils with or without addition of lime or cement very high
Soil stabilisation or subgrade stabilisation: construction of roadways high
parking areas high
foundation for runways high
Land reclamation: agriculture very high
turf (for example golf courses) very high
park land very high
Soil amendment: improve infiltration very low
decrease subsurface porosity very high
fertiliser high
Slurried flowable ash very high

d Miscellaneous civil engineering applications

Backfills: between foundations and existing soil very high

retaining walls very high
utility trenches very high
Excavation in streets and around foundation very high
Fills for abandoned tunnels, sewers and other underground facilities very high
Grouts very high
Hydraulic fills very high

Cement and concrete – benefits and barriers in coal ash utilisation 19

Production and utilisation of coal residues

Table 4 Key features and benefits of fly ash (STEAG, nd; Heidrich, 2003)

Spherical shape allows fly ash particles to flow and blend freely in mixtures

Ball bearing effect creates a lubricating action when concrete is in its plastic state

Low density after compaction is only about 60% of that of a similar sand so fly ash is ideal for backfilling over soft soils

Higher strength as fly ash continues to combine with free lime, increasing structural strength over time

Decreased permeability and
increased durability
Reduced sulphate attack
Reduced efflorescence
dense packing and long term pozzolanic action, binding free lime, results in fewer bleed
channels, keeps aggressive compounds on the surface where destructive action is less,
concrete is more resistant to sulphate, mild acid, soft water (lime seeking) and seawater
since fly ash ties up free lime, preventing it combining with sulphate to cause destructive
expansion
due to chemical bonding with free lime and salts which can cause efflorescence; these
compounds are held inside.

Reduced shrinkage because the lubricating action of fly ash reduces water content and drying shrinkage.

Reduced heat of hydration
Reduced alkali silica reaction
Improved workability
since the pozzolanic reaction between fly ash and lime generates less heat, resulting in
reduced thermal cracking when fly ash is used to replace Portland cement
as fly ash combines with alkalis from cement that might otherwise combine with silica
from aggregates, causing destructive expansion
because concrete is easier to place with less effort, responding better to vibration to fill
forms more completely

Ease of pumping since less energy is required and longer pumping distances are possible

Improved finishing where sharp, clear architectural definition is easier to achieve, with less concern about
in-place integrity
Reduced bleeding decreases porosity and chemical attack so bleed streaking is reduced for architectural
finishes, and improved paste to aggregate contact results in enhanced bond strengths
Reduced segregation due to improved cohesion of fly ash concrete, reduces rock pockets and blemishes due to
segregation
Reduced slump loss makes concrete more dependable, allowing greater working time, especially in hot
weather

Marketing of fly ash is more successful where ash
associations are promoting co-operation between the relevant
industries, and are involved with the development of
standards and environmental legislation (see Brennan, 2003;
Brennan and others, 2003). Networks to promote transfer of
knowledge from utilities to ash users also play a major role.
For example, a small or medium enterprise may wish to save
virgin raw materials by deploying coal combustion residues.
By using only 5 wt% substitution of fly ash for clay in
bricks, pipes, roof and floor tiles in Germany, Italy, the
Netherlands and the UK, the industry could save 2.8 Mt/y of
the 60 Mt/y of clay used (Janssen, 2003). Brendel and others
(2003) make a case for combined disposal and utilisation
contracting in order to promote utilisation. For example,
transport costs are otherwise incurred by two separate
contractors and reimbursed by the utility. By covering both
functions under one contract, the utility can reduce transport
costs and expect a more efficient and less costly management
of the residues. In India, the Fly Ash Mission is working
closely with the Bureau of Indian Standards to update
existing standards for fly ash and its products in order to
promote wider acceptance of the material (Kumar and others,
2003a,b).
Storage may be an issue for dry PFA, used in high value
applications. At Longannet power station in Scotland, the
greatest production of PFA is during winter and the greatest
need for it in the construction industry is during the summer
(McCaffrey, 2003). Storage capacity in the silos may limit
the chances of a utility delivering all its fly ash to the market.
In the Netherlands, 1 t of storage capacity is considered
sufficient for each 5 t of fly ash produced (Backer van
Ommeren, 2003). Wet fly ash may be stored easily but is
mostly used in landfill. In many cases, for example in India,
fly ash and bottom ash are mixed together and disposed of in
a slurry to ash ponds, making the ash unsuitable for
demanding applications (Prasad and Singh, 2002). Handling
and storage have been a handicap to fly ash utilisation in
India. Pneumatic conveying systems are more expensive than
mechanical systems but preferable for dust free operations
and economy of space. If a user facility is within 2–3 km of
the power station, a pneumatic conveying system is
preferable to transport by rail or road in bulk carriers. The
ash can be blown into the silo at the user site. Wet and semi
wet ash may be better dried at the ash dumps and then fed to
silos. The economics need careful examination (Sharma and
others, 2003).
Another issue has been changes in fly ash due to the
installation of NOx reduction equipment. Low NOx burners
can result in an increase in unburnt carbon in fly ash while
SCR and SNCR may lead to the problem of ammonia in ash
(see Nalbandian, 2004). Dealing with this issue generally
results in disposal of the separated carbon or burning it in the

20 IEA CLEAN COAL CENTRE

 Production and utilisation of coal residues

combustor. However, Maroto-Valer and others (2002) at the
Pennsylvania State University describe the development of
valuable products from fly ash carbons. Unburnt carbon may
be used to produce activated carbons by steam activation. The
low sulphur content of unburnt carbon from coal combustion
could make it a strong competitor to petroleum coke for the
production of carbon artefacts, the carbon acting as a filler. A
technology has also been developed at the University of
Kentucky to recover high carbon spiral product from fly ash
ponds and landfills. This may be activated and used as
sorbent for mercury and NOx capture in flue gas (Andrews
and others, 2003). Increased ammonia in ash is likely to
affect leaching of metals, for example nickel (Wang and
others, 2003a,b).
Cofiring coal with biomass and waste matter is an attractive
option to reduce greenhouse gas emissions (see Smith and
Rousaki, 2002). The technically acceptable amount of
secondary fuels is restricted by furnace design and
combustion technology. Hence cofiring should not change the
properties of coal ashes and have no adverse effect on
homogeneity, effectiveness and environmental compatibility
(Vale and others, 2003). However, the fly ash characteristics
change as the proportion of secondary fuel is increased. For
example biomass ashes are not alumino-silicates but mixtures
of simple inorganic salts, principally the oxides, phosphates,
carbonates and sulphates of silica, calcium and potassium.
Biomass therefore increases the alkali metal concentrations in
the ash (Hall and Livingston, 2001).
Studies on the release of mercury from coal ash to the
atmosphere, carried out in the USA, the Netherlands and
Finland, suggested that volatilisation and leaching of mercury
from fly ash were minimal. A study in India confirmed that
the leaching of arsenic, mercury and selenium from fly ash
was negligible due to the high pH of >8.0. Where a wet
disposal method is adopted at large power stations, the
alkaline nature of most fly ash (pH 9.29) and pond ash
(pH 8.86) results in a low risk of mercury leaching from the
ash pond (Mukherjee and Zevenhoven, 2004).
Future controls for mercury emissions using activated carbon
sorbent will increase the carbon in ash. This prevents use of
the ash in concrete since carbon attracts air entraining agents.
High temperature uses of ash may also be affected. Mercury
trapped in the ash is not likely to be released after
solidification of concrete. High carbon ash is desirable as a
feedstock in cement kilns but the high temperatures release
mercury and the amounts have to be determined relative to
that entering the cement kiln from other raw materials
(Golden, 2003). As mercury control technologies are
implemented in the USA, the potential release of mercury
from coal combustion by-products becomes increasingly
important. Plans for demonstration of mercury sorbents are
outlined by Nelson and others (2003) and the Energy and
Environmental Research Center (EERC) has launched a
three-year effort to study potential releases of mercury and
air toxic elements from coal combustion products (CATM,
2003).

Cofiring with petroleum coke also changes ash characteristics.

The ash contains vanadium, nickel and iron compounds from
the oil, sodium, calcium and magnesium compounds from
seawater contamination and silica and alumina from
contaminants in the crude oil or from catalytic cracker fines.
Fly ashes from petroleum coke contain relatively greater
amounts of vanadium, nickel and sulphur, and have more sub-
micron material. This is because the vanadium and sodium
compounds tend to be volatile at flame temperatures, and can
form a finely divided fume (Hall and Livingston, 2001).

Cofiring at high substitution rates (>10 wt%) may increase

the content of mercury and other trace elements in ashes.
This was investigated at KEMA in the Netherlands (Meij and
te Winkel, 2003; Meij and others, 2001a,b, 2002, 2003). On
average around 50% of the mercury present in coal was
found in the fly ash. This was a greater proportion than that
found by other authors in Germany (6%, 17%, 26%). In the
USA the fly ash contained very little mercury. This was due
to the high operating temperature of the ESPs studied. The
higher temperatures were necessary to prevent condensation
of sulphuric acid from the higher sulphur coal. Similar
partitioning of mercury was obtained at KEMA during
cofiring with sludges and biomass up to 10 wt% (Meij and te
Winkel, 2003; Meij and others, 2002). In general the cofiring
ashes complied with the limits set in the 2001 European
Waste Catalogue for non-hazardous substances except at high
substitution rates for some elements. Hence the ashes from
cofiring coal with waste wood at $30 wt% exceeded the
limits for lead and chromium content. For petroleum cokes,
limits for vanadium were exceeded at cofiring rates of
$50 wt% (Meij and others, 2001a,b).

Cement and concrete – benefits and barriers in coal ash utilisation 21

 3 Cement
Fly ash from pulverised fuel combustion may be added to the
cement kiln as raw material or inter-ground with the clinker
to make blended cement. It can replace over 80% of the
clinker in a blended cement mixture (Naik and others,
2003b).
3.1 Cement raw material
Fly ash contributes silica, alumina, iron and calcium to the
raw material mix for cement clinker. The amounts of fly ash
used depend primarily on the raw material available at a
cement works, that is on the composition of the limestone
and marl deposits (VDZ, 2002). Fly ash is generally used as a
source of alumina in the raw meal mix (van der Meer, 2004).
There are several limits to the amount of fly ash which can
be used in cement raw material and this differs from country
to country. For example, the chemical composition of Indian
fly ashes is similar to that of clays and they may be used as a
clay substitute. However, the limestone used in making
cement clinker also contains around 8–10% silica or more
and the primary fuel contributes argillaceous components so
that the amount of fly ash may be limited in many cases
(Sharma and others, 2003).
In Japan, the limestone is pure, containing on average
92–98% CaO whereas it may only contain 80% CaO in some
regions of Europe. A greater proportion of the clay may
therefore be substituted by fly ash in Japan. Some European
limestones may contain sufficient clay minerals without
adding clay and this may limit the amount of fly ash which
can be added to the raw materials. Clay amounts to around
15% of the total raw materials used in cement raw materials
in Japan (see Figure 4). As noted in Section 2.1, a larger
proportion (62%) of the coal ash produced in Japan is used as
cement raw material (see Figure 3) than for fly ash in Europe
(12%). The difference is not due to the data for coal ash
including bottom ash in addition to fly ash in Japan. In part it
is due to greater amounts being substituted for clay. The rate
of fly ash substitution is about 5% of the cement raw
materials. It is fed with the limestone at the preheater stage.
In 2002, 5.7 Mt fly ash was used for a total Portland cement
production of 80 Mt (Harada, 2004). Fly ash contains less
SiO2 and more Al2O3 than clay and this may limit the
others 10 oil coke 11 others 3
iron oxide 24 coal 92 heavy oil 1
silica stone 59 gypsum 37 power
95 kwh
clay 212
limestone 1098
Figure 4 Raw materials and fuels needed to
produce 1000 kg of Portland cement in
Japan (Harada, 2004)
22
replacement rate of clay by fly ash (Roof, 2001). In Japan,
the fly ash composition is very similar to that of clay and
some power stations choose appropriate coals in order to
produce fly ash which is most suitable for use as a clay
substitute. A cost effective transport arrangement also
promotes this fly ash application. Cement companies send
limestone for FGD sorbent by ship to power stations and
receive fly ash or gypsum back for use in cement raw
material. In Japan slag is preferred to fly ash as cement
extender (blended cement) so this may also explain why
greater use is made of fly ash in cement raw materials
(Tanosaki, 2004). In Korea the quantity of coal ash which
could be used as raw material for cement clinker production
is about 2.4 Mt/y but the amount used in 2000 was only
about 0.8 Mt. This was because the price of coal ash,
transport and facility costs were not competitive with those
for clay (Cha, 2001). Meanwhile, as noted in Section 2.1,
Japan is exporting fly ash to Korea and this may distort the
utilisation data.
The cement plant at Maastricht, The Netherlands, has only a
small quarry and has therefore tried to reduce the rate of use
of raw materials from the quarry by deploying waste
products. The plant has a long dry kiln from the 1960s with
2 stage preheater and precalciner. The use of limestone has
decreased by 10–15% by substituting fly ash, blast furnace
slag and secondary fuels, mainly sewage sludge. However,
fly ash has to be injected into the preheater and precalciner
rather than into the main kiln. This precludes high carbon fly
ash because the temperature is too low in the preheater. The
fly ash is not ground and the amount which can be used is
limited to only 3–5% of the raw materials (van der Meer,
2004).
Miskiewicz and others (2003) discuss the utilisation of lignite
fly ash as raw material for cement clinker production. The
amount of chlorine, sulphur and alkalis are especially
important since the high temperatures cause losses of volatile
material. Most of the lignite fly ashes in Germany show
higher amounts of alkalis and sulphur compared to limestone
and marl. Hence the amount of these components limits the
use of lignite fly ash in cement kilns and a by-pass may be
required. In this case no great added value is expected and
transport costs limit the use of lignite fly ash to within close
proximity to the power stations.
The main benefits and barriers to be overcome when using
fly ash in the raw material for production of cement clinker
are discussed:
Benefits of using fly ash as part of the cement raw material
are that natural materials are saved and less ash has to be
stored (Ladenhaufen, 2004). Greater quantities of fly ash are
claimed to be usable in eco-cement, developed in Australia
and using magnesium carbonate to replace part of the
limestone in the cement kiln. The eco-cement incurs less CO2
emissions in its manufacture and then absorbs more CO2 in
the products than Portland cement (ENDS Report, 2003).
IEA CLEAN COAL CENTRE

In some cement works fly ash is used to alter the chemistry
of the cement. The sodium and potassium alkali in the final
product is reduced by adding low alkali fly ash to the raw
meal. This has environmental and practical benefits, reducing
the kiln temperature and producing a more saleable, lower
alkali product (Sear, 2002). In India, Reddy (2003) reports
that clinker quality is improved when using fly ash compared
to clay in the raw meal. The alumina to ferrous ratio was
higher when using fly ash and the reactive silica in fly ash
improved the quality. In addition the raw meal was finer,
improving the grindability of the raw mix.
In the USA, Goss (2003) points out that replacing clinker raw
materials, natural clays, shales and other ores, with fly ash has
the advantage that ASTM quality standards are not mandatory
as in concrete applications. Fly ash containing high amounts
of unburnt carbon (up to 21%) can be used and help to reduce
the energy requirements of the cement kiln. This reduces
costs, for example, at a kiln in Illinois, use of fly ash yielded a
10% production increase and a 4% fuel saving.
Transport from the power station and mixing of fly ash in
the raw meal at the cement kiln need careful design. It is
important that ash utilisation programmes form an integral
part of the planning of any new thermal power station while
the collecting system of existing plants should be modernised
and upgraded. Fly ash is required in dry state whereas most
power stations send wet fly ash to disposal sites. Dry
collection of fly ash may be achieved by modifying existing
systems. Both mechanical and pneumatic conveying systems
or a combination of the two can be considered for use at the
power station. Pneumatic conveying systems are costly but
preferable for dust free operations and economy of space
(Sharma and others, 2003).
pneumatic conveying
from ESP
silo
hopper hopper
1 2
loading
conveying
by road
by rail
Figure 5 Collection, handling and transport of dry fly ash (Sharma and others, 2003)
Cement and concrete – benefits and barriers in coal ash utilisation
Cement
Dry transport implies sealed pneumatic tankers for road
transport of fly ash or dedicated pipelines for short distances
(<1 km) where pneumatic conveying can be used. Road
tankers give total flexibility as to delivery destination but at
the price of a specialised transport vehicle. Pneumatic
conveying is excellent for delivery to an on-site processing
facility, but the fixed nature of pipework means that it is
totally inflexible (Heeley, 2003).
Where the user facility is within 2–3 km of the power station,
a pneumatic conveying system can be adopted for dry fly ash
in preference to transport by rail or road in bulk carriers used
for greater distances. Handling of dry fly ash at the user end
involves pneumatic discharging by the conveying duct of the
built in blowers of the bulk carrier into the storage silo. The
suggested system design for collection, handling and
transport of dry fly ash is shown in Figure 5. When using wet
and semi wet fly ash from ash dumps, it is probably best to
dry it there and then feed it to the storage silo so that a
unified approach is maintained for subsequent handling
(Sharma and others, 2003).
In the case described by Reddy (2003) in India, the fly ash is
transported from the power station by bulk carriers and
evacuated using compressed air to a separate silo. The ash is
dosed by valves and solid flow meters to control the raw mix
in the kiln.
Storage of fly ash is vital in order to cope with the heaviest
fly ash production not occurring at the same time as the
highest market demand. Concrete domes are efficient and
economic for storing large quantities of bulk materials, for
example in the range of 15–100 kt. The storage and
automated reclaim system are integrally related and not all
2 km
(max)
silo to cement
mill hopper
upto
10 km
more than
10 km
23
Cement

reclaim systems work equally well for every size and shape
of dome. Their main advantages are (Hunter, 2003):
● better protection of stored materials, preventing fugitive
dust emissions;
● efficient use of land space, for example 40 kt of fly ash
can be stored within a 51 m diameter dome;
● strength and durability, allowing materials to be piled up
high against the walls, and able to withstand hurricanes,
typhoons and earthquakes;
● rapid construction, usually within one to four months
after the foundation is finished and during bad weather
since most of the work is done inside an insulated
form;
● simplicity and cost since the spherical shape involves
less surface area than other shapes, minimising materials
for their construction; and, since they are tolerant of
settlement (15–50 cm or more), domes can be built on
relatively poor soils using simple and inexpensive
foundations.
A 40 kt capacity fly ash storage dome was constructed in
1995 for the Alsen cement plant, Lägerdorf, Germany by
DOMTEC® International. Fly ash is used as a raw material
in cement production. The large storage dome (58 m diameter
by 31 m high) allows the purchase and stockpile of sufficient
fly ash for six to eight months production during times of the
year when it is least expensive. The fly ash is received from
self-discharging bulk trucks and the trucks pump the ash into
the dome by two pneumatic lines. Fly ash is withdrawn from
the dome by means of a Cambelt automated mechanical
reclaim system which feeds a drag chain conveyor installed
in a tunnel beneath the floor. Dome construction took about
four months. The entire project was completed over
11 months, including engineering, site preparation,
fabrication, construction, equipment installation, electrical
work, testing and start up (Hunter, 2003).
Carbon in ash can prevent use of fly ash in cement kilns, for
example, at the Maastricht plant, in the Netherlands
mentioned previously. There is pressure to find a large
volume market for fly ash containing unburnt carbon from
the implementation of combustion measures to reduce NOx
emissions and this is currently a concern in the USA.
Bhatty and others (2003) describe a commercial
demonstration of use of high carbon fly ash in cement clinker
production. Fly ash with nearly 13% loss of ignition (LOI)
from Ameren’s Coffeen Power Station, IL, USA, was tested
at Illinois Cement. Nearly 200 t of the fly ash was used at a
rate of 3.5% addition to the cement plant raw mix and ran for
nearly three days. The composition of the kiln feed with and
without 3% high carbon ash prior to the demonstration is
shown in Table 5a. The fly ash was also tested by differential
scanning calorimetry to determine its fuel content and the
presence of any organic volatile species which could affect
emissions. A large exothermic peak at temperatures above
450°C confirmed substantial heat content in the fly ash
whereas a lack of any exothermic peak at temperatures below
450°C suggested an absence of volatile matter in the fly ash.
An endothermic hump below 450°C, consuming heat,
indicated the tendency for the fly ash to reduce the
temperature in the upper portion of the preheaters at cement
plants. This would lead to clearer pathways and smooth
material flow of the feed load.

Table 5 Effect of using a high carbon fly ash (13% LOI) in a cement kiln (Bhatty and others, 2003)

a Composition of kiln feed (wt%) with and without fly ash

Analyte Kiln feed Kiln feed + 3 wt% fly ash

SiO2 19.5 22.4
Al2O3 5.40 6.64
Fe2O3 2.32 2.84

CaO 66.7 61.9

MgO 3.25 3.06

SO3 0.94 0.91
Na2O 0.30 0.44
K2O 1.04 1.30
TiO2 0.28 0.37
Mn2O3 0.21 0.20

LOI 0 0

b Compressive strength (MPa) of cement before, during and after use of 3.5 wt% fly ash

Before During After ASTM C 109

3-day 21.6 24.1 20.1 12.0
7-day 28.1 29.3 27.2 17.0
28-day 34.6 36.5 34.8 28.0

24 IEA CLEAN COAL CENTRE


The clinker composition before and during the three-day
demonstration was similar but photomicrographs showed
some differences in the crystal development. During the
demonstration, the crystal structure indicated somewhat faster
cooling than for samples taken before the test. The cement
clinker complied with the ASTM C 150 specification both
before, during and after the demonstration but the use of fly
ash gave the best strength performance (see Table 5b),
despite a slightly lower fineness. The time of set, air contents
and autoclave results were normal for the demonstration
cement. Emissions of NOx were lower for the period during
which the fly ash was included in the mix. SO2 emissions
were low throughout and were not changed significantly.
However, CO emissions were higher during and after the fly
ash burn than before it, increasing from 43.3 kg/h to 125 kg/h
and then decreasing to 71.7 kg/h respectively. The
demonstration was successful and pointed to the emergence
of a market in the USA for the otherwise non-usable high
carbon fly ashes (Bhatty and others, 2003). The increased CO
emissions may indicate organic emissions and both need to
be avoided. Burning alternative fuels in the precalciner could
reduce the CO emissions from the use of high carbon fly ash
but this could make the problem worse if combustion in the
precalciner is not adequate (van der Meer, 2004).
As noted above as a benefit, studies conducted by
Construction Technology Laboratories Inc, Skokie, IL, USA,
have shown that fly ash containing up to 21% of unburnt
carbon can be used and help to reduce the energy
requirements of the cement kiln. This requires careful
regulation of the high carbon fly ash in the raw feed to allow
the combustion of the unburnt carbon in the fly ash to release
energy in the kiln which, in turn, reduces the amount of fuel
required for the kiln (Goss, 2003). The unburnt carbon is
fixed carbon which has an ignition temperature of about
850°C. This temperature is reached at about the third stage in
a preheater kiln. The low temperature may increase CO
emissions from the kiln although only slight increases have
occurred. Kiln instability has been encountered when more
than 15% of the fuel for a preheater kiln comes from the
carbon in kiln feed fly ash. High LOI fly ash (>30%) has
been placed on the feed shelf of a preheater kiln to recover
the energy better, but the carbon burned in the load caused
localised reducing conditions which increased sulphur
volatilisation and build-up in the tower. Insufflation of high
LOI fly ash into the riser duct of a preheater or precalciner
kiln is the better approach for high LOI fly ash. If the total
carbon in the fly ash is too high, insufflation into the burning
zone is another possibility (Haverland, 2004).
Cofiring coal with other fuels may affect the quality of the
fly ash produced. The requirements for use of fly ash as raw
material for cement clinker production are based on bilateral
agreements between consumers and producers. The amount
of phosphate in the fly ash is limited since this element
affects clinker formation. The amount of free lime is also
important. Tests were carried out at pilot-scale, pulverised,
dry firing system at KEMA in the Netherlands to investigate
the effects of cofiring with waste wood, chicken litter and
refuse derived fuel. High proportions of waste wood (up to
20 th%) and of refuse derived fuel (up to 15 th%) could be
used without affecting the fly ash quality but only a small
Cement and concrete – benefits and barriers in coal ash utilisation
Cement
percentage of chicken litter was possible due to the increase
of several components such as free lime, alkalis, chlorine and
sulphur (Sarabèr and others, 2002).
Other tests at KEMA reported by Romey (2002) investigated
the residues from burning fuel blends from coal and plastics.
Without additional treatment, the residues could not be used
in construction materials due to high chlorine, sulphate and
heavy metal content and high electrical conductivity.
Recycling these residues as raw materials for cement kilns is
suggested. However, the cement works would have to be
equipped with the requisite gas cleaning facilities and the
mineral composition of the residue would have to fit the raw
materials requirements at the kiln.
Mercury could be released from ash use in clinker
production according to a US EPA study. Test methods to
determine Hg volatilisation and leaching are being reviewed.
Changes in the Hg content of fly ash, as a result of
implementing Hg control technologies, and the effects of its
use in cement kilns are under evaluation in the NETL
co-operative agreement mentioned in Section 2.1
(Thorneloe, 2002). High carbon fly ash is a suitable
feedstock for cement kilns but is likely to contain a higher
mercury content (Golden, 2003). However, this could be
balanced by appropriate choice of other raw materials in the
kiln mix. Preliminary results from the NETL study of
potential release of mercury from products such as cement
indicate that a minimal amount of mercury is leached from
coal combustion residues (Clean Coal Today, 2004).
The different forms of Hg, whether elemental or oxidised in
various chemical compounds, affect the control of its
emissions and transport in the environment. Hence it is
important to understand the speciation of Hg in the raw
materials and fuels used for cement manufacturing and in the
exhaust gases from cement kilns. In a literature review, it was
found that there were only limited data on the amount of
mercury in cement raw materials. None of the studies
determined the Hg variability that may exist within a give
raw material or Hg speciation. A research and testing
programme was recommended to combine bench-scale
testing as well as testing at cement plants (Johansen and
Hawkins, 2003).
3.2 Blended cement
Ordinary Portland cement, also known as grey cement, has at
least 95% clinker and 5% gypsum. There are many other
cement products, containing less Portland cement, for
example in Europe, cement may be blended with other
constituents such as ground granulated blast furnace slag,
silica fume (the finely divided residue resulting from the
production of silicon, ferro-silicon, or other silicon
containing alloys, that is carried from the burning area of a
furnace by exhaust gases) or fly ash (see Table 6). Portland
pozzolana cement can consist of 15–35% pozzolan material,
such as fly ash, and the rest is clinker (ZKG International,
2003). The use of fly ash in a blended cement in Europe is
defined by DIN EN 197-1 for both siliceous and calcareous
fly ash (see Table 7).
25
Cement

Table 6 The 27 products in the family of common cements defined by EN 197-1 (CEN, 2000)

Composition (percentage by mass*)

Main constituents
Main Notation of the 27 products
Blast Pozzolana Fly ash Minor
types (types of common cement) Silica Burnt
Clinker furnace Limestone additional
fume natural silice- calcare shale
slag natural constituents
calcined ous -ous
K S D† P Q V W T L LL

CEM 1 Portland cement CEM I 95-100 – – – – – – – – – 0–5

CEM II/A-S 80–94 6–20 – – – – – – – – 0–5

Portland slag
cement
CEM II/B-S 65-79 21–35 – – – – – – – – 0–5

Portland silica fume

CEM IIA-D 90–94 – 6–10 – – – – – – – 0–5
cement

CEM II/A-P 80–94 – – 6–20 – – – – – – 0–5

CEM II/B-P 65–79 – – 21–35 – – – – – – 0–5

Portland pozzolanic
cement
CEM II/A-Q 80–94 – – – 6–20 – – – – – 0–5

CEM II/B-Q 65–79 – – – 21–35 – – – – – 0–5

CEM II/A-V 80–94 – – – – 6–20 – – – – 0–5

CEM II/B-V 65–79 – – – – 21–35 – – – – 0–5

Portland fly ash
CEM II cement
CEM II/A-W 80–94 – – – – – 6–20 – – – 0–5

CEM II/B-W 65–79 – – – – – 21–35 – – – 0–5

CEM II/A-T 80–94 – – – – – – 6–20 – – 0–5

Portland burnt shale
cement
CEM II/B-T 65–79 – – – – – – 21–35 – – 0–5

CEM II/A-L 80–94 – – – – – – – 6–20 – 0–5

CEM II/B-L 65–79 – – – – – – – 21–35 – 0–5

Portland limestone
cement
CEM II/A-LL 80–94 – – – – – – – – 6–20 0–5

CEM II/B-LL 65–79 – – – – – – – – 21–35 0–5

CEM II/A-M 80–94 6–20 0–5

Portland composite
cement‡
CEM II/B-M 65–79 21–35 0–5

CEM III/A 35–64 36–65 – – – – – – – – 0–5

Blast furnace
CEM III CEM III/B 20–34 66–80 – – – – – – – – 0–5
cement
CEM III/C 5–19 81–95 – – – – – – – – 0–5

CEM IV/A 65–89 – 11–35 – – – 0–5

CEM IV Pozzolanic cement‡
CEM IV/B 45–64 – 36–55 – – – 0–5

CEM V/A 40–64 18–30 – 18–30 – – – – 0–5

CEM V Composite cement‡
CEM V/B 20–38 31–50 – 31–50 – – – – 0–5

* The values in the table refer to the sum of the main and minor additional constituents
† The proportion of silica fume is limited to 10%
‡ In Portland composite cements CEMII/A-M and CEMII/B-M, in pozzolanic cements CEM IV/A and CEM IV/B and in composite cements CEM V/A and CEM V/B
the main constituents other than clinker shall be declared by designation of the cement

Blended cements vary considerably from country to country,
depending on local traditions and materials availability. In the
Netherlands, fly ash is used to 25% in one type of blended
cement, and, with blast furnace slag at 50% and up to 5%
filler, the cement is made with only 47% clinker. The average
amount of clinker in cement is 47% for three cement plants
and 10–12 types of cement produced in the Netherlands. This
is quite different to the UK for example which has 95%
clinker in cement or to Germany at 82%. The average for
Europe is 85% clinker in cement. Use of fly ash in blended

26 IEA CLEAN COAL CENTRE


Table 7 Requirements for fly ashes in cement according to DIN EN 197-1 in Europe (Miskiewicz and others,
2003)
Siliceous fly ash,
Parameter
V W1
Loss on ignition, wt% #5
Reactive CaO, wt%* #10
Free CaO, wt% #1†
Reactive SiO2, wt%‡ $25
Compressive strength at 28 days, N/mm2§ – –
Expansion, mm¶ – –
* total CaO reduced by fraction calculated as CaCO3 and CaSO3
† up to 2.5 wt% accepted when expansion is given
‡ fraction of SiO2 which is soluble after treatment with HCl and boiling KOH solution
§ mortars with binder of ground fly ash, amount <40 µm between 10 and 30 wt%
¶ mixture with 30 wt% ground fly ash, 70 wt% cement
cement is preferred by cement companies over use in
concrete because they retain control over the ensuing building
quality (van der Meer, 2004). In South Africa, a high
proportion of between 20% and 40% fly ash is also used in
blended cement (Kruger, 2003). By contrast in Canada the
concrete industry generally prefers to incorporate fly ash and
ground granulated blast furnace slag into the concrete
mixtures at the batching plant to give them more flexibility in
concrete mixture proportioning. Silica fume and slag are used
there more than fly ash for blended hydraulic cements
(see also Section 2.1) (Bouzoubaâ and Fournier, 2004).
Lignite fly ashes from the main German mining areas contain
over 10 wt% of reactive CaO and may be characterised as
calcareous fly ash as defined by DIN EN 197-1. However,
they fail to meet the requirement for $25 wt% of SiO2.
Lignite fly ash cements, produced by inter-grinding cement
clinker with 10, 20 and 30 wt% of fly ash, were tested for
water demand, setting, soundness, compressive strength and
durability. They showed slightly reduced water demand and
accelerated setting but reduced compressive strength until
after storage, the time required increasing with the amount of
fly ash added. The blended cements should find good market
opportunities but need a technical approval from the German
building authority (Miskiewicz and others, 2003).
An important benefit of blended cement is avoidance of CO2
emissions. Every tonne of cement clinker replaced with fly
ash is estimated to avoid the emission of about 1 tonne of
CO2 to the atmosphere. The CO2 is emitted by calcination
and fuel burning in cement kilns which is estimated at 0.83 t
of CO2 per tonne of cement (80% clinker) in Europe
(Cembureau, 1999) and 1 t or 1.2 t of CO2 by US authors
(Walker and others, 2002; Deju, 2003 respectively). There are
also CO2 emissions from transport and further process
changes which need to be considered in calculating the
overall reductions (Sear, 2002). Using fly ash to replace some
of the Portland cement has become standard practice but
rarely comprises more than 40% of the cementitious
materials in the USA. However, use of class C fly ash for
rapid hardening hydraulic cements (MRT Cements, TX,
USA) is now possible at over 80% fly ash substitution, with
Cement and concrete – benefits and barriers in coal ash utilisation
Cement
Calcareous fly ash
W2
#5 #5
10–15 $15
– –
$25 –
$10
#10
various additives. Producing this cement uses much less
energy than Portland cement with no gaseous emissions from
the process so that CO2 emissions are avoided. Masonry
cements using 80–90% class C fly ash have improved
workability, better board life, reduced shrinkage and are
sulphate and acid resistant (Hicks, 2003).
Cement companies are under pressure to reduce their CO2
emissions so that there is considerable incentive to reduce
cement clinker production by substituting fly ash. For
example, recently proposed legislation in the US Congress
pressures producers of cement and energy to reduce their
CO2 emissions. Partnerships with utilities, coal combustion
product marketers, cement producers and others may help
reduce the production of Portland cement and therefore
reduce CO2 emissions (Goss, 2003).
However, all around the world, engineering standards and
experience are based on the properties of Portland cement
concrete. Changing them to cements based on other materials
is hindered by the conservatism of cement producers and their
commercial interests. Whilst the properties of alkali cements
are attractive, the commercial risks of introducing them are
often considered too high (Heeley, 2003). Despite providing a
certified cement, the European regulation, DIN EN 197-1 may
also be regarded as a barrier to greater use of fly ash in
cement. For example, commercialisation of a patented
technology from the Swedish firm, EMC (see also Chapter 5),
developed seven years ago, is claimed to have been blocked
by the European standard effectively guaranteeing the
dominance of Portland cement. The company claims that its
technology could reduce the amount of Portland cement
clinker by 50%, reducing CO2 emissions by some 40%. If
applied to the cement industry worldwide, this would reduce
global CO2 emissions by 3% (ENDS Report, 2004).
Barriers to use of fly ash in blended cement also include
marketing, transport and storage, carbon and/or ammonia in
fly ash, cofiring issues and the potential for mercury in ash.
Marketing
Partnerships are the key to promoting fly ash utilisation. An
27
Cement
example of successful marketing of fly ash in the cement
industry is given by ScotAsh the Lafarge-Scottish Power joint
venture, ash utilisation company which started in 1999
(McCaffrey, 2003). From the point of view of Scottish Power
this reduces the amount of ash going into lagoons, landfill and
environmental concerns. For Lafarge, use of the ash has the
benefit of reducing the amount of calcined raw material needed
for each tonne of cement, while reducing their CO2 emissions.
The joint venture has a robust business plan with the intention
of generating revenue from the project. The transport facilities
are shared to bring cement and the blended products to the
markets. The products include the Lafarge interground cement,
Phoenix, with up to 30% PFA with 70% cement and the Trojan
grout from ScotAsh with up to 90% PFA with 10% cement.
The aim it to use the entire ash production from Longannet and
Cockenzie power stations in sustainable applications. In 2003
ScotAsh is on target to save 40 kt CO2 and avoiding extraction
of around 600 kt primary aggregates. The key to successful
marketing is the favourable siting of the power stations and
cement works as well as a long-term agreement between the
interested parties (McCaffrey, 2003).
In South Africa, Kruger (2003) considers that use of fly ash
in blended cement has the advantage of becoming an integral
part of an existing cement market. The amount of classified
fly ash added can be varied to produce a series of binders,
each suited for a particular application. The addition can be
done either by interblending classified fly ash and cement or
by inter-grinding the clinker with fly ash. In the latter case,
the cement manufacturer may not wish to tie up this milling
capacity. With interblending the output of a cement factory
can be increased economically by using blend ratios of
between 20% and 40%. The fly ash is 87.5% 45 µm which
allows higher blend ratios to be achieved without
compromising the quality and consistency of the blended
cement.
Supply of fly ashes of suitable quality hinders their use as
supplementary cementitious materials. The emergence of
alternative cementitious systems which are inherently less
CO2 intensive, for example the Third Cement Series
(sulphoaluminate-belite-ferrite cements) developed in China
may fill gaps in availability of fly ashes in future. Those
based on calcium sulphate will benefit from the more
widespread implementation of FGD systems producing
gypsum (Gartner, 2004).
Transport and storage
In cement replacement applications a dry powder is required.
The issues relating to transport and storage reviewed in
Section 3.1 are also relevant here.
Carbon in ash
As shown in Table 7 the LOI of both siliceous and calcareous
fly ash has to be #5 wt% for use in cement in Europe.
However, up to 7% was found to be acceptable for the LOI of
Indian fly ashes when inter-ground at 20–30% in Portland
Pozzolanic Cements (PPC) with 65% cement clinker and 5%
gypsum and examined by Venkateswaran and others (2003).
The inter-grinding resulted in more than 70% of the coarser
fraction of the fly ash being ground to <45 µm in the final
product, minimising any negative effects from coarser
28
fractions. The mortar strength was not affected and the fly
ash based cement showed better flow properties compared to
ordinary Portland Cement.
Ammonia in ash
In view of the current trend towards ammonia-based NOx
controls, further study is needed to evaluate the potential
effect of ammonia on leaching of metals from cement
products using fly ash (Wang and others, 2003b). The issue
has been studied more with respect to concrete and is
therefore dealt with in Chapter 4.
Cofiring issues
The quality of fly ash must not deteriorate as a result of
cocombustion. When cofiring waste wood, chicken litter and
refuse derived fuel, components such as lead, zinc and
phosphate in the fly ash may influence the setting behaviour
of cement. Tests at KEMA in the Netherlands were
mentioned in Section 3.1. Limits on cofiring rates to avoid
undesirable effects on blended cement were 20 th% for wood
waste, about 15 th% for refuse derived fuel. The pozzolanic
behaviour of the generated fly ash is the determining factor
because the activity index is reduced by cocombustion of
refuse derived fuel. Only a small percentage of chicken litter
was possible. The results needed verifying with real-scale
experiments (Sarabèr and others, 2002).
Mercury in ash
Some information on the general issue of mercury in ash was
reported in Chapter 2 but no further information specific to
blended cement was found. As already noted, the NETL of
the US DOE is sponsoring research to evaluate potential
leaching and volatilisation of mercury and other trace metals
from products manufactured using coal ash. Preliminary
results indicate that a minimal amount of mercury is leached
from coal combustion residues (Clean Coal Today, 2004). An
extensive evaluation by CONSOL Energy includes cement
made using coal utilisation by-products and is scheduled for
completion in October 2004 (Feeley and others, 2004). As
mercury control technologies are implemented in the USA,
the potential release of mercury from coal combustion
products becomes increasingly important. Plans for
demonstration of mercury sorbents are outlined by Nelson
and others (2003) and the Energy and Environmental
Research Center (EERC) has launched a three-year effort to
study potential releases of mercury and air toxic elements
from coal combustion products (CATM, 2003).
3.3 Comments
Use of fly ash in cement has the benefit of reducing use of
natural raw materials. Blended cements also offer CO2
emissions avoidance and high fly ash substitution rates
(#40% or >80% for some calcareous fly ashes). Regulations
act both as a benefit and a barrier to fly ash utilisation. They
need to be broadened to include all potential markets for fly
ash in cement. In some respects, use of fly ash in the raw
material in cement kilns has the advantage of less rigorous
requirements but appears to be limited to 3–5% of the raw
material input, depending on the availability of other raw
materials. It also improves clinker quality.
IEA CLEAN COAL CENTRE
 Cement

Marketing barriers are being overcome to achieve CO2

emissions reduction through greater co-operation between the
different industries concerned. Close proximity of power
station and cement works or well-planned transport
arrangements as well as long-term agreements favour
successful marketing. Large storage domes smooth out
seasonal differences in supply of fly ash and demand for
cement.

High carbon fly ash is not regarded as suitable for injecting

fly ash into the preheater of the cement kiln where
temperatures are relatively low. However, a demonstration in
the USA has shown that fly ash containing up to 21%
unburnt carbon can be used in cement raw material, using
special feed procedures. This has the benefit of reducing the
energy requirements and hence costs.

Cofiring coal with other fuels may affect the quality of the
fly ash produced for both cement kilns and for blended
cements, although up to 20 th% waste wood, up to 15 th%
refuse derived fuel and a small percentage of chicken litter is
acceptable.

Cement and concrete – benefits and barriers in coal ash utilisation 29

 4 Concrete
Fly ash may be blended with cement to replace part of the
cement in concrete. The rate is typically 15–25 wt% of the
cement content but it can exceed 50% in some concretes. It
may also be added as fine aggregate or partially replace
cement, fine aggregate and water (Copeland and others,
2003; Naik and Chun, 2003b; Naik and others, 2003b).
When Portland cement hydrates it produces lime. Pozzolans
such as PFA react with this lime to form stable calcium
silicate and aluminate hydrates. These hydrates fill the voids
within the concrete, removing some of the lime (UKQAA,
2000). The types and amount of hydration products formed
when mixing cement with water depend upon many factors
such as duration of hydration, water to cementitious materials
ratio, properties of constituent materials, temperature, soluble
alkalis, and chemical admixtures. The formation of hydration
products causes an increase in the stiffness of cementitious
matrix over time. This stiffening behaviour of the matrix is
determined by the initial and final set times. At the initial set
time, the mixture begins to solidify and at this stage concrete
can neither be properly re-tamped nor can it be handled and
placed. The final setting refers to the stage when the mixture
attains sufficient hardness to support stress. The rate of gain
of strength is called hardening. Both setting and hardening
are considerably influenced by inclusion of both mineral and
chemical admixtures (Naik and others, 2001b).
A knowledge of setting characteristics of concrete
incorporating both mineral and chemical admixtures is
needed for efficient scheduling of concrete construction,
specifically floor slabs, roadways, pavements and other flat
surfaces. Generally the setting and hardening of mortar is
retarded when ASTM class F fly ash is added to it. However,
ASTM class C fly ashes have shown both rapid and delay
setting of concrete depending on their properties and the
quantity used. The setting behaviour can be more readily
modified for concrete when chemical admixtures such as
water reducer, superplasticiser, retarder, or gypsum are used
in mixtures containing fly ash. Studies involving chemical
admixtures are detailed by Naik and others (2001b) and Payá
and others (2001a).
The setting time of concretes using fly ash from South
African power stations to replace 15% Portland cement has
been shown to increase to 30–60 minutes above that of
concrete without fly ash. A 30% replacement increases it by
two to three hours. Temperature has the greatest influence on
the setting times of both Portland cement and fly ash
concrete. Differences between use of selected and classified
fly ash led to the suggestion that the retardation could be due
to the presence of trace elements in fly ash. One study
concluded that boron was the most likely trace element
responsible for the retarding effect on the setting time due to
some fly ashes in concrete (Krüger, 2003).
Two major factors affecting the function of fly ash as
pozzolan in structural concrete are fineness and the unburnt
carbon residue. The finer the fly ash and the lower the carbon
30
content, the better is the quality of the fly ash. Both greater
fineness and a low carbon content reduce water demand.
Finer fly ash improves the performance of the concrete to
sulphate attack. A lower carbon content in fly ash improves
the efficiency of chemical admixtures in the concrete,
especially those governing air entrainment. Typical fly ash
has a mean particle diameter in the range 15–35 µm.
Specialised air classification systems can reduce this range to
2.5–4.0 µm. Technology is now available to reduce the
carbon content of fly ash to about 2% (Ravina, 2003). The
carbon content must be less than 3% to make a valuable
cement additive (Ozdemir and others, 2001).
The addition of fly ash to a concrete mix as aggregate
replacement for sand is described by several authors (see
Agarwal and others, 2003; Corinaldesi and Moriconi, 2001;
Ishiga and others, 2003; Naik and Chun, 2003b; Sridhar and
others, 2003).
There are many different requirements for using fly ash in
concrete and some of these are discussed in Section 4.1. The
production and use of fly ash in concrete is detailed in the
handbook by vom Berg and others (2004) and some
examples are included here. The CD available from the South
African Coal Ash Association provides monographs on the
research and development of the utilisation of fly ash in
concrete (Krüger, 2003). Partial substitution by fly ash in
concretes bring substantial engineering (see Section 4.2) and
environmental (see Section 4.3) benefits. Issues which may
hinder utilisation of fly ash in concrete include inadequate
marketing, transport, storage, carbon or ammonia in ash,
effects from cofiring and the fate of heavy metals, especially
mercury (see Sections 4.4.1–4.4.6).
4.1 Requirements for use of fly ash
Specifications for use of fly ash in concrete vary considerably
but there is a trend towards unifying standards. For Europe,
factors required by DIN EN 450 for use of fly ash in
concrete, as well as the test frequencies in quality control are
summarised in Table 8. Frost resistance of concrete is
expected to decrease with an LOI above 10% (Miskiewicz
and others, 2003). The revision of this standard will permit
three categories of LOI as shown in Table 8. South European
countries which are not prone to freezing temperatures in
winter may be allowed to use fly ash with higher LOI
whereas Central European countries where freezing occurs
may keep to the present limit of 5.0 or category B (Vale and
others, 2003). In the UK, the fineness permitted under BS
3892 for concrete should be <12% retention on the 45 µm
sieve and a maximum loss-on-ignition (LOI) of up to 7%.
Moisture content is limited to 0.5% but BS EN 450 does not
require a water reduction (Sear, 2001; UKQAA, 2000).
McCarthy (2003) reports on a laboratory study to investigate
the effect of using BS EN 450 fly ash instead of BS 3892 on
concrete in the UK. The results show that the use of coarser
fly ash has a small effect on strength characteristics, causing
IEA CLEAN COAL CENTRE
 Concrete

Table 8 Requirements for fly ashes in concrete according to DIN EN 450 in Europe (Miskiewicz and others,
2003; Vale and others, 2003*)

Parameter Requirement Test frequency

a Chemical requirements
Loss-on-ignition, % A maximum 5.0 daily
proposed future range* B 2.0–7.0
proposed future range* C 4.0–9.0
SO3 maximum 3.0 monthly

Cl maximum 0.1 monthly

Free CaO maximum 2.5† weekly

b Physical requirements

Soundness, mm‡ maximum 10 weekly

Fineness, wt%§ maximum 40 daily

Fineness variation, wt% ±10¶ daily

Activity index, %
after 28 days minimum 75 twice monthly
after 90 days minimum 85 twice monthly
Density variation, kg/m3 ±150¶ monthly
* current status of proposed future categories of LOI
† fly ash with amount of free CaO >1.0 but <2.5 wt% must comply with the requirements for soundness
‡ required only if amount of free CaO >1%
§ mass proportion of ash retained when wet sieved on a 45 µm sieve
¶ average value as declared by the producer

Table 9 Requirements for fly ash in concrete according to JIS A 6201 in Japan in 1999 (Nagataki and
others, 2001)

Fly ash Class-I Class-II Class-III Class-IV

LOI, % 3.0 5.0 8.0 5.0

Fineness, % on 45 µm sieve or 10 40 40 70
Blaine method, cm2/g 5000 2500 2500 1500

Flow ratio, % lower limit 105 95 85 75

Pozzolanic activity index, % 28 days 90 80 80 60

91 days 100 90 90 70

Density, g/cm3 lower limit 1.95 1.95 1.95 1.95

SiO2, % lower limit 45.0 45.0 45.0 45.0

Moisture content, % upper limit 1.0 1.0 1.0 1.0

Fineness variation*, cm2/g lower limit ±450 ±450 ±450 ±450

% lower limit sieve residue ±5 ±5 ±5 ±5

* average of ten continuous samples, warranty sample set between user and supplier

minor reductions. These could be accommodated by slight
adjustment to the mix proportions and a method to carry this
out was developed. It was found that at equivalent strength,
other engineering properties and aspects of concrete
durability were not affected for the range of BS EN 450 fly
ashes tested.
The Japanese standard for fly ash in concrete (JIS-A 6201)
was revised in 1999 to classify four grades of fly ash and
promote its utilisation (see Table 9). Class I fly ash is a finer
grade than the former class II fly ash. Class III ash with high
LOI is produced by certain combustion conditions and this
grade promotes use of fly ash from such boilers. The coarse
class IV fly ash includes a high percentage of non-spherical
particles and may find applications as grouting material or to
supplement sand (Nagataki and others, 2001). The Japanese
standard has a basis similar to the US ASTM C618 to cover
different types of fly ash (Roof, 2001).

Cement and concrete – benefits and barriers in coal ash utilisation 31

Concrete

In the USA, the existing standard specification for 100% coal
fly ash in concrete, covered by ASTM C618 (see Table 10),
relates to class F and C fly ashes (Dockter and Eylands,
2003). High-calcium ASTM class C fly ashes are relatively
finer than class F fly ashes (Naik and Chun, 2003b) and the
LOI is specified at 3–5% for use of fly ash in ready-mix
concrete. Only fly ashes that meet these specifications can be
used as a stand-alone product to replace up to 50 wt% of the
cement in a concrete mix (Haverland, 2004).
In India IS 456-2000 permits the use of fly ash as a mineral
ingredient and defines fly ash specifically as conforming to
Grade I of IS 3812. This can be used as part replacement for
Portland cement provided the blending is uniform. Another
standard is IS 1489-1991 Part1-2000 which permits addition
of fly ash up to 35 wt% of total cementitious materials, either
as cement or sand replacement (Agarwal and others, 2003).
The maximum LOI is 12% under the Indian fly ash standards
for use in concrete (Chatterjee, 2003).
Specific fly ashes may be used for special concretes using
rapid hardening cements (Hicks, 2003) and high performance
concretes (Kruger, 2003) offering unique benefits. Fly ash is
also used to make aerated concrete and lightweight concrete
blocks. A block may contain over 80% by-product material but
natural aggregates still account for a significant proportion of
blocks produced (Sear, 2002). Vom Berg and others (2004)
give examples of lightweight concrete, high strength
lightweight concrete and self-compacting concretes, using fly
ash at rates of 50 kg/m3 (13 wt% of cementitious components)
for CEM1 42.5R, 40 kg/m3 (9 wt%) for CEM1 52.5R and
230 kg/m3 (41 wt%) for CEMII/A-LL 32.5R respectively.
Research in the USA indicates that mixing cement with fly ash
and slag cement may offer synergies, yielding a better concrete
at reduced cost (Goss, 2003). Fly ash may sometimes be used
with bottom ash to replace sand rather than cement in
lightweight concrete.
4.2 Engineering benefits
Three properties of fly ash are mainly responsible for its
advantages as a component in concrete:
● ability to combine with free-lime (pozzolanic reaction);
● rounded particle shape;
● reduced water demand.
By combining with free lime, fly ash reduces the risk of
damage due to expansive reactions between the free lime and
certain chemicals, mainly sulphates. This may cause some
reduction in early strength of concrete but can be
accommodated in the mix design. Although concrete
enhanced with fly ash has a lower initial strength than pure
Portland cement it provides higher strength in the long term.
The rounded particles improve the flow properties, aiding
pumpability and workability of concrete when mixed with the
more angular shapes in cement and some aggregates. This
leads to greater compaction and hence more resistance to
attack by aggressive chemicals such as sulphates. This has a
benefit for below ground and marine works, for example fly
ash was used in the concrete for the Cape Town Waterfront
and Aquarium in South Africa to withstand the aggressive
marine environment. Being finer than cement, fly ash fills
voids in concrete normally occupied by water. The reduced
water demand usually helps to avoid segregation and
bleeding in fresh concrete as well as improving strength and
long-term durability (DTI, 2002; Kruger, 2003; UKQAA,
2001a; Walker and others, 2002).

Table 10 Specification for ASTM C618-92a fly ash concrete (Dockter and Eylands, 2003)

Class F fly ash Class C fly ash

Chemical requirements

(SiO2+Al2O3+Fe2O3) minimum % 70 50

SO3, maximum % 5.0 5.0

Moisture content, maximum % 3.0 3.0

LOI, maximum % 6.0* 6.0

Available alkalis as Na2O, maximum %† 1.5 1.5

Physical requirements

Fineness, maximum% retained on 325-mesh sieve 34 34

Strength activity index with Portland cement:
7-day, minimum % of control 75‡ 75‡
28-day, minimum % of control 75‡ 75‡
Water requirement, maximum % of control 105 105

Autoclave expansion, soundness, maximum % 0.8 0.8

* up to 12% may be approved by the user if either acceptable performance records or laboratory tests are made available
† applicable only when specifically required by the purchaser for mineral admixture to be used in concrete containing reactive aggregate and
cement to meet a limitation on the alkali content
‡ meeting the 7- or 28-day strength activity index will indicate specification compliance

32 IEA CLEAN COAL CENTRE

 Concrete

Fly ash reduces the alkali silicate reaction (ASR). This
phenomenon causes premature and severe cracking and is
due to the development of chemical reactions between the
siliceous materials in concrete aggregate and the alkali
hydroxides in cement. The reactive silica in power plant fly
ash combines with the cement alkalis (NaOH and KOH)
more readily than the silica in aggregate. The resulting
calcium-alkali-silica gel is non-expansive, unlike the
water-absorbing expansive gels produced by conventional
alkali-aggregate reactions. Hence the fly ash increases ASR
resistance, improving the ultimate strength and durability
while lowering the cost of the concrete (see Knowles, 2004;
Power Engineering, 2004). For example, 30 wt% PFA in
concrete effectively prevents the reaction occurring
(UKQAA, 2001a) although the amount required depends on
the calcium content of the fly ash. A 15% replacement of
cement with low calcium (<2% CaO) class F fly ash is
considered sufficient to mitigate ASR. However it requires a
25% replacement with class F fly ashes having higher
calcium contents (2–10% CaO). A low addition of fly ash can
increase ASR so it is important to establish the correct dose
(Knowles, 2004). A study by McCarthy (2003) indicates that
both dry and conditioned fly ash is effective in limiting ASR
with little difference in expansions for a wide range of
fineness of the fly ash.
Play and others (2003) present detailed results of a long-term
study of the effectiveness of fly ashes with different alkali
contents to prevent ASR in concrete. Two fly ashes were used
with a low alkali content of 2.12% and the other with a
higher total alkali content of 3.36%. Both had #7% LOI,
#40% retained on a 45 µm sieve, silica, aluminium oxide
and iron oxide totalling $70% and a low calcium content
(class F). The results after five years of testing showed that
the fly ash with higher alkali content also prevented ASR.
The efficiency of the fly ashes to inhibit expansion of the
concrete was influenced by the reactivity of the aggregates.
Use of two reactive aggregates reduced expansion when
using 30% fly ash but the most reactive aggregates (siliceous
limestone) caused expansions, although lower than those of
control concretes without fly ash (see Figure 6). This
suggested it was preferable to use a greater rate of fly ash
replacement ($30%) with highly reactive aggregates.
High calcium fly ashes show variable performance with
respect to sulphate resistance. The ASTM C 1012 mortar bar
expansion test for sulphate resistance was applied by
Shashiprakash and Thomas (2001) to Portland cements with
varying content of calcium and aluminium oxides, high
calcium fly ashes, an ultra fine fly ash and a silica fume
cement. The performance of high calcium ashes could be
improved by addition of small amounts of silica fume (for
example 3–6%) or ultra fine fly ash (for example 8–16%).
The high calcium fly ash appeared to perform well when
blended with a moderate or low tricalcium aluminate (C3A)
cement. It is suggested that these blends provided sulphate
resistance by reducing the permeability of the mortar but not
necessarily its chemical resistance. The mechanisms
determining sulphate resistance are discussed and may
involve not only the CaO content of the fly ash but the ratio
of reactive alumina to sulphate in the cement-fly ash blend.
The alumina content of fly ash is thought to bind chlorides
and reduce its diffusion, improving chloride resistance. The
low permeability of the microstructure hinders migration of
sodium and potassium ions. Finally the lower heat of

concretes with 30% fly ash (av): concretes without ash: control T=active alkali content in concrete
(fly ash with 2.1% and 3.4% total alkali content)
0.20 (1) PR+ av=2.1%
T=3.0 kg/m3
Test with curing at 60°C and R.H.=100%
0.18 (2) PR+ av=2.1%
T=3.5 kg/m3
(11)
0.16 (3) PR+ av=2.1%
(9) T=3.7 kg/m3
0.14 (4) PR+ av=2.1%
(10)
T=3.9 kg/m3
0.12 (5)
(5) PR+ av=2.1%
(7) T=4.4 kg/m3
Expansion, %

(8)
0.10
(2) (6) PR+ av=3.4%
(3) T=3.5 kg/m3
0.08 (4)
(6) (7) PR+ av=3.4%
(1) T=4.4 kg/m3
0.06
(8) PR+ control
T=3.5 kg/m3
0.04
(23) (9) PR+ control
0.02 T=3.7 kg/m3
(10) PR+ control
0.00 T=3.9 kg/m3
(11) PR+ control
-0.02 T=4.4 kg/m3
0 52 104 156 208 260 (23) NR av=2.1%
Age, weeks T=4.4 kg/m3

Figure 6 Expansion of concrete mixtures made with potentially reactive siliceous limestone aggregates,
and non-reactive limestone with 30% fly ash and without fly ash (Play and others, 2003)

Cement and concrete – benefits and barriers in coal ash utilisation 33

Concrete

hydration reduces cracking (DTI, 2002; Kruger, 2003;
UKQAA, 2001a; Walker and others, 2002).
The advantages of using fly ash based, blended cement in
concrete are summarised by Jha and others (2003):
● reduced heat of hydration;
● better workability;
● superior microstructure leading to lower permeability;
● higher long-term strength;
● better performance in aggressive environments;
● higher electrical resistivity reducing corrosion of the
reinforcement.
4.2.1 Strength and workability
The pozzolanic property of EN 450 fly ash to react with
Ca(OH)2 to form durable hydrates in solid matrix with
different cement mixtures is shown in Figure 7. There is a
significant gain in compressive strength over the long term
compared to 100% Portland cement.
In general early age strength is decreased when fly ash
replaces part of the cement, especially for class F fly ash.
Adding fly ash to the concrete mixture without reducing the
cement content, that is substituting for aggregate, generally
increases strength and overall quality at all ages but does not
provide any saving for the cost of cement. On the other hand,
the partial replacement of cement, fine aggregate and water
by fly ash produces early age compressive strengths of
concrete comparable to or greater than Portland cement
concrete containing no fly ash. This is for the case when the
total mass of cement and fly ash exceeds the total mass of
Portland cement used in a comparable mixture with no fly
ash (Naik and Chun, 2003b).
Studies have shown that superplasticised structural as well as
high-strength concretes can be manufactured with high
volumes of class C fly ash for cement replacements in excess
100% Portland cement
+ 20% EN 450 fly ash
60
80% Portland cement
+ 20% EN 450 fly ash
Compressive strength, MPa
of 50 wt%. For high early strength in precast/prestressed
products, the maximum amount of cement replacement by
class C fly ash is about 35 wt% (Naik and Chun, 2003b). One
company in British Columbia, Canada, experimented with up
to 50 wt% cement replacement by fly ash in regular pre-cast
production and achieved adequate early strength (Bouzoubaâ
and Fournier, 2004). High volume fly ash blends (50%, 60%)
with Portland cement can be activated by sulphates (for
example 5% calcium sulphate) to achieve strength
development rates similar to those of Portland cement alone.
Activation of alumina present in the glass phase of fly ash
leads to ettringite formation and contributes to strength at
early ages while the pozzolanic reactions are slow and
contribute to long-term strength (Bhanumarthidas and
Kalidas, 2001). Calcium chloride based accelerating
admixtures have traditionally been used to speed set times
but potential corrosion of reinforcement and embedded
metals should be considered a drawback to its use. A high
volume fly ash cement with 51 wt% fly ash achieved early
strength because the water to cement ratio was reduced to
<0.35 by a high range water reducer. This also helped to
reduce the set time (Copeland and others, 2003).
Lean mix PFA concrete was used for airport paving in the
UK. The design incorporated PFA at 30 wt% of the total
cementitious content with Portland cement, and limestone for
coarse and fine aggregate with sand. The concrete showed a
slower rate of gain of strength at early ages. This allowed
cutting of clean movement joints at about 18 hours after
laying. Strength gains continued after 28 days, resulting in
stronger and more durable concrete in the longer term. The
concrete achieved the required flexural strength of 6.9 MPa at
28 days and 8.7 MPa at 56 days. The extended set time
allowed the concrete to be properly compacted and finished
even in hot weather. The reduced temperature rise reduced
thermal movements and the risk of cracking
(UKQAA, 2001a).
Since existing practice with fly ash as a cement component in
concrete requires dry ash, stored moist fly ash cannot be used
in the UK. A feasibility study was carried out to examine the
effect of moisture addition on fly ash properties at both low
and high levels and its use in concrete. It was found that
moisture in fly ash has little effect on concrete performance

50
100% Portland cement as long as the water in the ash is taken into account in the
water content of the concrete mix. Full-scale tests are
currently in progress (McCarthy, 2003).
40
80% Portland cement
+ 20% inert filler Setting characteristics are generally retarded by addition of
30
class F fly ash to concrete mixtures but class C fly ashes
show mixed behaviour. The initial and final set time may
increase, decrease or remain unaffected due to inclusion of
20 class C fly ash. At extremely high cement replacement, above
60 wt%, high dosages of set retarding admixture should be
considered to keep concrete workable throughout the mixing
10 and placing period (Naik and Chun, 2003b).
2 7 28 16
Days In cold weather the set time of fly ash concrete mixtures
increases more and in Atlantic Canada, less fly ash can be
Figure 7 Pozzolanic property of EN 450 fly ash to used for this reason in winter than in summer. In Ontario, up
react with Ca(OH)2 to form durable to 25% fly ash is used in ready-mixed concrete during warm
hydrates in solid matrix (Blondin, 2002) weather in the summer while the proportion decreases to

34 IEA CLEAN COAL CENTRE


about 10–15% during the colder months of the year
(Bouzoubaâ and Fournier, 2004). However, this delayed
setting characteristic may be beneficial in some applications.
As noted in Section 3.1.2, mainly class C fly ash can be used
to make rapid hardening hydraulic cements (MRT Cements,
TX, USA) at over 80% fly ash substitution. When concrete
paving mixes are based on these cements, the roads, bridges,
or runways can be opened to traffic in four hours after
pouring the concrete. This has obvious advantages for high
density traffic areas. The ASTM C 78 flexural strength of
3.5 MPa (500 psi) is attainable in four hours and the final set
time is adjustable between 15 to 50 minutes by varying the
accelerator and retarder. This can be laid in one step with all
ingredients going into the final screw conveyor of the mixer
but a two-step process is preferable for transport by trucks. In
this case the water, any wet additives and accelerator are all
added at the pour site. Further details of this and other
applications for rapid hardening, class C fly ash cements are
described by Hicks (2003).
Use of large quantities of class F fly ash (up to 50 wt% of
Portland cement) in concrete masonry products was
investigated by Naik and others (2001a). Early strength
development is required for bricks. At 7 days, all brick
mixtures with up to 30 wt% fly ash exceeded the
compressive strength requirement for grade N bricks
(24 MPa); and the 50 wt% fly ash bricks exceeded the lower
requirement for grade S bricks (17 MPa). At 91 days, all
brick mixtures met the grade N strength requirement.
Concrete blocks met the ASTM strength requirement of
13 MPa at the age of 7 days, except at 40 wt% fly ash
replacement. Test results for paving stone mixtures (up to
30 wt% fly ash) did not meet ASTM requirements but were
sufficient for use in normal construction work. Inclusion of
fly ash did not cause significant reduction in density of the
products and reduced drying shrinkage.
In India class C and class F fly ashes were tested as partial
replacement for cement in various concrete mixes used in
hydraulic structures. The compressive strength of concrete
increased with up to 15 wt% replacement by class C or class
F fly ash and decreased at higher percentages in all grades of
cement and concrete investigated (Grades 43 and 53; and
M15, M20, M25 respectively). The increase in strength was
greater for samples made with class C fly ash than those
using class F fly ash (Mathews and others, 2001).
The extended set time of fly ash in concrete allows the
concrete to be properly compacted and finished without
problems even in the hottest of weather, although the delay in
set is greater at lower temperatures. At a mix temperature of
25°C, the set time may be extended by one hour when using
a fly ash content of 30 wt% and by two hours for 50 wt%
substitution. Even at high mix temperatures, fly ash does not
appear to contribute positively to temperature rise until
20–30 hours after casting and may retard the heat evolution
of the Portland cement component prior to this time. Other
workability benefits of using fly ash in concrete included
reduction in bleeding and segregation, reduction in cracking
and increased durability after 28 days. Such characteristics
indicated that fly ash should be used in concrete road
Cement and concrete – benefits and barriers in coal ash utilisation
Concrete
construction in India as long as the manufacture has
predictable and reliable results from use of quality assured fly
ash. This results in the double economic benefit of giving
lower cost concrete in construction and lower maintenance
cost concrete throughout its life (Watkins, 2003).
Several examples are given by Bouzoubaâ and Fournier
(2004) of structures in Canada which have benefited by use
of fly ash. These include the Park Lane Hotel/Office
Complex and Purdys Wharf Development in Halifax which
were constructed with structural elements containing 56 wt%
of cementitious material by fly ash. Concretes containing
50 wt% of Type CI fly ash were used for columns, walls and
suspended slabs in the computer studies centre at York
University in Toronto, achieving the specified strength of
30 MPa. Dams have been built using roller compacted
concrete with over 50 wt% fly ash, for economic reasons or
to decrease the heat of hydration. Roller compacted concrete
was also used at a high replacement rate for cement at the
Platanovryssi dam in Greece. Brown coal fly ash (225 kg)
was used with a low Portland cement content (50 kg) within
the dam structure. The fly ash did not conform to any
standard and had to be milled and hydrolysed to make it
suitable for the application (ECOBA, 1999). Practical
experience in Germany of roller compacted concretes for
roads suggests that a ratio of cement:fly ash of around 2:1 to
3:2 gives the required binding strength (vom Berg and others,
2004).
Self-compacting concrete, developed in Japan, has been
successful in many countries where there is a shortage of
skilled workers for placing and consolidation of concrete
structures. The concrete flows into the form-work, without
segregation, to fill uniformly and completely every corner of
it by its own weight without application of vibration or other
energy during placing. Large volumes of fly ash, partially to
substitute for cement and partially as filler, can be used since
self-compacting concrete requires considerably more fines
compared to traditional concrete. Alternatives such as silica
fume are much more expensive than fly ash. Mixture
proportions containing 45 wt% and 60 wt% of fly ash
complying to EN 450 from Fusina power station in Italy were
tested. At 28 days the compressive, flexural and indirect
tensile strengths were improved over the normal mix, slightly
more for the 45 wt% fly ash concrete and continued to
increase with age. Bond to steel and concrete was also
improved, probably due to the cohesive nature of the
self-compacting concrete (Khurana and Saccone, 2001).
High performance concretes are usually produced using
expensive silica fume and selected high quality fly ash and
aggregates. The high production costs have limited the
application of high performance concrete with 28-day
strength of 60 MPa which would be acceptable for ordinary
structures. More than 80% of concrete produced is applied in
ordinary structures, traditionally using concrete with
compressive strength in the range of 25–35 MPa. Hence a
high volume application of high performance concrete could
be anticipated if production costs could be reduced. Research
work in Portugal focused on using locally received fly ash
and available crushed granite aggregates. The amount of fly
ash was tested at 0, 20 wt%, 40 wt% and 60 wt% cement
35
Concrete
replacement in mixtures with different quantities of total
binder (400 kg/m3, 500 kg/m3 and 600 kg/m3). To reduce
costs superplasticiser (naphthalene sulphonate formaldehyde
condensates) at only 0.5 wt% of the binder was adopted
(Camões and others, 2003).
Compressive strengths of 60 MPa at 28 days and 65 MPa at
56 days could be achieved using 500 kg/m3 binder and up to
40 wt% cement replacement. Increasing the binder content to
600 kg/m3, increased the compressive strength. Adding
60 wt% fly ash weakened the concrete considerably in terms
of compressive strength but the workability was improved
when compared to the control concrete mix. Even these
mixtures enhanced the performance with regard to
environmental and economic aspects. The cost of the fly ash
was about 20% of the cost of cement. Hence an increase in
the proportion of fly ash to 40 wt% decreased costs by 32%
and using 60 wt%, the costs were almost halved (Camões and
others, 2003).
High strength concretes (CEM 1 32.5R) with a greater
proportion of sand have been developed in Germany where
some areas in the north have a surplus of fine sand
(DIN 4226 part 1). Fly ash according to DIN EN 450 is a
good filler for the cavities between the sand grains in
proportions $80 kg/m3 (20 wt% of cementitious
components). The addition of fly ash has a positive effect in
concretes rich in sand through a reduction in the air content
of the fresh concrete. The pozzolanic reactions of fly ash
improve the durability of the concrete. Self-compacting
concretes with high volumes of sand (65–80% by volume of
aggregate) were produced by using 80–160 kg/m3 fly ash
(20–33 wt%) with cement to optimise the interstices of the
coarse particles which were reduced from for example
50 wt% to >20 wt%. This improved the properties of the set
concrete at higher strength classes than C 20/25. Examples of
such concretes, for which there should be great demand, are
given by vom Berg and others (2004).
Ultra fine fly ash is used instead of silica fume to make high
performance concrete with dense matrix and superior strength.
The main advantage of this fly ash is its ability to disperse in
the concrete, requiring either less water and/or superplasticiser
which also reduces the cost. The ultra fine fly ash from
Lethabo power station, South Africa, with an average particle
size of 4 µm and a top size of 20 µm, provides an ideal product
and is marketed as Super-Pozz®. As shown in Figure 8, the
development of compressive strength was equal to or better
than in concrete specimens with no extender or silica fume for
concrete containing 400 kg/m3 total binder, that is cement with
or without extender (Kruger, 2003).
Fly ash with other materials as cement replacement in high
performance concretes have recently been studied in India.
Mixes of fly ash with silica fume are under investigation.
Silica fume is 100 times finer than fly ash and a very reactive
pozzolan. This increases the rate of gain of strength and
improves impermeability of concrete at a much earlier age
than a fly ash mix. Mixtures of 30% fly ash and 5 to 10%
silica fume with Portland cement were tested by Rao and
Rafeeq (2003). The addition of silica fume resulted in an
average increase of 49% at the 28-day strength. Seshasayi
36
120
100
Compressive strength, MPa
80
60
40
20
0
1 3 7 28 56 90
Days
nil 10% silica fume 10% fly ash 15% fly ash
Figure 8 Development of compressive strength for
concrete specimens of equal slump
containing ultra fine fly ash (Super-Pozz)
or silica fume as extender (Kruger, 2003)
and others (2001) tested cement replacement by 10%, 20%,
30% and 40% fly ash from Ramagundam power station in
Andhra Pradesh and 4%, 8%, 12%, and 16% silica fume
from a local ferro-alloy factory. The 28-day and 56-day
strengths were determined. The highest fly ash replacement
of 40% and 16% silica fume (56% cement replacement)
increased the 28-day compressive strength by 10%. However,
a maximum increase of 43% in the 28-day compressive
strength to 82 MPa was observed at 32% cement replacement
with 20% fly ash and 12% silica fume. This mixture also
gave the highest 56-day compressive strength, at 85 MPa.
Strengths as high as 80 MPa were achieved at 120 days by a
structural concrete containing up to 35 wt% of fly ash and
silica fume in Bankers Hall West Tower, Calgary, Alberta,
Canada. (Bouzoubaâ and Fournier, 2004).
The use of ground granulated blast furnace slag as a
hydraulic binder for concrete showed lower strength
development than a 33 wt% fly ash cement concrete at 3 days
but achieved a higher compressive strength at 28 days of
about 67 MPa compared to 50 MPa for the fly ash cement
(Novac, 2003; 2004). Mixtures with 25% fly ash and 40%
ground granulated blast furnace slag as partial cement
replacements in high performance, reinforced concrete beams
were compared to normal Portland cement concrete at the
Structural Engineering Research Centre, Chennai, India. The
fly ash was class C from lignite. The compressive strength
for the fly ash based mixture exceeded 35 MPa at 3 days
although it was lower than that of normal Portland cement
concrete. It reached almost the same compressive strength at
56 days. The flexural strength and split tensile strength were
also reduced a little until 56 days. The stiffness was not
affected by use of fly ash or ground granulated blast furnace
slag and there was little effect on cracking. The bond
characteristics required further investigation. The replacement
materials avoided problems incurred by using large amounts
of Portland cement to reach high strength (Gopalakrishnan
and others, 2001).
IEA CLEAN COAL CENTRE

The ash from rice husks is siliceous with a cellular
microstructure and acts as a superpozzolan, giving early
strength to concrete produced with ASTM type III Portland
cement. Even without a superplasticiser, high volume fly ash
concrete mixtures of 35–40 MPa, 28-day strength could be
produced. The rice husk ash also reduced the permeability
considerably (Bhanumathidas and Kumar Mehta, 2001;
Bhanumathidas and Kalidas, 2001). In addition to rice husk
ash, other pozzolanic wastes, such as ash from sewage
sludge, silica fume and spent fluidised bed catalyst from a
petrol refinery, may be used to improve the workability of fly
ash/Portland cement concretes. These were tested at rates of
10% or 20% with 20% fly ash. The mixture with 20%
sewage sludge ash and 20% fly ash was considered to be
favourable for strength development (Payá and others,
2001a).
New research indicates that a tri-blend of cement, fly ash and
slag cement may offer increased cost savings as well as better
concrete performance. A combination with 50% cement, 30%
slag and 20% fly ash of total cementitious components works
well. This results in concrete with less water and a slower
curing time, giving a higher 28-day strength than other
cement alone or with either fly ash or slag, without affecting
next-day strength or set performance. The tri-blend had a
lower 7-day strength than for cement only but it was higher
than for 35% slag or 20% fly ash mixes. The concrete has
proved successful in the residential market in the USA and is
now acceptable to structural buyers (Cement Americas,
2003).
Fibre-reinforced concretes benefit from use of fly ash.
Strain hardening may be promoted by fly ash in hybrid
fibre-reinforced cement composites due to its much finer
particles than ordinary Portland cement. When about 50% of
the cement was replaced by fly ash, in a composite with 1.5%
steel fibres and 0.5% polyvinyl alcohol microfibres, the
composite had high flexural strength, high flexural toughness
and high ductility. Further optimisation of the material
properties could be achieved by tailoring the length and
diameter of both the fibres (Ramanalingam and others, 2001).
Steel and glass fire-reinforced concretes have been used in
Germany for around 25 years. They are especially useful for
industrial floors. Contrary to current recommendations from
fibre producers, the amount of cement in such concretes can
be reduced by 80 kg/m3 of fly ash. Examples are given of
concretes using 80–200 kg/m3 of fly ash (18–40 wt% of
cementitious components), according to DIN EN 450. The
industrial floors are more dense and free of cracking due to
the reduced heat of hydration. A special application called
SIFCON (Slurry Infiltrated Fibre CONcrete) is useful to
improve the base of materials which are deleterious to water.
A high strength steel fibre bed is covered and finished with a
layer of fly ash mortar using up to 70 wt% fly ash (vom Berg
and others, 2004). A specially designed steel fibre underwater
concrete with a fly ash content of up to 280 kg/m3 was used
at the Potsdamer Platz area in Berlin (ECOBA, 1999).
Fibre-reinforced concrete artificial supports, based on
40–85% coal utilisation by-products, have been demonstrated
for use in underground mines. These give a considerably
Cement and concrete – benefits and barriers in coal ash utilisation
Concrete
better performance than wooden posts (Chugh and others,
2003).
Finally Rostami and Brendley (2003) report on the benefits
of alkali ash material in which 40–95% class F fly ash is used
as cement to bind sand, stone and fibres to make concrete.
This concrete has potential applications now in blocks, pipe,
median barriers, sound barriers and overlaying materials and
in the future may find use in high strength construction
products, such as bridge beams, prestressed members,
concrete tanks and highways. The compressive strength of
such concretes reached a maximum over 100 MPa, equal to
that of Portland cement concrete, after 24 h curing at
temperatures above 40°C. Activating chemicals may also be
used to increase the strength.
Fly ash as a substitute for aggregate in concrete is under
investigation by several authors. In India, Mathews and others
(2001) studied the effects of fly ash on strength and
durability of hydraulic structures with various grades of
cement and concrete. They found the compressive strength of
concrete improved with up to 20 wt% sand replacement by
both class C and class F fly ashes for all grades of cement
and concrete tested (Grades 43 and 53; and M15, M20, M25
respectively). The compressive strength was higher for the
sand replacement than for the cement replacement in the
study.
Fly ash has recently been investigated at greater rates of
partial replacement for sand fine aggregate in concrete by
Sridhar and others (2003). The fly ash was obtained from
Vijayawada thermal power station, India, and substituted for
sand at 25 wt%, 50 wt%, 75 wt% and 100 wt% in 1:3:4
concrete (Portland cement, river sand, crushed stone
aggregate). The 50 wt% replacement rate was most
advantageous since the compressive strength, tensile strength,
flexural strength, modulus of elasticity all reached maxima
which were substantially greater than plain concrete for both
7 and 28 days curing. The improvement in maximum strength
was attributed to better packing and a ball bearing effect
produced by the spherical fly ash particles and interspatial
forces which influence both the hydration and packing
efficiency of concrete. Improved deflocculation of cement
agglomerates resulted in increased production of lime which
stimulated pozzolanic activity in the fly ash. The strength was
also increased as a result of increased cohesiveness, total
absence of bleeding and decreases in voids. The high
modulus of elasticity was achieved due to a considerable
portion of unreacted fly ash acting as glassy spherical fines to
fill the voids in the fine aggregate. In addition the cost of
replacing sand by 50 wt% with fly ash decreased by 3.23%.
Lightweight or cellular concrete may contain fly ash used as
aggregate. Most fly ashes reacted adversely with the typical
foam reagents used to produce cellular concrete, especially
ashes with higher carbon contents. Recently developed foam
from an engineering firm in Colorado, USA, allows the use
of coal combustion products in virtually any mix design,
depending on the application, at 30% to 90% of the total
solids content. The cellular concrete using coal ash is lighter
in weight and has greater heat resistance. There are
considerable cost benefits since the coal combustion residues
37
Concrete
cost less than half of the cement and commercial aggregates
they replace (Colaizzi, 2003). In Japan a lightweight
aggregate was developed to reduce costs and improve
earthquake resistance of concrete. Fly ash is mixed with
bentonite and a foaming agent, followed by pelletising and
baking. The aggregate has a dry specific gravity <1.25. A
pilot plant of 0.3 t/h scale is being used to test the product
(Harada and others, 2000).
In Israel, Nisnevich and others (2003) used binary mixtures of
fly ash as additive and bottom ash as aggregate in lightweight
cement. The fly ash was low in lime (ASTM C618, class F). It
was applied in various ratios by volume to the total volume of
fly ash and cement from 0 to 0.8. The fly ash improved the
properties of the concrete by reducing the volume of air voids
in the fresh concrete. This resulted in increased density and
compressive strength of the hardened concrete and gave a more
effective use of the combined by-products.
4.2.2 Durability
Corrosion of reinforcing steel in concrete bridges and
highways has become a considerable economic and social
burden for many states and safety issue to taxpayers in the
USA. The processes and its control are described by
Bargaheiser and Butalia (2003). Mineral components can be
used to enhance the corrosion control potential of concrete by
reducing permeability. Designers focus on maintaining the
alkalinity at pH 12–13 to sustain the steel in a non-corrosive
environment. This is amply provided by the Portland cement
which may contain up to 15–40 wt% of calcium hydroxide.
Fly ash tends to be less alkaline so that designers do not
readily regard it as a means of mitigating corrosion. However,
fly ash improves the density of concrete, its pozzolanic
reactions reduce permeability, and this therefore more than
compensates for the slightly lower pH. It is not uncommon to
find fly ash concrete with a chloride diffusion coefficient
100 times less than a control Portland cement after 20 years
of curing. Thus fly ash can improve durability such as alkali
attack, sulphate attack, chloride and CO2 ingress, and
corrosion in concrete.
In Alberta and Atlantic Canada, many quarries contain
sediments which are alkali-aggregate reactive, causing ASR. In
this case the use of fly ash or other supplementary cementing
materials becomes mandatory to reduce the risk of premature
deterioration of concrete (Bouzoubaâ and Fournier, 2004).
The amount of cement replacement should be 40 wt% or less
in order to achieve satisfactory durability of fly ash concretes,
especially scaling resistance. Freeze and thaw durability of
concrete is normally improved by air entrainment. Studies
have shown that use of fly ash in concrete increases the
requirement for air entraining agent. This is thought to be
primarily due to the presence of unburnt carbon or increased
fineness of fly ash compared to cement and applies to use of
either class C or class F fly ash at 25 wt% cement
replacement rates or higher. Class C fly ash concrete
demanded less air entraining agent than concretes with
class F fly ash. Various factors such as the type of agent and
cement, concrete temperature, consistency and use of other
38
mineral additives with fly ash are known to influence air
entrainment. Hence this should be optimised for each
constituent in the concrete, including fly ash. Since the
permeability of properly cured class C fly ash concretes is
lower than reference concretes with no fly ash, fly ash
concretes are expected to outperform Portland cement
concretes for freezing and thawing resistance. However, not
enough is currently known about the long-term strength and
durability properties of class C fly ash in high volume fly ash
concretes (Naik and Chun, 2003b).
Increased fly ash content in cement has been found to
improve concrete performance when exposed to de-icing salts
in highway structures. This is due to increased chemical
binding of chlorides and improved concrete microstructure
(McCarthy, 2003). Frost resistant concretes in Germany are
normally produced without air entrainment. Sufficient frost
resistance is achieved through low porosity and high strength
although air entrainment improves it. Concretes containing
fly ash, reducing the minimum cement content to 270 kg/m3,
are permitted. There is also a need for concretes to withstand
use of de-icing materials in addition to frost, on roads,
bridges, and tunnels. A reduction in minimum cement content
and equivalent water:cement ratios are not permitted for use
of fly ash in low water saturated (XF2) and high water
saturated (XF4) concretes. This issue is under investigation
(vom Berg, 2004).
The use of fly ash in self-compacting concrete
(see Section 4.4.1) in Italy proved beneficial in freeze and
thaw tests (ASTM C666). After 300 cycles, the relative
dynamic elastic modulus (%) of the concrete was greater for
mixes with fly ash addition (Khurana and Saccone, 2001):
Fly ash, wt% %
0 79
45 103
60 111
The masonry products containing class F fly ash
(see Section 4.4.1, Naik and others, 2001a) were tested for
freeze and thaw. The weight loss was quite small (<1% at
100 cycles) for brick, block and paving stone mixtures
containing up to 30 wt% fly ash for Portland cement, meeting
ASTM C 1262 but not for bricks and blocks at 50 wt% fly
ash substitution. This limits the bricks to interior use in cold
climates for 50 wt% fly ash. Similarly, blocks with over
30 wt% fly ash could only be used for interior walls in cold
climates. All other mixes would be suitable for use on
exterior walls in cold climates. Use of high volume fly ash
concrete in Canada similarly requires long-term field
demonstrations of durability before a widely based adoption
of such a technology occurs (see www.ecosmart.ca and
Bouzoubaâ and Fournier, 2004).
Durability when exposed to sulphates or chlorides is an
important requirement for concrete since these ions are
commonly present in ground water, seawater, sewerage,
industrial spillage and even in rainwater around industrial
areas. The less permeable nature of concrete made with fly
ash addition renders it less prone to chemical attack than
concrete prepared only with normal Portland cement.
IEA CLEAN COAL CENTRE

Australian research (Khatri and others, 2003) examined the
influence of the type of sulphate and pH of attacking solution
on the expansion and compressive strength of mortars
containing different binders. The main chemical processes of
sulphate attack on concrete are:
● recrystallisation of ettringite (Ca6Al2O6(SO4)3.32H2O),
causing expansion, cracking and disruption;
● formation of gypsum (Ca2SO4-2H2O); and
decalcification of calcium silicate hydrates which are
associated with loss of strength and mass.
High pH and the availability of alumina in solution are
required for recrystallisation of ettringite while lower pH and
a supply of calcium favour the formation of gypsum. Use of
Portland cement with low alumina is helpful while fly ash
lessens calcium hydroxide and increases calcium silicate
hydrate and is therefore effective against formation of
gypsum. The Australian fly ashes tested enhanced the
sulphate resistance of concrete by reducing expansion and
improving strength retention characteristics. This was
applicable for a range of sulphate solutions kept at different
pH and type of cation. The 40 wt% fly ash mix exhibited
both low expansion and favourable strength development in
sulphate solution over different pH values. The 20 wt% fly
ash mix showed much less expansion than Portland cement
mixes but exhibited considerable strength loss. But as the pH
was lowered, its behaviour relative to Portland cements
improved. For optimal sulphate resisting characteristics, it
was important to use appropriate concrete mix design
parameters such as water to binder ratio, fly ash replacement
percentage and fly ash source. Evaluation of sulphate
resistance of cementitious binders might require the use of
multiple criteria, for example expansion and strength
obtained over reasonable exposure periods in appropriate
sulphate solutions (Khatri and others, 2003).
The service life of fly ash concrete in a marine environment
was compared to that of normal Portland cement concrete by
Khatri and Sirivivatnanon (2003). Three grades of concrete
(20, 40 and 50) were prepared with normal Portland cement
and with 30 wt% substitution of the cement by fly ash and
cured for 28 days. A model for service life evaluation was
based on Fick’s second law of diffusion and used to calculate
the service life from the chloride ion penetration resistance
after one year of immersion in 3% NaCl solution. The service
life of fly ash concretes was found to be significantly higher
than that of normal Portland cement concretes.
The optimum fly ash content in concrete based on durability
and on cost was studied by Khatri and Sirivivatnanon (2001).
The samples of concrete prepared with15 wt% and 30 wt% of
cementitious material as fly ash were immersed in 3% NaCl
solution for a period of 33 months and analysed for chloride
penetration. Similar samples were tested for sulphate
resistance according to ASTM C1012 and expansion of
mortar prisms measured after immersion in 5% Na2SO4.
Increased fly ash content reduced the chloride diffusion
coefficient and the expansion in a sulphate environment.
Other studies showed that up to 40 wt% fly ash substitution
would give the best resistance to both chloride and sulphate.
The study of high performance concretes in Portugal
Cement and concrete – benefits and barriers in coal ash utilisation
Concrete
(see Section 4.2.1) concluded that 40 wt% fly ash gave the
highest electrical resistivity and a low coefficient of chloride
ion diffusion. This suggested that the fly ash concrete was
especially suitable for environments that would promote
degradation of reinforced concrete due to chloride ion
penetration (Camões and others, 2003).
In Sydney, Australia, the price of normal Portland cement
was 160 $/t and fly ash 50 $/t with 0.8 $/L for chemical
admixture. The optimum fly ash content based only on cost
was about 28 wt% for a grade 20 concrete and about 10 wt%
for a grade 50 concrete. For a benign environment, the
optimum fly ash content was that obtained from cost only but
for aggressive environments, the optimum fly ash content was
the highest tested.
A 30 wt% fly ash blended cement concrete was specified for
the Malaysian-Singapore Second Crossing to extend the
service life of structures in the marine environment. The fly
ash concrete showed better resistance to chloride penetration
than normal Portland cement of similar strength grade and
better resistance to sulphate solution (Kidav and others,
2001).
The tests on fly ash in self-compacting concrete
(see Section 4.2.1) indicated excellent resistance of fly ash
mixes to aggressive water-borne agents such as chlorides and
sulphates. They showed that maximum water penetration (in
mm, by ISO 7031) was lower for fly ash mixes than normal
concrete (Khurana and Saccone, 2001):
Fly ash, wt% mm
0 23
45 3
60 6
The specification for CEM I 32.5R concrete used in the
acidic regions of a cooling tower at Niederaußem, Germany,
contained 75 kg/m3 fly ash in 350 kg/m3 cementitious
components (21 wt%) and 128 kg/m3 water. In durability
tests with exposure to sulphuric acid at pH=2 over six
months, this did not show the pitting from the acid which was
evident on the normal concrete used for cooling tower skins
(ECOBA, 2004; vom Berg and others, 2004).
The alkali ash material concretes discussed by Rostami and
Brendley (2003), in which 40–95% class F fly ash is used as
cement to bind sand, stone and fibres to make concrete, have
shown greater resistance to attack from acids (100% acetic,
20% nitric, hydrochloric and sulphuric acids) than silica fume
Portland cement concretes. This is because the fly ash only
contains a small amount of CaO and is therefore not
vulnerable to low pH environments. Research in the Czech
Republic has studied alkali activated class F fly ash as a
means of improving the resistance of concrete to chemical
attack by acids such as sulphuric, nitric, hydrochloric and
organic acids. The mechanism for improving acid resistance
is considered to be a framework of polymeric Si-O-Al
bonding which is more durable in acidic media than
structures based on foiled sheets of vulnerable calcium
silicate hydrates which are dissolved by acidic solutions in
normal Portland cement (Allahverdi and Škvára, 2001).
39
Concrete
An airport hangar in Central Texas, USA, needed an
impermeable concrete floor so that potential spillage of fuel
and chemicals would not damage the floor prematurely. A
high volume fly ash mix of 50 wt% class F fly ash with an
equal proportion of Portland cement gave the required design
strength and durability (Copeland and others, 2003).
Naik and Chun (2003b) report on chloride penetration
resistance studies of concretes containing ASTM class C
and F fly ashes, some with containing silica fume. The
ASTM C 1202 test results for chloride ion penetration at ages
of 91 days and beyond were designated very low for
concretes with 40 wt% class F, and 10, 20, 25 and 50 wt%
class C fly ashes as well as for the control mix with no fly
ash and for the mixes containing 8 and 11 wt% silica fume.
Tests with cement replacements of up to 50 wt% class C fly
ash gave good results with respect to chloride ion penetration.
Those with up to 70 wt% fly ash concrete showed higher
resistance than the no fly ash concrete mixture at the 2 month
age. Variable temperature curing cycles improved the
resistance of concrete to chloride ion penetration and high
performance concretes generally showed decreased chloride
ion penetration with increasing compressive strength and age.
Both class C and class F fly ashes were used to replace
cement and sand in India. The loss in strength from sulphate
attack decreased with increasing cement replacement up to
20 wt%. The sulphate resistance of concrete was higher for
cement replaced concrete than for replacing sand although
permeability was lower for the sand replaced concrete
compared to the cement replaced method (Mathews and
others, 2001).
Marine durability of 15-year-old concrete specimens made
with ordinary Portland cement, slag and fly ash cement were
compared by Mohammed and others (2001b). Type B fly ash
was used at <10 wt% and it satisfied the Japanese standard
JIS R 5213. The slag cement type C showed the best
performance against chloride ingress and corrosion of steel
bars in concrete although the fly ash concrete was better than
ordinary Portland cement for chloride ingress. The fly ash
concrete gave a better performance for steel corrosion at a
water-to-cement ratio of 0.45 rather than 0.55 and with cover
concrete of 40 or 70 mm depth rather than 20 mm. Use of
seawater for mixing the concrete resulted in a gain in early
strength. Similar tests were carried out on cracked concrete
and narrow cracks (#0.5 mm) were found to heal for all
types of cement. This was due to precipitation of calcium
carbonate crystals in the cracks. Corrosion was worse for slag
cement than for the other types of concrete around wider
cracks ($1.5 mm) (Mohammed and others, 2001a).
In Austria, Novac (2003, 2004) reports on the merits of a new
hydraulic binder, Slagstar, which is based on ground
granulated blast furnace slag with gypsum and alkaline
additions. The concrete showed a higher resistance to both
sulphate, acid attack and to chloride corrosion than a 33 wt%
fly ash CEM I 32.5 cement concrete. However, no tests are
reported with higher substitution rates for fly ash in cement
concrete or for mixtures of slag with fly ash. Nevertheless,
competition from such a material may affect the market for
fly ash cement concrete, despite its benefits (see also
Section 4.3) over Portland cement concrete.
40
The bond strength of new underwater, self-consolidating
concrete with old concrete was increased by using 20 wt% of
a class F fly ash and 6 wt% of silica fume or 10 wt% silica
fume and with reductions of the water to binder ratio from
0.47 to 0.41. Tests for compressive strength, adhesion in
slant-shear and residual adhesion of specimens cast in water
were made at 7 and 28 days. The fly ash and silica fume
mixture again exhibited greater adhesion than the concrete
made with 100% cement mixture (Sonebi, 2001).
In Japan, fly ash containing too much unburnt carbon for
high quality applications is being tested for use as
replacement for aggregate, rather than cement, in concrete.
The fly ash had a LOI of 5.6%. It was used for flow type
concretes at 86 wt%, 62 wt%, and for slump type concretes at
42 wt% and 18 wt% of the weight of the cement. The cement
proportion was kept constant at 285 kg/m3, with water to
cement ratio kept constant at 65%. The fly ash substitution
appears to be equivalent to 46 wt%, 38 wt%, 30 wt% and
15 wt% of total cementitious components respectively.
De-salted sea sand and crushed limestone sand were also
used as aggregates. Test specimens were exposed to a marine
environment for one year and others to sea water sprayed
twice a week for 2–3 minutes. Chloride penetration of fly ash
concretes decreased with an increase in the amount of fly ash
added. A rapid chlorine permeability test showed a similar
relationship, especially for longer curing periods. These
trends also reflected the higher compressive strength
development, which increased with the amount of fly ash
used, compared to the control concrete. There was no
corrosion of steel reinforcement in the concrete (Sorn and
others, 2001).
Further examples of successful applications of concretes with
up to 40% fly ash are described by ECOBA (1997). These
include the Torness nuclear power station, Scotland, an
underground railway tunnel in Vienna both of which required
impermeability as well as sulphate resistance as well as use
of wet fly ash from stockpiles in France for the binder in
highly durable concrete for the Puylaurent dam.
4.3 Environmental benefits
Greenhouse gas emissions reduction and avoidance of
primary aggregates are the main environmental benefits of
substituting some cement by fly ash in concretes.
4.3.1 CO2 reduction
As noted in Section 3.2, every tonne of cement replaced with
fly ash is estimated to avoid the emission of approximately
1 t of CO2 to the atmosphere (Cembureau, 1999; Deju, 2003;
Walker and others, 2002). For example, through ash
utilisation in the cement industry, the joint venture between
Lafarge and ScotAsh was able to avoid extraction of around
600 kt of primary aggregates and was on target to prevent
40 kt of CO2 emissions in 2003 (DTI, 2002; McCaffrey,
2003).
The lean mix fly ash concrete for airport paving in the UK
IEA CLEAN COAL CENTRE

(see also Section 4.2) also showed environmental benefits.
The use of 30 wt% PFA in concrete can reduce greenhouse
gas emissions by 17% and energy use by 14% (UKQAA,
2001a).
In San Francisco, CA, USA, the Two Folsom office building
was designed for environmental sustainability prior to the US
Green Building Council’s leadership to promote green
buildings. It used high volume fly ash concrete at 33–50%
replacement of cement in appropriate mixes for various areas,
such as foundations and slab on a grade, requiring 50% and
columns, curbs and deck slabs with 33% fly ash. The fly ash
gave increased impermeability for areas where the integrity
of the waterproofing system was a potential concern,
increased durability and greater long-term strength. Some
applications were ruled out due to the initial retardation of
strength development but the required design strengths of
21 MPa (3000 psi), 28 MPa (4000 psi), 35 MPa (5000 psi)
were all achieved by the mixes at the 56-day milestone. A
total of 1600 t (1800 tons) of class F fly ash was used on the
project. This diverted the fly ash from landfill and avoided
roughly 1800 t (2000 tons) of CO2 emissions (Brooks and
Fox, 2003).
The Australian standard 3600 for concrete structures permits
the replacement of up to 40% of the cement in a normal
concrete mix with fly ash. It would probably not be worth
attempting to increase this high substitution rate since
commercial issues within the cement and concrete industries
drive the utilisation rates. The benefits of CO2 reduction
through increased use of fly ash as a direct cement
replacement could be an advantage to countries accepting
Australian export coal. At present the amount used in
concrete is often less than that used as a source of
alumino-silicates in cement manufacture which has lower
CO2 reduction benefits (see Chapter 3) (Heeley, 2003).
Concrete made from the innovative magnesium based
eco-cement (see also Section 3.1) is claimed to be capable of
deploying greater quantities of fly ash (ENDS Report, 2003).
In Austria, the new hydraulic binder, Slagstar, which is based
on ground granulated blast furnace slag with gypsum and
alkaline additions (see also Section 4.2), has sulphatic
activation. No burning process is required for the production
of Slagstar. Hence CO2 and NOx emissions are avoided and
energy sources are not required. The use of Slagstar in
concrete foundations in an office building in Vienna,
requiring a volume of concrete amounting to 3400 m3
avoided around 90% of the CO2 emissions (Novac, 2003,
2004). Where available, ground granulated blast furnace slag
may be used in preference to fly ash for this reason.
4.3.2 Saving primary aggregates
The use of conditioned and dry fly ash in conventional,
normal weight concrete and ultra-lightweight foamed
concrete was studied at the University of Dundee, Scotland,
UK. The aim was to overcome the difficulties created by
higher carbon contents and coarser particle size which has
made run-of-station fly ash less attractive as a cementitious
component in concrete, in order to avoid further processing
Cement and concrete – benefits and barriers in coal ash utilisation
Concrete
and promote fly ash utilisation. The limits for use of
conditioned fly ash in concrete permitted under BS 3892-2 as
a fine aggregate component are up to 60% retention on a
45 µm sieve and 12% LOI. The work showed that there is
scope for combining conditioned fly ash with sand at the
quarry and marketing the product as an ‘active’ sand. The fly
ash may be used at up to 15 wt% to improve the grading of
sand deficient of certain fractions and hence contribute to
more effective packing of particles in the aggregate. The
higher compressive strengths of the fly ash concrete (by
10–15% compared to the reference concrete) indicated a
potential for saving cement. However, this would be offset by
the cost of adding superplasticiser admixture to overcome
loss of workability. Replacing sand with coarse fly ash
improved the fresh properties of foamed concrete, although
the high carbon content of the ash meant that up to 2.5 times
more foam had to be added to achieve the required density.
Drying shrinkage strains were up to 2.7 times lower with the
coarse fly ash mixes. The replacement of both Portland
cement and sand with fine and coarse fly ash respectively
greatly reduced the maximum strength that would be
achieved. Hence this practice should only be deployed where
there is no strength requirement for the concrete, that is in
void and back filling. The UK consumes around 205 Mt of
aggregate in total. If 25% of this is used in the manufacture
of concrete, that is around 50 Mt, and 5% of that could be
replaced by fly ash, then a market of around 2.5 Mt could be
developed. However, many impediments to these types of
applications would need to be overcome (Jones and others,
2003).
Naik and others (2003a) point out the need for greater use of
ponded fly ash in the USA to avoid landfilling it, especially
what they term clean coal fly ash which is presumably mixed
with FGD residues. They investigated concrete made with an
ASTM class F fly ash from a wet collection process with as
received moisture content of about 29%. This was tested with
concrete without fly ash and two concrete mixtures
proportioned with clean coal fly ash used as a partial
replacement of cement. The class F fly ash was used as a
partial replacement of both the fine and coarse aggregate due
to the coarse nature of this source of fly ash. They concluded
that non-air entrained concrete mixtures can successfully
incorporate up to 22 wt% clean coal ash and a blend of
25 wt% clean coal ash with 25 wt% class F fly ash. The
flexural strength of the mixture containing 22 wt% clean coal
ash improved over a comparable reference mixture at 28 days
or later so that the concrete was suitable for general
construction. Clean coal ash and class F fly ash could also be
used with high range water reducing admixture using 35 wt%
clean coal ash and a blend of 33 wt% clean coal ash and
5 wt% class F fly ash. However, the early age strength was
low and the concrete was suitable only for general concrete
construction requiring later age strength. Other tests with
FGD fly ashes used in permeable roadway base construction
are detailed by Naik and others (2003b).
In South Africa fly ash concrete is used to encapsulate
ferro-vanadium waste. Mixes with up to 15% fly ash and
10% ferro-vanadium waste were tested and gave satisfactory
strength development at a saving of nearly 7%. The
encapsulation was intended to deploy the ability of fly ash to
41
Concrete
Table 11 Cost of substituting for natural aggregate in concrete (Corinaldesi and Moriconi, 2001)
Cost, US$/m3 concrete Traditional
Natural aggregate 30.0
Recycled rubble aggregate 39.4
with fly ash 47.8
with silica fume 68.8
* at 2001 Italian costs of disposal in landfill (0.05 US$/kg for rubble and 0.23 US$/kg for fly ash)
adsorb heavy metals but leaching tests would be required to
assess the best treatment option for the waste (Potgieter and
others, 2001).
In Italy, Corinaldesi and Moriconi (2001) investigated
increased use of rubble from building demolition as coarse
aggregate in concrete to save natural aggregate. The resulting
loss of strength could be compensated by substituting a fine
recycled aggregate fraction with mineral components, a low
calcium fly ash (ASTM C 618 class F) and a silica fume.
These were added at the rates of 30 wt% of cement for fly
ash or at 15 wt% for silica fume. An acrylic based
superplasticiser was also necessary to achieve the preferred
workability at 1 wt% with fly ash or 1.5 wt% for silica fume.
The compressive strength of the concrete could be improved
to equal or exceed that of concrete made with natural
aggregate (30–35 MPa), keeping the mixture consistency
generally constant at a reduced water to cement ratio of 0.4.
The cost of using fly ash on a traditional basis was greater
than using natural aggregate but it was less than the other
options when disposal costs were included (see Table 11).
Changing economic and environmental drivers, at least
partially dictated by ratification of the Kyoto protocol in
Canada, could justify the increased costs of fly ash
beneficiation technologies to use the unexploited, ever
growing volumes of fly ash currently stored in landfills
(Bouzoubaâ and Fournier, 2004).
In Japan the need to avoid putting fly ash in landfill when the
demand for cement is decreasing has led to the development
of a slagging process to convert fly ash to a fused slag
(see also Chapter 5). This can then displace natural aggregate
in concrete in large quantities. The slag is similar to that from
a cyclone furnace system or wet bottom boiler and is less
likely to leach trace elements (Ishiga and others, 2003).
4.4 Overcoming barriers
The main issues which can hinder ash utilisation are:
marketing; handling, transport and storage; carbon and
ammonia in ash (due to use of NOx reduction technology);
cofiring coal with other fuels; and potential for increased
concentrations of mercury in ash.
4.4.1 Marketing
Expansion of ash markets can be achieved by investment in
42
Eco-balanced *
>30.0
–18.1
–40.7
15.1
marketing networks that ensure reliable availability of coal
combustion products to those who need them. Interested
parties should help develop technologies that ensure the
products are suitable for their intended traditional
applications and that any negative effects of pollution control
technologies such as NOx reduction are properly addressed.
They should also develop new technologies to use large
volumes of coal residues in new applications (Blankinship,
2001).
Ward (2003) considers that the marketability of fly ash could
be improved by avoiding selling bias. Hence a marketing
company prefers to sell what it already makes whereas a
market-driven company tries to provide what a customer
wants. In developing a market-driven strategy, companies
should consider:
1 Product definition: its values or benefits, its positioning,
its physical dimensions.
2 Market segments: target audiences and their
requirements.
3 Delivery system for bringing the product to the user.
4 Communication strategy to make the potential buyer
aware of the product, induced to try and persuaded to
re-buy.
5 Price relative to the alternative product choices.
The benefits outlined above should be explained, pointing
out that they can be obtained without increased cost to
concrete users. Positioning fly ash as an inexpensive
replacement for cement is avoided. This allows for
investment to provide the augmented services that are vital
to continued expansion of utilisation volume and product
value. Although concrete producers are the actual
purchasers of most fly ash used in concrete, architects and
engineers are particularly important as specifiers of
concrete ingredients and should also be targeted. Storage
and terminal capacity is essential to help meet peak fly ash
demands (often when power stations are shut down).
Essential distribution channel functions are detailed under
selling, financing, order management and post-sales
service. The communication strategy should address the
individual concerns of each audience, for example building
aesthetics and the environment for architects, performance
aspects for engineers and quality, consistency and
reliability of supply for concrete producers. The industry
must price its product based on the value of the augmented
services to be offered. This is easier if the fly ash industry
chooses to price its material as a product rather than a by-
product (Ward, 2003).
IEA CLEAN COAL CENTRE

In Hong Kong, the problem of matching supply to seasonal
demand is managed by using coals with a wide variety of ash
contents. Accurate forecasting, close liaison with ash
customers and integrating the ash marketing, coal
procurement and coal handling functions, can generally
prevent shortages of ash and keep surplus production to a
minimum (Lancaster, 2001).
In Canada the relatively new position of the ready-mixed
concrete industry to produce concrete as a ‘manufactured
product’ like steel is a barrier to increased use of fly ash.
Here the proportioning of materials is carried out internally
and the amount of supplementary cementing materials, if any,
is unknown. The question then arises whether there is any
incentive for the concrete producers to expand use of fly ash,
unless it reduces costs (Bouzoubaâ and Fournier, 2004).
4.4.2 Handling, transport and storage
Management of ash at Hemweg power station is directed to
maximum ash utilisation by flexible handling facilities. The
fly ash from the ESP is conveyed pneumatically to silos
where it is loaded into lorries or ships. Both systems are
equipped with facilities to handle both wet and dry ash. The
fly ash can also be loaded into storage silos with similar
handling facilities. Quality control is carried out to guarantee
its use, mainly to replace cement in concrete (DTI, 2001).
Screw conveyors are generally used between the silo and the
mixer. The slope has to be maintained at such an angle that a
worn conveyor still carries the ash forwards to prevent
blockages. The material is dosed with first cement and then
fly ash to guarantee sufficient binder. The correct mixing
time has to be reached in order to obtain the specified
concrete characteristics (vom Berg and others, 2004).
Transport and storage are the only real economic barriers to
using fly ash since it sells at around 38–80% of the price of
Portland cement in Canada. Some of the smaller producers in
rural and remote areas do not find it cost effective to
transport fly ash long distances. The competitive distance for
road deliveries from a cement works is said to be up to
roughly 200 km. However distances of 300–900 km do not
represent an economic barrier in some cases, using rail or
truck for transport (Bouzoubaâ and Fournier, 2004).
Where transport logistics are dominant it is more cost
effective to use fly ash blends produced on site. This method
provides the versatility to choose a blend ratio that minimises
the cost and maximises the volume of fly ash without
compromising performance for concrete products made to
exacting standards, for example railway sleepers, precast
floors (Kruger, 2003).
Bagged PFA and pre-blended PFA cement should be stored
as one would Portland cement. The lower particle density of
PFA means that less can be stored in a silo than Portland
cement. PFA in a silo should be kept well fluidised with dry
aeration to prevent self compaction and in addition silos must
be water tight (UKQAA, 2000). Storage is often a barrier to
using fly ash for smaller producers who only have one silo
Cement and concrete – benefits and barriers in coal ash utilisation
Concrete
for cement and are reluctant to invest in the cost of a second
silo for fly ash (Bouzoubaâ and Fournier, 2004).
A fly ash storage facility as a dome was chosen by Carmelo,
a producer of concrete products in Puerto Rico. The dome
could be built quickly, withstands hurricane force winds and
provides a hermetic, emission-free structure for automated
bulk handling operations in environmentally sensitive areas.
It has a footprint of only 2000 m2 and has a 50 kt storage
capacity. Pneumatic unloaders using a pipeline to the dome
were chosen so as not to obstruct other activities in the
harbour. The facility is described by Figueroa and others
(2003).
4.4.3 Carbon in ash
The carbon content of fly ash has to be lower than 7% when
selling it to mix with cement for the construction industry. A
high carbon content affects air entrainment and any chemical
admixtures in the concrete. At Longannet in Scotland, the
PFA may have a carbon content in the range 7–10% or more
due to the low NOx burners. The critical carbon content
depends on the form of the carbon in the PFA. Some ashes in
the USA need to have less than 2% carbon due to the
particular type of carbon (Armstrong, 2004; McCaffrey,
2003) although ASTM C618 stipulates a carbon content
below 6% for the concrete market (Shilling, 1999).
Efforts to reduce NOx emissions from coal combustion
facilities in the USA may have a negative effect on the
utilisation of fly ash in concrete. Some low NOx emission
technologies operate at lower temperatures than traditional
boilers. This may result in an increase in the content of
carbon and ammonia (see Section 4.3.4) in fly ash. The
specification for LOI in the USA is 3–5% for use in
ready-mix concrete. Low NOx technologies may increase the
LOI above 5% and reduce fly ash utilisation in concrete
applications. For example, in 1998, the ACAA reported that
19 out of 20 coal-fired utilities in Ohio may be affected by
the low NOx emission technologies and 46% of all coal-fired
utilities may be required to control NOx (Walker and others,
2002).
High free carbon contents up to 12–16% in class F fly ashes
generated in southern Ontario and in Atlantic Canada make
them unusable as supplementary cementing materials in their
current form in concrete. These ashes also have high alkali
contents which causes problems when used with reactive
aggregates (Bouzoubaâ and Fournier, 2004).
Beneficiation and separation are used to solve the problem of
carbon in ash and are discussed in Chapter 5.
4.4.4 Ammonia in ash
As noted in Section 4.4.3, greater use of ammonia-based
NOx control systems in the USA is prompting studies on
release of ammonia during mixing, curing and from concrete
products (Rathbone, 2003). Samples of fly ash in accordance
with ASTM C618 from six different power stations were
43
Concrete
60 0 L/min ventilation
Maximum NH3 concentration in air, ppm
8.3 L/min ventilation
50 building stable
40
30
20
10
0
0 50 100 150 200
NH3 concentration in concrete, mg NH3/L H2O
Figure 9 Maximum ammonia concentration in the
air above concrete for ventilated and
non-ventilated conditions
(Rathbone, 2003)
selected. Three samples had ammonia contents of 90 mg/kg,
280 mg/kg and 298 mg/kg ash. The fly ashes were used in
three different concrete mixes with low water-to-cement ratio
of 0.44, medium at 0.55 and high at 0.68, all at 20 wt% of
cementitious components. The ammonia losses during
mixing, above the air over fresh concrete and in the long term
were determined. The results showed that there were no
safety concerns regarding ammonia exposure when working
with ammoniated fly ash. The only area where potentially
hazardous levels of ammonia in the air were measured was
within the ready-mix concrete truck drum during mixing. The
amount of ammonia lost during mixing depended on the mix
proportions and batch size. Between 75% and 95% of the
initial ammonia remained in the concrete after 30 minutes
mixing. For an 11 cm concrete slab, over 50% of the initial
ammonia concentration remained after one month. The
ammonia loss then slowed to a very low rate. The data
suggested that the rate of loss of ammonia from concrete was
limited by diffusion through the concrete and not by the gas
phase concentration of ammonia above the concrete. The
concentration of ammonia in the air depended on ventilation
conditions and concrete mix proportions. For non- or
poorly-ventilated spaces, the concentration of ammonia in
concrete should be less than 50 mgNH3/L of water in order
not to exceed 10 ppm ammonia in the air. With some
ventilation present, the suggested maximum concentration is
70 mg/L and large-scale field tests support these
recommendations (see Figure 9).
4.4.5 Cofiring issues
It was noted in Section 4.2.1 that other pozzolanic ashes from
rice husks, and sewage sludge enhanced the early strength
and reduced the permeability of fly ash concrete. The
products from cofiring such materials with coal might
therefore bring benefits.
EC regulations for use of fly ash in concrete did not include
fly ash from cocombustion and this obstacle to fly ash needed
resolving in order to promote the wider exploitation of
44
alternative fuels. The revision of EN 450 is to accept fly ash
from coal-fired power stations with cocombustion of
secondary combustion materials. This is necessary in order to
avoid the development of separate markets for fly ashes from
combustion of coal and cocombustion as this could lead to
negative commercial consequences and image problems
regarding the use of fly ash. The fly ash from cocombustion
has to be tested and properties relating to concrete
technology and environmental compatibility have to be
checked before a certificate may be issued at an individual
power station. EN 450 will initially refer to national
regulations (Vale and others, 2003).
250 By a special provision in Germany the commercial utilisation
of fly ashes from power plants is not affected for the case of
cofiring municipal sewage sludge when the input fraction
does not exceed 5 wt% on a dry basis. The trace element
content of the sewage sludge is controlled for use in power
stations (Spliethoff and others, 2002). According to the
review including various countries by van den Berg and
others (2003), new tests have started recently in some
German power stations to assess the effects of cocombustion
of petroleum coke, animal meal and paper sludge on the
physical, chemical and environmentally relevant properties of
fly ash.
In the Netherlands, the cocombustion of a maximum of
10 wt% of secondary fuels with coal is permitted and, since
the year 2000, higher percentages are allowed in principle.
The quality of concretes from the fly ashes from
cocombustion were evaluated from both a technical and
environmental viewpoint. The following fuels were tested
(Lamers and others, 2001):
● several types of biomass pellets;
● pellets from paper sludge, composted sewage sludge and
wood thinnings;
● undried paper sludge (heating value of about 4 MJ/kg);
● petroleum cokes;
● dried sewage sludge (heating value of about 12 MJ/kg);
● wood chips;
● liquid hydrocarbons.
Cocombustion of sewage sludge may result in increased
phosphates, calcium oxide and zinc in the fly ashes. The
calcium oxide is not present as free lime but always
associated with phosphate. Calcium phosphate has low
solubility and therefore has no effect on fresh concrete. The
major and trace element concentrations are otherwise similar
to fly ash obtained from coal combustion. Similar
conclusions are valid for cocombustion of biomass as for
sewage sludge. Paper sludge increases calcium oxide in fly
ashes but the free lime does not exceed the requirements of
EN 450. No trace elements are enriched in the fly ash.
Petroleum cokes lead to increased nickel and vanadium in fly
ashes. The ash content of petroleum coke is smaller at
0.5–1 wt% than for coal at 8–15 wt%. Hence the overall
elemental concentrations show no deviation from the
reference fly ashes. In addition results of Danish tests with up
to 20 wt% straw are available. There is a significant increase
in potassium oxide and a small increase in sodium oxide.
These alkalis are usually fixed into the glass matrix of the fly
ash and are only partially soluble. No conclusions can as yet
IEA CLEAN COAL CENTRE
 Concrete

be drawn as to whether cocombustion of straw would lead to
an enrichment of the alkalis in the pore solution of the
concrete. The content and type of unburnt carbon in fly ashes
could also be affected by cocombustion. In the UK concrete
is approved for use in contact with drinking water but this
approval may not apply to fly ash from cocombustion. In this
case leaching tests may have to be carried out (Lamers and
others, 2001; van den Berg and others, 2003; Vissers and
others, 2001).
Concrete samples using fly ash from cocombustion at up to
10 wt% alternative fuels were compared to samples prepared
only with fly ash from the same coal. Strength development,
durability (water suction after 28 and 91 days, carbonation,
chloride penetration and freeze-thaw de-icing salt resistance),
action of superplasticisers, air-entraining and retarding
admixtures as well as the leaching behaviour of concrete
samples were tested. The fly ashes from cocombustion
proved comparable to coal fly ashes in all tests, for example
for chloride penetration and workability, using the same
superplasticisers, the test results show no significant
differences (see Figure 10). A procedure was developed to
show that fly ashes from a maximum of 10 wt%
a) chloride penetration
10
Chloride samples, %
cocombustion are technically equal to fly ashes without
cocombustion. Here the tests of EN 450 are extended with a
conformity analysis to establish the effects of fly ashes on
durability and on cement additives in concrete. The research
programme established that only part of the tests were
necessary for future characterisation of an unknown fly ash
from cocombustion: only the resistance of concrete to
penetration by chloride ions and the freeze-thaw salt
resistance were necessary for durability and only one type of
superplasticiser needed to be used. Fly ashes from
cocombustion of paper sludges and of biomass pellets were
shown to conform to the standard. Conformity tests are in
progress for fly ashes from cocombustion of poultry litter,
cocoa shells, coffee grounds, sewage sludge and demolition
wood. Revisions of the European Standard EN 450 will
probably simplify the Dutch procedure (Lamers and others,
2001; van den Berg and others, 2003; Vissers and others,
2001). Each secondary fuel has to be tested to ensure the ash
gives the same performance as that of coal (Moret, 2004).
Cocombustion experiments in the Netherlands are
summarised by Sarabèr and others (2002).
They report on biomass cocombustion tests with waste wood,
chicken litter and refuse derived fuel in the 1 MWt KEMA
test boiler. The results indicated that waste wood up to about
20 th% was possible without significant negative effects on
the technical quality of the fly ash, although

8 micro-components (copper, lead, antimony and zinc), the

amount of free lime and soluble matter increase.
6 Cocombustion of chicken litter would only be possible at a
small percentage without influencing the quality of fly ash
4 due to the increase in several components such as free lime,
chlorine, sulphur and phosphorus. It was expected that refuse
2 derived fuel could be used at up to about 15 th% without
affecting the technical quality of the fly ash.
0
In 2002, an agreement was made between the Dutch
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government and the electricity producing companies to

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reduce CO2 emissions by direct and indirect cocombustion of

alternative fuels. Alternative fuels are to replace about
b) workability
25 wt% of the coal. For cocombustion at rates exceeding
800 10 wt%, most elements are enriched in the fly ash to a
similar extent to the fly ash from combustion of coal alone.
Only the elements which leave the power station entirely or
600 partly in the gaseous phase are sometimes captured to a
greater extent in the fly ash. These are sulphur, mercury,
Flow, mm

chlorine and fluorine. The presence of calcium in the

400
alternative fuel is an important parameter with respect to the
capture of these elements. The effect of cocombustion at rates
200 exceeding 10 wt% are under investigation (Meij and others,
2003).

0 A project is currently in progress at the University of

10

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Dundee, Scotland, UK, to characterise cocombustion fly ash,

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produced from a range of secondary fuels. The effects of

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using the ash in concrete, including influences on cement

blank
Figure 10 Chloride penetration into concrete and
workability of concrete with fly ash
obtained from cocombustion of different
materials (van den Berg and others, 2003)
cocombustion hydration and leachate are being tested. Investigations to
establish the impact on the fresh, hardened and durability
properties are also in progress (McCarthy, 2003).
In the USA, class C and F fly ashes have been standardised

Cement and concrete – benefits and barriers in coal ash utilisation 45

Concrete
for industrial use in concrete in ASTM C618 (see Table 10)
but this excludes fly ash from cofiring. There is a debate in
progress to decide whether the current definition of fly ash
should be modified or an alternative standard developed for
cocombustion fly ash. The Energy & Environmental Research
Center, University of North Dakota, continues work in this
area to provide an adequate database (Dockter and Eylands,
2003). Samples of fly ashes from full-scale combustion
systems, from bituminous and subbituminous coals with
waste paper, sunflower hulls, wood waste and furniture waste
were tested for compatibility with ASTM C618. The total
silica, alumina and iron oxides ranged from 27% to over 90%
so that many exceeded the minimum requirements shown in
Table 10. The LOI mostly exceeded 10% and therefore did
not meet requirements for partial cement replacement in
concrete. In addition to higher amounts of calcium oxide,
greater amounts of magnesium, sodium and potassium oxide
can be found in the biomass samples. The fineness range also
often exceeded the standard and ranged from 1.2% to over
54%. Air classification (see Section 5.1.1) of such fly ashes
was recommended to meet the LOI requirements. The
biomass fly ash samples did perform well in tests for
expansion due to ASR and sulphate resistance.
Wang and others (2003c) report on the effects of adding
biomass fly ash to concrete. Experiments were designed to
see whether the additional alkali oxides in wood fly ash
would exhibit deleterious effects on the build-up of strength
in the concrete. Combinations of the fly ashes were tested for
effects on slump, air content, flexure, compression, rapid
chloride permeability, freeze-thaw and set time of concrete.
The coal fly ashes according to ASTM 618 were a class C fly
ash from Alabama Power Plant with LOI 1.58% and a class F
fly ash from Georgia Power Company with 0.52% LOI. A
wood ash with 5.44% LOI and two switchgrass/galatia coal
cofiring ashes with LOI around 2.6% at mix proportions of
20:80% and 10:90% respectively were tested. Almost without
exception, the addition of fly ash derived from biomass-based
fuel did not adversely affect the properties of concrete and in
some cases improved the properties investigated. Hence, the
concrete with class C and 20% switchgrass cofiring ash
showed higher strengths 3 months after mixing than concrete
without the additive. The fresh concrete tests showed that
concrete mixes with biomass fly ash require a large amount
of surfactant to obtain the desired air content. Concrete with
the higher percentage of calcium oxide (such as wood,
class C, and the 20% switchgrass biomass) exhibited higher
compressive strength at 90 days. Class F and biomass fly ash
decreased the chloride permeability.
In Australia the effects of cocombustion of coal with biomass
are not well understood in practice. This issue may affect the
ability of fly ashes to comply with Australian standards and
its impact requires assessment because the Australian
government has mandated renewable energy targets (Heeley,
2003).
4.4.6 Mercury in ash
Studies in the Netherlands, Canada and the USA have shown
that leaching of trace elements from concrete containing fly
46
ash was within the specifications of the regulatory authorities.
Concrete incorporating fly ashes is therefore considered
stable. In general the fly ash concrete samples showed similar
or higher trace metal contents compared to Portland cement
concrete (Zhang and others, 2001). In tests on the potential
for thermal release of mercury from ashes used in
by-products, most of the mercury was released only above
300°C, making it stable for most concrete applications (Rubel
and others, 2003).
Mercury emission controls, which are to be enforced in the
USA in 2008, may affect ash sales because they are usually
based on activated carbon. Any activated carbon in ash
severely limits its use in concrete. The carbon attracts air
entraining agents which are used in concrete for workability
and freeze-thaw capabilities. The release of mercury during
curing is considered unlikely but is being confirmed by EPRI.
Laboratory tests at Ohio State University are comparing
concrete made with Portland cement, coal fly ash and
mercury laden sorbent. The worst case scenario is taken, that
is mass concrete because it has higher curing temperatures.
Preliminary conclusions indicate that (Golden, 2003):
● the temperature is not high enough to liberate mercury;
● less mercury may be released with powdered activated
carbon than with fly ash mix or 100% Portland cement;
● there is no known release mechanism for mercury once
the concrete has solidified.
Zhou and others (2003) describe the development of mercury
sorbents which do not interfere with air entraining agents.
Tests with powdered activated carbon at the Pleasant Prairie
Power Plant in Wisconsin in late 2001 indicated mercury
emissions reductions of 40–70% were achievable. This
resulted in the following percentage carbon in ash:
Mercury removal, % Carbon in ash, %
0 0.6
40–50 1.1
50–60 1.6
60–70 3.6
The increased carbon in ash would have required a foam
index of >72 drops for a stable foam, whereas the contract
limit is 25 drops. The plant currently produces about 200 kt/y
of fly ash which is all sold. The mercury emission control
would cause a loss of this revenue and an additional cost of
about $7 million to landfill the fly ash that had previously
been sold. One alternative is to add a baghouse and inject the
mercury sorbent between the old and new particulate control.
Retrofitting a baghouse is extremely expensive and the added
pressure drop would increase operating costs. A carbon
burnout or ozone treatment system could be added but also
have high capital requirements and operating costs. Even
mercury sorbents made without carbon may still render the
fly ash incapable of use in concrete. For example,
silicate-based sorbents were also shown to limit air
entrainment (Zhou and others, 2003).
Modified halogenated sorbents have been tested at Ohio State
University where they achieved 60–70% mercury removal. A
newly-developed mercury sorbent (A6), for which patents are
pending, achieves the same mercury removal but with a lower
IEA CLEAN COAL CENTRE
 Concrete

foam index than the normal (untreated) fly ash and around
10% of the foam indexes required with two commercial
powdered activated carbons. The effect is consistent when
using other fly ash samples, both type C and type F, from
seven diverse power plants. The captured mercury did not
leach out during Toxicity Characteristic Leaching Procedure
tests. Other air entraining admixtures also proved successful
with the A6 sorbent. Tests on concrete made with fly ash
containing the A6 sorbent showed compressive strength
development equivalent to that of the control mix after 8 and
28 days (Zhou and others, 2003).

4.5 Comments
The main effects of using fly ash in concrete are:
● lower heat of hydration;
● longer set times;
● better workability;
● lower early strength, higher late strength;
● lower ASR;
● improved microstructure leading to lower permeability;
● better performance in aggressive environments, higher
sulphate and chloride resistance;
● higher electrical resistivity reducing corrosion of the
reinforcement.

These effects are deployed by various means to meet the

requirements for and improve the many types of concrete
produced in different countries. The following examples of
successful fly ash substitution rates for cement in concrete
are found to satisfy various requirements in the information
reviewed:
wt%
Reduction of ASR 15–>30
Overall satisfactory early strength, up to 35
Durability, especially in aggressive environments 40
High performance concretes 40
Fibre-reinforced concretes 18–40
Self-compacting concretes 45
Roller compacted concretes in dams and roads 50
Sulphate and chloride resistance with
class C fly ash, up to 70

High substitution rates are used when fly ash substitutes for
aggregate in concrete, for example at up to 50 wt% of sand,
or 30–90 wt% of total solids in cellular concrete.

Increased use of fly ash in concrete brings effective reduction

in CO2 emissions and use of primary aggregates. Further
investigations are in progress on use of fly ash from power
stations cofiring at higher rates of secondary fuel substitution.

Cement and concrete – benefits and barriers in coal ash utilisation 47

 5 Treatments and beneficiation
Use of low NOx burners often results in increased carbon in
ash. The carbon may render previously marketed fly ash
unsuitable for application in the cement and concrete
industries.
The focus of most beneficiation methods has been to
minimise the negative effects that carbon has in concrete. The
carbon particles are generally of lower density than inorganic
matter in the fly ash and this can be deployed to separate
unburnt carbon from fly ash (Ozdemir and others, 2001).
Technology is now available to reduce the carbon content of
fly ashes to the commonly quoted target of 2% (Ravina,
2003) or less than 1% using froth flotation (Smalley, 2004).
Both SCR and SNCR may contaminate ash with ammonia as
well as use of ammonia to enhance electrostatic precipitators
and control SO3 emissions. Ammonia concentrations between
200 and 2500 ppm are common. Ammonia in ash is not
detrimental to concrete performance but when the ash is
mixed with the alkaline cement to produce concrete, the
ammonia is volatilised. This may cause odours and presents a
hazard to workers both at the concrete plant and during
placement and finishing of the concrete. Ammonia can also
be released from cured concrete at low levels upon repeated
wetting. This is non-hazardous but unpleasant. Hence fly ash
containing greater than 100 ppm is considered unacceptable
for production of concrete (Bittner and Gasiorowski, 2003).
Ammonia can be removed from ash to over 90%, reducing
the ammonia content to less than 30 ppm (Bittner and others,
2003).
Much of the coal combustion residues stored in the USA is
mixed fly and bottom ash, often contaminated with carbon
and, in some cases, pyrite (Robl and Groppo, 2001). When
the pond areas at power plants are full, the ash has to be
transported to landfills. It is therefore advantageous to
recover by-products from the stored ash to maintain adequate
storage capacity at the plant. The utilities do not need to alter
their ash disposal practice, they can avoid costly plant
modifications and the construction of temporary ash storage
facilities as in the case for a dry process (Groppo and Robl,
2001).
Re-drying of stockpiled fly ash is of particular importance in
France. About 30 Mt of stockpiled fly ash is available for
utilisation, mostly in the north and east of the country. Two
units for drying and upgrading the coal ash were built by
Surschiste, an ash marketing company in France, in 1980 and
1991. More than 500 kt of temporary stockpiled fly ash are
re-dried each year. This has resulted in a utilisation rate for
fly ash which exceeds the production rate in France. In
Germany a re-drying facility was constructed during 2000 for
fly ash stockpiled over winter. The plant is designed to
process 60 kt of fly ash per year (vom Berg, 2000; Brennan
and others, 2003; Vale and others, 2003). At Longannet
power station, Scotland, PFA is recovered from ash ponds,
stacked for draining and screened for infilling abandoned
coal mines and embankments. This releases lagoon space
48
(Armstrong, 2004). Ponded ash may not currently be dug out
at Maasvlakte power station in the Netherlands but there is a
prospect of using it for embankments from September 2004
(Moret, 2004).
Various treatments for dry and wet ash have evolved for
reducing carbon in ash and these are discussed in Section 5.1.
Ammonia reduction processes are considered in Section 5.2.
5.1 Carbon in ash
Treatments available to reduce carbon in ash may be divided
into classification, grinding, blending, separation and
combined processes (see Sections 5.1.1–5.1.5). More recent
developments include burnout, fusing and oxidation
processes (Section 5.1.6) and chemical neutralisation
(Section 5.1.7).
5.1.1 Classification
Fly ash may be extracted selectively from the ESP hoppers
containing the higher quality material or fine fly ash may be
obtained by grinding (Ravina, 2003). In examining the
capture of trace elements on fly ash from a 500 MW wall
fired unit burning a central Appalachian low-sulphur, high
volatile A bituminous coal blend, Sakulpitakphon and others
(2003) found that the distribution of carbon in fly ash was
asymmetric. The B-side ESP hoppers had a greater amount of
carbon and individual rows of ESP hoppers also showed an
asymmetric distribution of carbon. Most of the arsenic was
captured on the fly ash and the mercury content of the fly
was low, as expected for ash derived from a low-mercury
coal. Segregated ash collection from different stages of the
ESP is considered by Kumar and others (2003b) to have a
role to play in fly ash beneficiation in India but more
initiatives need to be taken to make treated fly ash available
in containers as well as in bagged condition to maximise the
returns from the resource. This basic approach is being
studied along with developments for fine particle capture in
ESP in order to combine ash collection with beneficiation
(see Pasic and Khan, 2003). Since this includes
triboelectrostatic charging, it will be discussed in
Section 5.1.4.
Air classification of fly ash is carried out commercially in the
UK for all fly ashes used for structural concretes (Ravina,
2003). It is not widely used throughout the European
community and yet it is long established in the UK and has
been shown to be beneficial to concrete. Most of the
differences between sources of fly ash are removed as UK
suppliers of PFA adjust the classification process to produce
a demonstratively similar material. According to the BS 3892
Part 1, the fineness of PFA shall be less than 12% retained on
the 45 µm sieve. Loss on ignition (LOI) of up to 7% is
permitted (Sear, 2001). The actual carbon content is typically
around 10% less than the LOI (Ozdemir and others, 2001).
IEA CLEAN COAL CENTRE

Classified fly ash is supplied to the same standard as in the
UK by CLP Power in Hong Kong. The ash classification
plant is fully integrated into the operation of Castle Peak
power station and the classified PFA can replace up to 40%
of the cement used in concrete (Lancaster, 2001).
Classified fly ash has solved problems in concrete production
for tunnel relining in Mumbai, India. Pozzocrete 63 has a
fineness of 10% retained on a 45 micron mesh and
Pozzocrete 83 is finer at 5% on 25 micron mesh. The finer
product was chosen and improved workability, producing a
self compacting concrete when substituted as part of the fine
aggregates (Joshi, 2003).
Ash Resources S.A. operates a classification process to
produce classified and super classified products marketed as
Dura-Pozz® and Super-Pozz® (see http://www.superpozz.com)
respectively. Details of the recovery rates are commercially
confidential (Kruger, 2005). Microspheres may be recovered
by air classification for use of fly ash as a filler in the
polymer industry. Two products of differing fineness are
commercially available in South Africa, under the trade name
of Plasfill. At a low relative density of just over 2 g/cm2,
these fillers result in a higher volume loading which leads to
significant savings of polymer which is substantially more
expensive (Kruger and others, 2001).
In Korea, use of the domestic anthracite coal ash is not
possible in the ready mixed concrete market due to the high
unburnt carbon of about 8–17%. This can only be reduced to
5% by the typical centrifugal classifier. However, a
multi-stage air classification process was developed in 2001,
based on a coarse sized cyclone followed by a larger cyclone,
bag filter and induced draft fan. The ash is smoothly inhaled
into the cyclone and this prevents crushing of unburnt carbon.
A pilot-scale plant achieved 2.9% LOI from fly ash with
unburnt carbon of 8.4% LOI. It was planned to construct a
full-scale 30 t/h capacity plant at the Seochon power station
in 2003 (Park and others, 2003). This would not be suitable
for blended coals (Moret, 2004).
Hydraulic classification may be used for stored ash in the
USA (see Robl and Groppo, 2001; Groppo and Robl, 2001).
The research focused primarily on class F (ASTM C-618) – a
type of fly ash which is low in calcium. Several approaches
were investigated and a cocurrent hydraulic classifier gave
the best operational flexibility with the least misplaced
material. The classifier was fed pre-screened fly ash at about
10 mm and set up to produce four size fractions. The
particles containing more carbon were shifted to the finer
range and the iron to the coarser range. The finest fraction
was fed to a froth flotation circuit (see below). Mid-size
particles could be sent to spiral concentrators for separation
of coarse carbon, ash and high density material. The
approach was adjusted according to the nature of the
materials. The coarse materials were used in anti-skid road
surfaces or as sand for making cement blocks.
Simple hydraulic classification did not succeed in separating
a filler grade material. This was due to flocculation. A group
of organic high molecular weight water-soluble sulphonated
polymers were found to be effective anti-flocculants at pH
Cement and concrete – benefits and barriers in coal ash utilisation
Treatments and beneficiation
ranges from 7.5 to 9.0. The amount of superplasticiser
needed to deflocculate samples of fly ash from an
Appalachian bituminous coal-fired power plant varied from
3 to 7 g/kg fly ash. Commercial plants for classification and
dewatering coarse ash are operating in South Carolina and
Kentucky. The materials produced are used as aggregate in
lightweight concrete blocks and as anti-skid materials in
asphalt road pavements. A second phase aimed to produce
aggregate and recover carbon for use as a fuel (Robl and
Groppo, 2001).
5.1.2 Grinding
An example of the application of ultra fine fly ash in
Section 4.2.1 showed positive effects on the compressive
strength of concrete (see Figure 8). Grinding was found to be
an effective treatment for improving the compressive strength
of mortars with fly ashes for long curing times when
comparing the long-term mechanical strength of fly
ash/Portland cement mortars (Payá and others, 2001b). The
increased Al content for ground fly ash mortars suggested
that the mechanical treatment increased the pozzolanic
activity more than sieving.
The Swedish firm, EMC is reported to have patented a
technology which uses an intensive grinding process to
improve binding performance. This permits a greater
proportion of materials such as fly ash or sand to be used
than the 15–20% which is customary. The company claims
that its technology could reduce the amount of Portland
clinker used to make cement by 50%, reducing CO2
emissions by some 40%. If applied to the cement industry
worldwide, this would produce a 3% reduction in global CO2
emissions (ENDS Report, 2004).
5.1.3 Blending processes
The fly ash processing plant at Maasvlakte power station,
near Rotterdam, The Netherlands, was commissioned by
Vliegasunie in 1995 to upgrade fly ash on a large scale,
having a capacity of 250 kt/y. The plant has two prime
objectives, storage and upgrading of the production of fly ash
by all five Dutch coal-fired power stations through sieving
(see also Section 5.1.1) and blending (see Figure 11). The
storage facility allows matching of production with demand,
while the upgrading of the material guarantees a constant
high quality to customers in the cement and concrete
industries. The intake silo may be fed from trucks, ships or
directly from the Maasvlakte power station and it consists of
nine concrete bins of 1 kt capacity each. Beneath the intake
silo bins is a blending installation which allows up to three
different flows of fly ash. The adjacent upgrading plant has
six sieves to reduce the carbon content of the fly ash <5%
and to improve the fineness to over 70% <45 µm. Every
tonne of fly ash is registered and ash derived from cofiring
has to be checked to ensure it is physically the same as fly
ash from burning only coal. Samples are analysed for quality
control in a small laboratory in the upgrading plant and in the
main laboratory of the power station. Up to 25 product
quality characteristics are examined for intake and despatch
49
Treatments and beneficiation
supply
250,000 t/y
sieving
140,000 t/y
blending
225,000 t/y
dispatch
250,000 t/y high quality PFA
20,000 t/y high carbon PFA
Figure 11 Flow chart for fly ash processing plant,
Rotterdam, The Netherlands (Moret, 1995)
testing. The end product silo consists of four concrete bins of
8 kt capacity each. The ash may then be transported to users
by loading directly from the bins to bulk trucks or barges
(Moret, 1995, 2004; Brennan and others, 2003; Vale and
others, 2003).
5.1.4 Separation
Gravity and magnetic separation was tested on fly ash from
Tunçbilek power station, in Turkey. The gravity methods
were considered to be particularly suitable as the density of
the fly ash particles showed considerable variation. Magnetic
separation was used to reduce the iron content to 2%, a
requirement for the ceramic industry. The fly ash came from
lignite and was classified as a C type fly ash according to
ASTM C 618 with 1.41% carbon and 11.3% iron. Unburnt
carbon was separated from the pozzolan by gravity separation
resulting in 1.1% carbon pozzolan. The carbon product was
used as a fuel in the power station. Magnetic separation gave
a magnetic product containing 35% iron which could be used
in heavy medium plants (Ozdemir and others, 2001).
Magnetic separation with aerodynamic drag is the basis of a
prototype separator tested by Brandner and others (2003).
Small dry particles are difficult to separate because of their
high surface area which makes them susceptible to air drag,
electrostatic and hydrophilic agglomeration forces which are
often difficult to control. The separator overcomes these
problems with a combination of magnetic and aerodynamic
forces. Thirteen fly ashes were tested from different power
station configurations, with or without low NOx burners,
burning different coals and with LOI varying from
1.73–12.98%. The fly ashes were separated into magnetite,
particles with less than 4% LOI and particles with specific
gravity <2.2 g/cm3 at feed rates of up to 1500 kg/h. The
50
magnetite could be used in heavy media coal cleaning
circuits, the low LOI fractions for Portland cement, and the
low density fractions in the production of low density
aggregate and blocks.
Froth flotation is the basis of a process developed by
RockTron Limited since the early 1980s. Extensive trials
were carried out on pilot and commercial scale. It was
selected for installation at Aberthaw power station and
Fiddlers Ferry power station in the UK in 2003. The process
is designed to produce solid microspheres which have
potential for use in concrete or as high value fillers in the
paints, plastic and paper industries. In addition the process
separates unburnt carbon for use as solid fuel, magnetite for
use in thermoplastics, as well as coarse and fine ash for use
in the construction industry (Brennan and others, 2003;
Vale and others, 2003). Thus 100% of the feed is recovered
as products, including cenospheres, wet and dry carbon, a
magnetic ash product for heavy media separation and filler,
as well as the alpha product for concrete, cement
manufacture, replacement, blended cement and fillers, and
delta product for concrete bricks, tiles and blocks
(see Figure 12). Some reasons given for the choice of the
process for Fiddlers Ferry power station included (RockTron,
2004; Smalley, 2004):
● wet conditioned and lagoon ash as well as dry freshly
arising fly ash can be treated – giving full land
reclamation from stockpiled PFA;
● the process could handle the required ash throughput of
100 t/y throughout the year;
● it was based on well understood and readily available
physical process equipment so there were no technical or
engineering issues associated with the plant;
● there were no issues with respect to obtaining
environmental permits, and the products were not subject
to a UK Waste Management Licence .
Other benefits of the RockTron Process over dry processes
include (Smalley, 2004):
● improved pozzolanic reactivity because alkali salts are
removed from the surface of ash particles;
● it can handle carbon contents in excess of 8% and has
been tested with 20% carbon material, still achieving
<1% carbon in the product;
● the recovery of ash product is much higher at >95%;
● the grade of carbon product is higher at >90% carbon;
● ash recovery and carbon grade are less sensitive to
variations in the carbon content of the feed.
Electrostatic separation was chosen by Carolina Power and
Light Company for the Roxboro Plant in North Carolina,
USA, in preference to froth flotation or carbon burnout. This
was because the equipment was compact, had low power
consumption (1–2 kW/t of material processed), did not
generate emissions, could process up to 40 t/h and reduce the
carbon content in the fly ash from 30% to 2% (±0.5%). There
were already successful installations in the USA. Froth
flotation was rejected on account of its high capital cost, low
capacity, and long construction lead time. There were no
existing installations and permitting issues. Carbon burnout
was also limited in capacity, the cost was much higher and
there were no commercial installations (Shilling, 1999).
IEA CLEAN COAL CENTRE
 Treatments and beneficiation

power station

cenospheres dewatering
stockpile de-agglomoration cenospheres cenospheres product
or lagoon and particle recovery and cleaning
cleaning

carbon carbon product (wet)

carbon dewatering drying
carbon recovery and cleaning

carbon product (dry)

mag-ash dewatering
mag-ash recovery and cleaning
mag-ash product

alpha
drying
alpha dewatering

alpha product (dry)

cementitious
product recovery delta dewatering
delta product (wet)
Figure 12 RockTron PFA beneficiation process (RockTron, 2004)

Table 12 Commercial installations of the STI electrostatic separator (Bittner and others, 2003)

Utility/Power station Location Start of commercial operations

US Generating Co/Brayton Point MA, USA July 1995

Progress Energy/Roxboro NC, USA September 1997

Constellation Power Source Gen/Brandon Shores MD, USA April 1999

WPS Power Development/Sunbury PN, USA November 2000

ScotAsh (LaFarge/Scottish Power)/Longannet Scotland, UK October 2002

Jacksonville Electric Authority/St John's River FL, USA May 2003

Meanwhile, six commercial installations are using the
Separation Technologies Inc (STI) carbon separation process
(see Table 12). A similar unit was scheduled to be installed
by Innogy at Didcot power station, UK, during 2003 (Vale
and others 2003). The STI plant is shown in Figure 13 and
has a compact size, less than 10 m long, 1.5 m wide and little
over 2.7 m high. The particles are triboelectrically charged by
interparticle contact and attracted to opposite electrodes. The
counter current flow of the separating particles and continual
charging by carbon-mineral collisions provides for a
multi-stage separation and recovery in a single-pass unit
(Bittner and Gasiorowski, 2003; Bittner and others, 2003).
The fly ash is marketed as ProAsh which is a consistent
2%±0.5% LOI product processed from a wide range of fly
ash LOI from up to 30% and satisfies all standards
(ASTM C-618/AASHTO M295) for use in concrete
(Separation Technologies LLC, 2003).
The LOI of fly ash treated at Roxboro has been consistently
of average 1.95% (±0.25%). It is supplied to ready-mixed
concrete operations in Virginia, North Carolina and South
Carolina where it is used to mitigate alkali silica reaction in
concrete due to the use of reactive aggregate and
unavailability of low alkali cement. Fly ash utilisation has
expanded since the air entraining problems due to ash
variability have been eliminated (Bittner and Gasiorowski,
2001, 2003).
At St John’s River Power Park, up to 20 th% petroleum coke
is burned with coal. The fly ash has an increased carbon
content with LOI of 15–28%. The electrostatic separator
reduces this to <3.5%. The Florida Department of
Transportation would not initially permit the use of fly ash
derived from other than 100% coal in concrete for road
construction but allowed it in May 2003 after completion of

Cement and concrete – benefits and barriers in coal ash utilisation 51

Treatments and beneficiation
feed rate: 36 t/h
positive electrode
negative electrode
positively charged
particles (carbon)
negatively
charged
particles
(mineral)
sampler
product sampler
storage
silos
hopper
ash pump
dry truck blower
loadout
Figure 13 STI carbon separation process (Bittner and Gasiorowski, 2003)
successful durability tests on the processed fly ash from
cocombustion of coal and petroleum coke (Bittner and others,
2003).
At Longannet, Scotland, the carbon in ash has increased from
3% with old style burners to 7–10% with use of low NOx
burners and up to 15% if combustion is less efficient. Ash is
fed to three ports at the STI separator, depending on how much
carbon reduction is required. The LOI needs to be reduced to
5% for intergrinding in cement and this product is sent to the
Dunbar cement kiln. Both classification and STI separation are
needed for use of high C ash in blended cement as 65% needs
to be <150 µm. Classification is not necessary for raw material
in cement kilns (#5%) and this extends the life of the quarries
by replacing natural raw materials. High carbon ash is not used
as fuel in the cement kilns because of the high capital costs of
handling the powder. Hence the cement industry prefers to use
low cost fuels such as tyres and waste liquids (Armstrong,
2004). Eventually it was hoped that the ‘unburnt’ element of
the separated ash would be returned to the power station for
use as a fuel source and permission for combustion trials was
given by the Scottish Environmental Protection Agency
(World Cement, 2003).
Another electrostatic separation process called Tribo Flow
Separations (TFS) technology uses pneumatic transport
processing instead of mechanical means (see Jiang and
Stencel, 2001; Lockert and others, 2001). The first
demonstration of the TFS technology is at the Jack
McDonough Plant, Atlanta, GA, USA and the 0.9 t/h
continuous separation ran well. Utility requirements for a
9 t/h system would cost 0.77 $/t of processed ash.
52
raw ash silo
feeder
vibrating screen
air slide
STI separator
sampler
high hopper
carbon
silo
ash pump
to coal conveyor blower
for reburn
5.1.5 Combined classification and
separation processes
As noted in Section 5.1.1, electrostatic separation could be
part of ESP particulate control. Bench-scale experiments on a
new technology which combines ESP ash collection with
sieving for fly ash beneficiation are described by Pasic and
Khan (2003). A conventional ESP may be modified using
grounded screens positioned in alternation with high-voltage,
high-corona-density discharge electrodes and perpendicular
to the direction of flow. The technology combines
conventional sieving, electrostatic precipitation and, to a
certain extent, triboelectrostatic precipitation due to intense
friction between the particles and the screens. Experiments
on 2.4% low carbon fly ash from the General Gavin Power
Plant and 16% high carbon fly ash from the EPA Glen Lend
Power Plant, WV, USA, have confirmed that the screen-based
ESP technology can be used for both particulate control as
well as its classification in dry conditions. The first screen at
Glen Lend captured fly ash containing 36–41 wt% of carbon
while the ash collected afterwards had only 1.4 wt%, making
it suitable for use in the cement industry. The technology
should also be applicable to wet ESP. More experiments are
needed on capture of soot, chemical and physical
characterisation of captured ash components as well as at
high (149°C) and very high temperatures (760°C).
Robl and others (1997) discussed the relative merits of
hydraulic classification and froth flotation. Analysis of over
50 fly ash samples from a variety of source, showed that the
majority contained a substantial proportion of coarse carbon,
typically containing 35–45% carbon. Froth flotation was
IEA CLEAN COAL CENTRE

certainly capable of removing this coarse carbon, but it was
much simpler and less expensive to remove it by
classification. Flotation also provided limited control of
fineness. Classification had the advantage of removing the
coarse ash as well, providing control of the fineness of the
low LOI flotation product produced by flotation. This is
particularly important when processing ponded ash. When
mining a pond section that is especially coarse, it is necessary
to classify the ash to ensure that fineness is maintained. This
is simpler prior to flotation when the ash is in a dilute slurry.
Since the objective of ash beneficiation is to remove carbon
and produce a quality pozzolan, both low LOI and fineness
are required. This is achieved by classification followed by
froth flotation.
Pilot-scale froth flotation tests showed that the LOI could be
reduced to 0.5–2.5% carbon with reasonable reagent costs
and a yield of low LOI product of 75–80%. The remaining
20–25% of material recovered in the froth product contained
35–40% carbon which was suitable for reburning or further
upgrading as a value-added product. Fineness values were all
less than 10% retained on a 325 mesh screen (45 µm)
(Robl and others, 1997).
The Coleman Power Plant Project is detailed by Groppo and
Robl (2001). This is a co-operative effort between the US
Department of Energy (US DOE), the University of Kentucky
Center for Applied Energy Research and Western Kentucky
Energy. It uses the Fuel-Float™ process to recover high
quality fuel, a marketable lightweight aggregate and pozzolan
for concrete from stored coal combustion ash. The approach
involves integration of hydraulic classification followed by
gravity concentration for coarse products and recovery of a
fine carbon product by froth flotation. The fly ash carbon
resulting from gravity separation contained 43% fixed carbon
compared to 50% as received in the high volatile bituminous
coal used at the power plant. The ash content was 53%
compared to 14% in the coal. The fly ash carbon showed
relatively high reactivity, attributed to both the macro
porosity and high surface area. The flotation tailings product
could be processed further to produce highly active
superpozzolans and polymer filler, both higher value
materials (Robl and Groppo, 2001).
As noted above, value added carbons are being extracted
from PF ash ponds and landfills in research at the University
of Kentucky. Andrews and others (2003) report that coarse
carbon particles (>150 µm) resulting from classifying a slurry
of coal ash were concentrated by gravity separation and then
dewatered. Fine carbon particles (<150 µm) were
concentrated by froth flotation and then dewatered. Pilot-
scale testing of the process recovered coarse carbon products
with grades as high as 70% carbon while the fine carbon
products were up to 60% carbon. A demonstration facility is
being designed for installation at Coleman Station,
Hawesville, KY, USA.
The FastFloat™ technology provides the opportunity for total
utilisation of coal combustion by-products. A demonstration
plant, being built at Ghent power plant, is sponsored by the
US DOE and will produce a high-quality pozzolan by
thickening, filtration and drying of the carbon-free fine ash
Cement and concrete – benefits and barriers in coal ash utilisation
Treatments and beneficiation
rejected after flotation. It is envisioned that the beneficiation
plant will generate approximately 200 kt/y of processed coal
combustion by-products. A final stage will process a
slipstream of the flotation tailings through a secondary
classification stage to produce a mineral-grade filler suitable
for use in plastic resins or high-performance concrete
(CAER, 2004).
A combination of dry magnetic separation and hydrodynamic
classification processes was applied to fly ash from
Irsha-Borodinskii lignite, Kuznetskii and Ekibnastuzskii coals
in Russia. Magnetic microsphere and cenosphere products
were studied with a view to their application as catalysts for
deep oxidation of hydrocarbons and other types of waste
(Anshits and others, 2001).
Vassilev and others (2001) studied multicomponent utilisation
of fly ash from Spanish coal-fired power stations by a
combination of conventional methods, including sink-float,
magnetic, sieving and froth flotation separations, leaching
and crystallisation procedures. These yielded ceramic
cenospheres, water-soluble salts containing some trace
elements, a magnetic concentrate enriched in certain trace
elements, a char concentrate with some volatile trace
elements, a heavy concentrate containing various trace
elements and an improved fly ash residue suitable for
construction materials. The aim was to transform a low cost
by-product into useful, high-grade and expensive materials
which may find various applications.
5.1.6 Burnout, fusing and oxidation
processes
The approach to reducing carbon in ash in this section
includes commercial and pilot-scale operations based on
burnout, fusing and oxidation of the coal ash.
Burnout processes
In the USA, burnout processes are options for dealing with
this problem at coal-fired power stations burning Eastern
coals to improve the quality and attractiveness of their fly ash
streams. By contrast much of the fly ash derived from
Western and Midwestern coals is marketable without
beneficiation (Schimmoller, 2003).
This offers the solution of reburning high carbon ash from
one power station by transporting it to another where more
complete combustion occurs. Ramme and others (2001)
describe the case of one power station of Wisconsin Electric
burning bituminous coal and producing fly ash with an LOI
of 66.4% and bottom ash with an LOI of 44.8%. Both ashes
were being landfilled. Analysis of a second plant of
Wisconsin Electric burning subbituminous coal showed an
average LOI of less than 0.5% for the fly ash and 2.4% for
the bottom ash. This fly ash was used as a cementitious
material in concrete production. The high LOI fly ash can be
introduced with the pulverised coal stream entering the
pulveriser classifiers or at each burner location. It can also be
introduced with the secondary air flow stream as it enters the
furnace or through injection pipes into the furnace. For
example, a fly ash with LOI of 26.5% was introduced to the
53
Treatments and beneficiation
furnace through injection pipes at a rate of about 1–2% of the
coal flow into the furnace. This did not affect combustion and
the resulting fly ash had an LOI of between 0.2% and 0.5%.
Bottom ash may require grinding and it is therefore
preferable to add it to the store of coal before grinding. The
bottom ash and coal mixture has an acceptable grindability
index. A test reburning used an addition of 1% bottom ash
(with an LOI of 37.9%) to the coal. The LOI of the fly ash
from the test reburning of the bottom ash was 0.2% to 0.4%
and had a calcium oxide content of between 21.4% and
22.6%, which was lower than the normal average of 26%.
This may even improve properties of this blended fly ash for
use in concrete production. Tests with a recovery process for
coal combustion products from landfills, based on reburn, are
also described by Ramme and others (2001).
The carbon burnout process (CBO) is regarded in the USA as
an alternative to electrostatic separation. The process,
patented by Progress Materials Inc, relies on a proprietary
fluidised bed furnace to combust the carbon in the fly ash,
leaving a consistent fly ash product for the ready mix
concrete market. The flue gas from the CBO can be
integrated into the main stack of the power station. Hence
permitting is relatively straightforward (Schimmoller, 2003).
The CBO unit was installed at the 772 MW Wateree Station,
near Columbia, SC, USA, in 1999 (see Figure 14). It
processes 200 kt/y of ash, from LOI of 6.5–18% to yield a fly
ash product with a consistent average LOI of 2.5% or less,
regardless of feed LOI. Blending capabilities have been
important in accommodating operating periods during which
fly ash LOI values spike high or low. A lower limit of 9% is
targeted to ensure enough carbon is in the furnace to sustain
combustion. Since throughput decreases with increasing LOI,
an upper limit of 12% is maintained. Heat from the CBO flue
gas is used to preheat feedwater from one of the low-pressure
feedwater header trains, improving the power plant efficiency.
This does not require a heavy-walled heat exchanger and the
stream can be returned to the steam cycle ahead of the
deaerator at the required temperature and pressure. The heat
rate is improved, reducing the coal input by about 17 kt/y.
The exhaust gas is recirculated in order to control the
combustion process at an acceptable burn rate at different
Figure 14 Carbon burnout process installation at
Wateree Station, SC, USA (Keppeler,
2003a,b)
54
feed LOI rates. The CBO fly ash is finer than the low carbon,
class F fly ash produced by the units before low NOx burners
were fitted. It has performed well in concrete markets and has
good air entrainment, perhaps due to preferential combustion
of char type rather than graphitic carbon and corresponding
surface area differences (Keppeler, 2003a,b; Schimmoller,
2003).
A second CBO unit went into commercial operation in 2002
at the 1120 MW Winyah Station, near Georgetown, SC,
USA, and can process 190 kt/y with raw feed having an LOI
of 16%. Modifications to the design and eliminating
unnecessary features of the first installation have improved
the economics (Keppeler, 2001, 2003a,b).
A microwave carbon burnout (MCB) process is described by
Tranquilla and MacLean (2001). It uses microwave energy in
a fluidised bed reactor with air to oxidise the carbon to any
prescribed amount. The bed temperature is in the range
650–850°C and can be regulated to within less than 5°C. The
residence time is controlled by means of the input feedrate.
Where the carbon concentration is sufficient to support
autothermal operation (approximately 7–9% depending on
reactor design), the microwaves provide start-up and throttle
energy.
Tests were carried out with a pilot MCB test unit using fly
ash samples from several US and Canadian power stations,
the LOI ranging from 4–30%. The product LOI was
maintained to ±0.5%, regardless of the input LOI. Any
arsenic or mercury in the fly ash were present in the product
and were not transferred to the cooled exhaust gas stream.
The mercury was recondensed on to the fly ash upon cooling
(Tranquilla and MacLean, 2001).
Fusing processes
Ash modified clinker (AMC) technology is a process
developed in China and is based on fusing calcium oxide to
the coal ash. A lime-rich powder with additives is added to
coal at the pulveriser, increasing the calcium oxide content of
the coal ash. AMC technology is particularly suited to
enhancing the value of coals that produce class F fly ash with
high LOI and low calcium oxide content under normal or low
NOx burner combustion modes. An additional benefit is an
SO2 emissions reduction of up to 90% and a 2% reduction in
coal consumption. The fused ash is a cementitious clinker
which finds use in the cement market, developing a
compressive strength at 28 days of 66.2 MPa and a tensile
strength of 7.8 MPa (Khadilkar and others, 2003).
Commercial applications of this process are not mentioned.
In Japan, Ishiga and others (2003) describe a new coal ash
fusing system which is an additional furnace, capable of
treating the pulverised coal combustion residues from various
types of coal. The aim is to produce a slag from fly ash. The
slag can fill the need for more natural gravel in civil
engineering applications at a time when decreasing cement
production is limiting the use of fly ash in cement. A coal ash
fusing system has to satisfy the following requirements:
● the furnace must operate independently of the pulverised
coal-fired boiler;
● it must be capable of treating coal ash with a high fusing
IEA CLEAN COAL CENTRE

temperature of over 1500°C, using some flux and
oxygen;
● the exhaust gas from the furnace can be treated through
the same equipment handling the flue gas from the boiler.
The pilot-scale, coal ash fusing furnace has a diameter of
0.4 m and the length from the slag tapping hole is 3.7 m. It is
operated at atmospheric pressure and has three kinds of ports
for secondary air, coal and coal ash. The primary air is
divided to carry the coal and coal ash separately. All are
supplied tangentially to the furnace. A bituminous coal of
mean diameter 70 µm was fed at 20 kg/h in tests with a coal
ash of 20 µm diameter at zero or at 15 kg/h feed rate. The
temperature below the coal and coal ash port exceeded
1500°C. This was higher than that of the coal ash so that the
ash attached to the inner wall of the furnace and fused to
slag. The temperature around the slag tapping hole was kept
200°C higher than that of the flowing ash in order to
maintain a smooth flow. The test with 15 kg/h coal ash
resulted in a lower furnace bottom temperature (by about
20°C) than the test with no coal ash. This was due to the coal
providing heat to fuse the ash. The slag recovery rate was
85% and the resulting fly ash contained less than 5% unburnt
carbon. Hence the furnace is suitable for coal ash which is
hard to reuse because of its large diameter or high carbon
content. The addition of coal ash to the furnace increased the
NOx concentration by about 10% but to an acceptable
maximum value of 150 ppm. The coal ash slag satisfied
requirements with respect to trace element leaching and
alkali reactivity for use as aggregates in concrete (Ishiga and
others, 2003).
Oxidation
Hamley and others (2001) in the UK propose using
supercritical water to remove carbon from fly ash. This
would have the additional benefit of releasing the heat
content of the ash to improve the plant efficiency.
Supercritical water oxidation is a high temperature and
pressure technology which uses the properties of supercritical
water to breakdown organic compounds and toxic wastes.
Tests were carried out on a 1 MW combustor and
supercritical water oxidation rig to demonstrate the feasibility
of applying the technology to remove unburnt carbon from
fly ash. The preliminary results showed the LOI decreased in
all samples of fly ash after supercritical water oxidation. The
LOI varied from 4–22% before the treatment to 3–6%
afterwards, reductions ranging from 19% to over 80%. The
efficiency of carbon removal was variable. The highest
removal efficiencies were found with high LOI fly ash
samples from the more reactive South American coals from
Colombia and Venezuela. The lowest carbon removal was
with low LOI fly ash samples from Kuzbass, Russia. It is
possible that removal efficiency may be linked to the
reactivity of the coals and further work was aiming to
optimise the oxidations process and improve understanding
of probably links between the nature of the residual carbon
and its oxidation potential.
5.1.7 Chemical neutralisation
Another approach to make marginal fly ash marketable is to
Cement and concrete – benefits and barriers in coal ash utilisation
Treatments and beneficiation
neutralise the adsorptive capacity of carbon in fly ash prior to
shipment to the concrete producer. A liquid reagent is applied
to fly ash to bind with the carbon in order to negate its effects
on air entrainment in concrete (Blankinship, 2001).
For example, Boral FACT™ is a new proprietary fly ash
carbon treatment process (patent pending) which neutralises
the adsorptive capacity of fly ash carbon. It is claimed to be
applicable on demand, can be used at high doses with no
negative impact on concrete and to have low capital costs
(BORAL, 2003).
5.2 Ammonia
The ammonia in fly ash can be reduced by heat treatment at
150–200°C, for example the commercial ASH PRO
Liberation process (Hall and Livingston, 2001). Other
processes based on heat treatment are combined or separate
from the processes for reduction of carbon in ash described in
Section 5.1.
Burnout processes in Section 5.1.6 includes reburning high
carbon ash from one power station by transporting it to
another where more complete combustion occurs. Ramme
and others (2001) also describe laboratory tests with a
prototype ammonia liberation process developed by
Wisconsin Electric Power Company. The process is based on
application of heat to liberate the ammonia compounds from
the ash, consume undesirable carbon and render the ash a
marketable product. The design employs few moving parts to
keep wear and maintenance low. The system is adaptable to
meet the different ash characteristics generated by the various
NOx reduction systems as well as the quantity of ash needing
beneficiation. The process preheats the ash and then feeds it
to a processing bed where it is heated to about 538°C with
hot fluidising air. The fluidising air is supplied by a burner
and forced through a porous metal media. This provides
support for the ash and distribution for the air flow. The ash
is cooled through a heat exchanger and the reclaimed heat
may be used to preheat the incoming untreated ash. The
contaminated air is passed through a baghouse where any
fugitive ash is captured and returned to the ash exiting the
process bed. The process reduced the ammonia content of a
class C fly ash from 51 ppm to less than 2 ppm and of a class
F fly ash from 170 ppm to less than 2 ppm.
The ammonia contaminating fly ash is reduced to
non-detectable amounts as an important side benefit of the
CBO process. In pilot tests, feed ash with ammonia contents
of up to several hundred ppm resulted in product streams
with undetectable ammonia, even without process flow
changes. Long residence times of on average 45 minutes in
the fluidised bed together with average temperatures of about
732°C promote these reductions (Keppeler, 2003a).
Fly ash is typically difficult to fluidise because of the small
size of the particles. This is overcome by means of acoustic
enhancement in a dry process to remove ammonia from fly
ash described by Levy and Lawton (2003). Laboratory
experiments were carried out with a continuously operating,
inclined fluidised bed which is 15 cm wide and 6 m long.
55
Treatments and beneficiation

Scale-up to higher flow rates would be accomplished by
increasing the width of the bed. Ash is fed at one end and
ammonia is removed with the fluidising air and the fly ash
product is removed at the other end of the bed. The ash is
heated electrically and loud speakers are placed above the
distributor to promote bubbling fluidisation of the ash. In the
tests, the fly ash had an inlet ammonia concentration of
approximately 1100 ppm. The ammonia removal varied from
96% at a peak ash temperature of 432°C to 35% at an ash
temperature of 282°C. Ammonia removal depended primarily
on ash temperature and the residence times were long enough
in all cases. There were no difficulties with flow patterns of
ash or ash stratification which would lead to lower than
expected ammonia removal efficiencies. The energy costs to
operate the system were in the range of 2.75 US$/t of ash.
This could be reduced by preheating the ash with energy
recovered from the ash cooler heat exchanger.
In the MCB process, ammonia, usually in the form of
ammonium sulphate, decomposes thermally at temperatures
consistent with carbon burnout. The exhaust gas stream from
the fly ash burnout process is fed into the flue gas stream of
the coal combustion plant, replacing a portion of the
ammonia injection requirement. Four of the samples were
ammoniated fly ash with ammonia concentrations of
3–1194 ppm. The process reduced the concentrations to
below 10 ppm in most cases (Tranquilla and MacLean,
2001).
Another ammonia separation process using hydrated lime has
been patented by STI. This may be used alone or in
combination with the STI carbon separation technology
(Bittner and Gasiorowski, 2003) (see Section 5.1.4). The first
full-scale application of this ammonia removal process
started operation at the St John’s River Power Park, FL,
USA, in 2003 and is shown in Figure 15. The ammonia gas
collected is recycled to the flue gas of the generating unit,
reducing the ammonia addition required to control SO3
emissions. The ammonia content of the incoming fly ash
varies from around 200–900 ppm. Typical results at varying
feed rates from 18–36 t/h of contaminated ash are shown in
Table 13. The ammonia in the fly ash is reduced to 9–25 ppm

ammonia gas recycle to generating unit

ammoniated
ash
dry
alkali
mixer vent filter
dryer filter receiver

solids feeders

solids flow meter

water supply

product
ash
high-intensity
mixer M

low-intensity mixer M

flash dryer
dryer burner

Figure 15 STI ammonia removal process (Bittner and others, 2003)

Table 13 Full-scale ammonia removal process results (Bittner and others, 2003)

Fly ash feed, rate,t/h Lime rate, % of feed Water rate, % of feed Initial ammonia, ppm Final ammonia, ppm

19 1.35 1.9 910 25

36 0.70 2.05 350 12

16 0.82 1.52 242 20

23 0.88 2.6 190 9

56 IEA CLEAN COAL CENTRE

 Treatments and beneficiation

and the resulting fly ash meets all specifications for use in
concrete (Bittner and others, 2003).

ISG Resources Inc (now Headwaters Resources) has

developed a technology involving the oxidation of ammonia
using addition of agents such as hypochlorites to fly ash,
mortar or concrete slurried. The oxidisers can be introduced
in dry or wet form. When water is added, the reaction
produces monochloramine and chloride salts that are stable
and do not dissipate into the air. This eliminates odorous
emissions and, at the amounts tested, the salts are harmless to
concrete and concrete applications. The effects of oxidation
treatment on compressive strength and other tests for
concrete quality are positive (Power, 2002).

5.3 Comments
Treatments and beneficiation developed to commercial use in
order to increase utilisation of fly ash include:
● draining and drying of stockpiled fly ash, to release
lagoon space;
● air classification and hydraulic classification for stored
ash;
● grinding;
● sieving and blending;
● electrostatic separation;
● froth flotation;
● gravity and magnetic separation;
● reburning high carbon fly ash in another power station
with more complete combustion;
● carbon burnout.

Other processes reported to be in the development and testing

phase include:
● microwave carbon burnout;
● ash modified clinker technology;
● slagging furnace;
● supercritical water oxidation;
● chemical neutralisation of carbon in fly ash.

Most of these processes relate to reducing carbon in ash and

making the ash finer. Many also reduce ammonia in ash. In
addition, an ammonia separation process using hydrated lime
is now used commercially and a technology involving
oxidation of ammonia has been developed.

Cement and concrete – benefits and barriers in coal ash utilisation 57

 6 Conclusions
Use of fly ash in cement and concrete brings many
engineering benefits which have long been recognised and
deployed. All applications for fly ash reduce the use of
natural raw materials and therefore contribute to industrial
sustainability. Blended cements and concretes containing fly
ash offer the benefit of CO2 emissions avoidance and the
possibility of high substitution rates, especially for some
calcareous fly ashes. Nevertheless fly ash utilisation is still
hindered where it has a by-product rather than a product
status. Regulations for use in cement and concrete need to be
broadened to include all potential markets for a wider range
of fly ash specifications. In some respects, use of fly ash in
the raw material in cement kilns has the advantage of less
rigorous requirements than for blended cement or concrete
but the amount appears to be limited, depending on the
availability of other raw materials. Commercial treatments
include draining and drying of stockpiled fly ash,
classification, separation and burnout processes. These are
helping to meet the challenge of using high carbon fly ash in
traditional markets. The emphasis is turning towards total use
of fly ash by producing useful, high-grade and expensive
materials which may find various specialised applications.
Cement
Fly ash is used mainly for its alumina in cement kilns but
also contributes silica, iron and calcium to the raw material
mix. The amounts of fly ash used depend primarily on the
raw material available at a cement works, that is on the
composition of the limestone and clay deposits. The rate of
substitution is generally 3–5% of the raw materials. The
higher rate is practised in Japan where some power stations
choose coal in order to produce fly ash which is most suited
as a clay substitute. Utilisation of fly ash in this application is
also favoured by cost effective transport arrangements where
cement companies supply limestone for FGD sorbent by ship
to power stations and receive fly ash or gypsum back for
cement raw material.
Much greater quantities of fly ash can be used in blended
cement, usually substituting for 5–40 wt% of the Portland
cement clinker. Use of calcareous class C fly ash for rapid
hardening hydraulic cements is possible at over 80 wt% fly
ash substitution with additives in the USA. Requirements for
fly ash quality are tightly defined (see for example Table 7).
Despite providing a certificate, regulations can act as a
barrier to increased use of fly ash. Fly ashes with different
characteristics could find good markets but lack building
authority approval.
Improved clinker quality is a benefit of using fly ash in the
raw material mix. This is due to fly ash having a lower alkali
content, less SiO2, more Al2O3, and being finer than clay. The
advantage of this application is that the fly ash does not have
to meet the stringent quality standards required for blended
cements.
Avoidance of CO2 emissions is an important benefit of fly
ash blended cements. Every tonne of cement clinker replaced
58
with fly ash avoids the emission of 1.2 t of CO2. Marketing
barriers are being overcome to achieve CO2 emissions
reduction through partnerships, for example, between
utilities, coal combustion product marketers, and cement
producers. Close proximity of power station and cement
works as well as long-term agreements favour successful
marketing.
The requirements for handling dry rather than wet fly ash for
both uses in cement have to be met by modifications to
existing plant or designed for new plant. Pneumatic
conveying systems offer dust free operations and economy of
space over short distances and bulk carriers are used over
longer distances. Large storage domes allow the purchase and
stockpile of sufficient fly ash over seasons when fly ash is
least expensive to when it is most in demand for cement.
High carbon fly ash poses problems when injecting fly ash
into the preheater of the cement kiln where temperatures are
relatively low. However, studies in the USA have shown that
fly ash containing up to 21% unburnt carbon can be used in
cement raw material. This has the benefit of reducing the
energy requirements and hence costs. The highly alkaline
lignite ashes in Germany have limited use in cement kilns.
Restrictions are tighter for use of fly ash in blended cement,
for example, not exceeding a LOI of 5% in Europe but up to
7% LOI may also be acceptable in some cases.
Cofiring coal with other fuels may affect the quality of the
fly ash produced for both cement kilns and for blended
cements. Tests in the Netherlands show that up to 20 th%
waste wood, up to 15 th% refuse derived fuel and a small
percentage of chicken litter could be used without affecting
the fly ash quality. Only limited data are available on the
amount of mercury in cement raw materials and none on the
variability or speciation.
Concrete
Fly ash may be used to replace part of the cement in
concrete, sometimes exceeding 50 wt% of total cementitious
components in the case of calcareous fly ash. Substitution
rates up to 35 wt% for overall satisfactory early strength, and
40 wt% fly ash or less for durability, are frequently used. Fly
ash may also be added as fine aggregate or partially replace
cement, fine aggregate and water. In general, the quality of
the fly ash is greater when it is finer and has a lower carbon
content. Requirements for the many different concretes
produced vary considerably and examples are shown for
Europe, Japan and the USA in Tables 8, 9, and10
respectively. The specified loss on ignition (LOI) ranges in
these from 3–8% or 2–9% in future in Europe but 12% is
permitted in India. Countries where freezing occurs may limit
the LOI to 5%.
Fly ash is beneficial in concrete due to its pozzolanic
reactions with free lime, rounded particle shape and by
reducing the water demand. The latter helps to avoid
segregation and bleeding in fresh concrete as well as
IEA CLEAN COAL CENTRE

improving long-term strength and durability. Concretes
enhanced with fly ash may have a lower initial strength.
Probably the greatest engineering benefit from using fly ash
is the reduction of the alkali silicate reaction (ASR). This
occurs with some aggregates and often causes premature
and severe cracking of concrete. Fly ash substitution rates
of 15–>30 wt% are sufficient to mitigate ASR, depending
on the calcium content of the ash and the reactivity of the
aggregate. Low calcium ashes (<2% CaO) are effective at
lower rates than high calcium ashes. This benefit appears to
show little difference for a wide range of fineness and for
both dry and conditioned (stored) fly ashes. Other
advantages include lower permeability, and hence better
performance in aggressive environments, as well as higher
electrical resistivity, reducing corrosion of the
reinforcement.
Set time is generally longer through addition of fly ash to
concrete. The effect is greater in cold weather and this may
limit the addition of fly ash. Calcareous fly ashes show mixed
effects and class C fly ash may be used to make rapid
hardening hydraulic cements with over 80% fly ash
substitution, for use as concrete paving mixes for roads,
bridges or runways.
The lower early strength of fly ash concretes may suit some
applications. However, where early strength development is
insufficient, the water to cement ratio can be reduced or
sulphates may be added to activate the cement. Strength
development is improved by using ultra fine fly ash, for
example in South Africa, instead of the more expensive silica
fume (see Figure 8). Addition of other materials such as rice
husk or sewage sludge ashes enhanced the early strength of
fly ash concretes.
Many different types of concrete benefit from fly ash
components. Roller compacted concretes are used with high
fly ash replacement rates of over 50 wt%, for example in
dams and roads. Self-compacting concrete, which flows
uniformly into the form without segregation, requires
considerably more fines compared to traditional concrete. Fly
ash is a less expensive option than silica fume for this
purpose and large amounts of fly ash are successfully
substituted for cement and as a filler. Tests in Italy at a
45 wt% rate showed a 28-day compressive strength of
48 MPa and improved bond with steel. High performance
concretes achieved compressive strengths of over 60 MPa
using 40 wt% fly ash at lower cost than using only cement or
silica fume in research work in Portugal. High strength
concretes made with greater proportions of locally plentiful
sand in north Germany benefit from 20–33 wt% fly ash as
filler between the sand grains. Fibre-reinforced concrete
using 18–40 wt% fly ash as cement has resulted in denser
industrial floors with less cracking.
Use of fly ash to substitute for aggregate at high replacement
rates, for example in India at up to 50 wt% of sand, increases
the compressive, tensile and flexural strengths, as well as the
modulus of elasticity. Cellular concrete using coal ash
(30–90 wt% of total solids) in CO, USA, is lighter in weight,
has greater heat resistance and costs less than concrete made
with usual aggregates.
Cement and concrete – benefits and barriers in coal ash utilisation
Conclusions
Enhanced durability through adding fly ash to concrete
includes better resistance to alkali, sulphate, chloride and
CO2 ingress, corrosion and preventing deterioration due to
ASR. A 40 wt% fly ash mix showed low expansion and
favourable strength development in sulphate solution and
gave good resistance to chloride. Higher class C fly ash
contents up to 70 wt% gave good results. Sulphate resistance
of concrete was higher when replacing cement than for
replacing sand. However, tests for marine durability in Japan
for high carbon fly ash used to replace aggregate at up to
46 wt% in the concrete were successful. Freeze and thaw
durability and the ability to withstand use of de-icing
materials appear to improve in some fly ash concretes but
this issue is under investigation.
Environmental benefits include reduced CO2 emissions and
avoidance of primary aggregates. For example use of 30 wt%
fly ash in concrete can reduce CO2 emissions by 17% and
energy use by 14%. This benefit is enhanced by the higher
fly ash substitution rates indicated above and concrete based
on the new magnesium eco-cement gives an even greater
opportunity of using more fly ash. There is a large surplus of
stored fly ash in many countries and yet high consumption of
primary aggregates. Combining conditioned fly ash with sand
(at up to 15 wt%) at the quarry and marketing the product as
an ‘active’ sand would provide a solution. Higher fly ash
additions of 30 wt% may be added as fine aggregate with
recycled building rubble as coarse aggregate. This becomes
economic when avoided disposal costs for fly ash are
included (see Table 11).
Barriers need to be overcome to expand ash markets by
greater co-operation in marketing networks between suppliers
and users of fly ash. Fly ash should be marketed as a product
rather than a by-product, defined for targeted users who
include architects and engineers as well as concrete
producers. Accurate forecasting of seasonal demand and
integration of ash marketing with appropriate coal
procurement and handling functions optimise supply to
demand. Transport and storage may be economic barriers to
using fly ash and the competitive distance for road deliveries
from a cement works is said to be up to roughly 200 km. Fly
ash storage domes offer maximum capacity with minimum
footprint.
There are barriers through greater use of emissions reduction
systems. Higher carbon in ash as a result of NOx emissions
reduction prevents its application in many concretes. Hence
beneficiation and separation is used to solve the problem.
Studies of ammonia release from fly ash from power stations
using ammonia based NOx control show there are no safety
concerns for workers. The rate of loss of ammonia from
concrete was limited by diffusion through the concrete.
Ventilation would support a maximum concentration of
70 mg/L so as not to exceed 10 ppm ammonia in the air
(see Figure 9).
Cofiring coal with other fuels presents another barrier since
the fly ash is excluded from use in concrete in most
countries, although it is permitted with certain restrictions in
Germany and the Netherlands. Fly ashes from cocombustion
at up to 10 wt% of paper sludges and biomass pellets have
59
Conclusions

been shown to conform to the European standard for more complete combustion, and the carbon burnout process
concrete. Conformity tests are in progress in the Netherlands shown in Figure 14, which achieves a consistent LOI of
for fly ashes from cocombustion of poultry litter, cocoa #2.5% regardless of feed LOI. A microwave carbon burnout
shells, coffee grounds, sewage sludge and demolition wood. process is being tested in the USA and Canada on fly ash
The effect on fly ash of using greater amounts of alternative with LOI ranging from 4–30%. Fusing processes under
fuels is also under investigation. This issue requires better development include the ash modified clinker (AMC)
understanding in view of efforts to increase cocombustion technology from China, and a slagging furnace in Japan.
with biomass to reduce greenhouse gas emissions. Supercritical water oxidation is proposed in the UK to
remove unburnt carbon from fly ash. Chemical neutralisation
Leaching of mercury and other trace elements from concrete is a new approach to negate the effect of carbon in fly ash on
incorporating fly ashes has been shown to comply with air entrainment in concrete. This is carried out prior to
regulations. Most of the mercury is released only above shipment to the concrete producer.
300°C, making it stable for most concrete applications.
Mercury emission controls based on activated carbon may Ammonia from NOx control systems can contaminate fly ash
affect use of fly ash in concrete but new mercury sorbents at 200–2500 ppm and needs to be reduced to <100 ppm. It
under development are unlikely to have a detrimental effect. may be removed by heat treatment to <30 ppm and by
burnout processes to <2 ppm. Ammonia treatment may be
Treatments and beneficiation combined or separate from the processes for reduction of
Draining and drying of stockpiled fly ash is being used to carbon in ash. Other processes being developed include a dry
release lagoon space and increase utilisation of fly ash. Most process based on acoustic enhancement, another using
treatments focus on reducing the carbon in fly ash used in hydrated lime (see Figure 15, Table 13), and use of oxidising
concrete. The carbon may be increased through use of low agents such as hypochlorites.
NOx burners or by less efficient combustion to
loss-on-ignition (LOI) values as high as 30%. Fly ash is
classified in the different stages of the ESP hoppers. Air
classification is carried out in the UK and Hong Kong for all
fly ashes used in structural concretes, achieving a fineness
<12% on a 45 µm sieve and LOI <7%. Many fly ash products
are made with various degrees of fineness and carbon
content, depending on requirements. A multi-stage air
classification process can be used to achieve low LOI from
high carbon fly ash. Hydraulic classification is used for
stored ash in the USA. Flocculation may be a problem when
fly ash is to be used as a filler and this requires a
superplasticiser. Grinding fly ash can improve the
compressive strength of concrete (see Figure 8). A patented
intense grinding process improves binding performance to
permit a greater proportion (>20%) of fly ash to be used.
Sieving and blending of fly ashes from different plants as in
the Netherlands, is used to produce a high quality fly ash and
high carbon fly ash (see Figure 11) with strict quality control.

Separation processes appear to be progressing towards total

use of fly ash by producing useful, high-grade and expensive
materials which may find various specialised applications.
Gravity separation is suitable for fly ashes with variable
particle density. Magnetic separation produces fly ash
suitable for the ceramic industry and extracts an iron product.
Aerodynamic drag can be added to the separation process to
give low LOI fractions and low density fractions for other
uses. Froth flotation may be used in combination with
classification to produce low LOI and fine fly ash products. It
also forms the basis of a multi-stage process (for example
Figure 12) to produce several products using all of the fly
ash. Electrostatic separation is used commercially
(see Table 12, Figure 13) and reduces the LOI to 2% from a
wide range of values up to 30%. Electrostatic separation may
be combined with ESP ash collection in a process under
development, which should also be applicable to wet ESP.

Burnout processes in commercial use in the USA include

reburning high carbon fly ash in another power station with

60 IEA CLEAN COAL CENTRE

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