Full Text 01

New Techniques for Continuous
Chemical Analysis in the

Pulp & Paper Industry
Matthew Rice
Department of Chemistry
Division of Analytical Chemistry
Royal Institute of Technology
SE-100 44 Stockholm
Sweden
Akademisk avhandling som med tillstnd av Kungliga Tekniska Hgskolan i Stockholm framlgges till granskning
fr avlggande av teknologie doktorsexamen, fredagen den 4 maj 2001, kl 10.00 i Kollegiesalen
Administrationsbyggnaden, Vallhallavgen 79, KTH, Stockholm. Avhandlingen frsvaras p engelska.
New Techniques for Continuous Chemical

Analysis in the Pulp & Paper Industry
PhD Thesis
Matthew Rice, 2001
ISBN 91-7283-063-8
Royal Institute of Technology
Department of Chemistry
Division of Analytical Chemistry
SE-100 44 Stockholm
Sweden
Printed by Universitetsservice US AB, Stockholm, 2001.
ii
An expert is a man who has made all the mistakes

which can be made, in a narrow field.
Niels Bohr (1885-1962)
This doctoral thesis is dedicated to the pursuit of a better

understanding of papermaking chemistry gained from new
analytical techniques for continuous chemical analysis.
iii
iv
Abstract
New Techniques for Continuous Chemical Analysis in the Pulp & Paper Industry
Matthew Rice, Royal Institute of Technology, Department of Chemistry, Division of Analytical
Chemistry, SE-100 44 Stockholm, Sweden.
This thesis presents some new techniques that were developed for continuous chemical analysis
of a paper furnish. First, a general background is presented, covering topics from the origins of
papermaking to present day. A short introduction to papermaking chemistry and a variety of
presently available on-line chemical analysers and measurement strategies are also discussed.
A method is described for the continuous fractionation of a paper furnish containing coarse
fibres (>10m) in order to obtain a sample for analytical purposes (Paper I). A consistent
sample, containing a representative fraction of the dissolved and colloidal substances (DCS)
present in the bulk furnish, was achieved by preventing cake formation on a filter surface. A
combination of turbulent flow above a membrane filter, while continuously withdrawing a
relatively low sample volume, were key factors in the prevention of filter fouling.
For the continuous flow-extraction of DCS, a technique is described whereby the extracting
solvent was injected at a high velocity into a continuous flow of analyte (Paper II). Comparison
with conventional flow extraction showed an extraction enhancement of up to 9 times for
colloidal triglycerides.
To achieve a continuous determination of chemical substances, a real-time fully automated
colorimetric titration apparatus was developed (Paper III & IV). This was achieved by using a
series of micro-machined mixing channels for the continuous flow of analyte, with a sequence of
detection units and titrant addition points along the flowpath (Paper III). A fuzzy logic
controller was implemented to continuously adapt for changes in the sample concentration,
providing the possibility of titrating over two orders of magnitude in sample concentration with
minimal loss of accuracy (Paper IV).
Also, a system is presented whereby the filtration apparatus (Paper I) is combined with the
titration device (Paper III & IV) in order to continuously determine total charge (or colloidal
charge) of a paper furnish in real-time (Paper V). This was achieved by utilising a back-titration
approach and selected examples are presented showing the dynamic interactions between wood
fibres and polyelectrolyte adsorption at various conditions of pH and polyelectrolyte molecular
weight.
Finally, some suggestions for a more comprehensive wet-end chemical monitoring platform are
discussed and the role of the present work in evaluated in this context.
Keywords: Chemical monitoring, continuous flow extraction, cross-flow filtration, dissolved
and colloidal components, fuzzy-logic control, on-line system, pitch analysis, polyelectrolyte
titration, process control, sample work-up, titrimetric analysis.
Matthew Rice, 2001
ISBN 91-7283-063-8
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List of Publications
This thesis is based on the following publications, which are referred to in the text by
their Roman numerals.
I.
Rice, M., Roeraade, J. and Holmbom, B. High-shear turbulent flow filtration

for chemical monitoring of pulp and paper process waters Nord. Pulp Pap.
Res. J., 14(4) 1999, 292-299.
II.
Rice, M., Roeraade, J. and Holmbom, B. Continuous-flow extraction of

colloidal components in aqueous samples Anal. Chem. 69(17) 1999, 35653569.
III.
Rice, M. and Roeraade, J. Continuous titration device for process analytical

applications Anal. Chim. Acta (submitted 2001).
IV.
Rice, M. and Roeraade, J. Fuzzy-logic to fully automate end-point control of

a continuous titrating apparatus for process analytical applications Anal. Chim.
Acta (submitted 2001).
V.
Rice, M. and Roeraade, J. Continuous filtration and titration apparatus for real
time monitoring of polyelectrolyte concentration and cationic demand of a
paper furnish Nord. Pulp Pap. Res. J. (submitted 2001).
Reprints are published with the kind permission of the journals concerned.
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Contents
1. Introduction .............................................................................................................................1
2. Papermaking.............................................................................................................................3
2.1. A Historical Perspective ...............................................................................................3
2.2. Modern Papermaking: A Global Industry ................................................................5
2.3. Papermaking Chemistry................................................................................................7
2.3.1. Papermaking Fibres ...............................................................................................7
2.3.2. Wood Fibre Chemistry ..........................................................................................8
2.3.3. Chemical Additives ............................................................................................. 10
2.3.4. Detrimental Substances...................................................................................... 12
2.4. Current Trends & Problems ..................................................................................... 13
2.4.1. Recent Changes in the Papermaking Chemical Process ................................ 13
2.4.2. Recent Developments of On-Line Instrumentation...................................... 14
3. Sample Work-Up.................................................................................................................. 17
3.1. Primary Separation Techniques [Paper I]................................................................ 17
3.1.1. Centrifugation...................................................................................................... 18
3.1.2. Filtration ............................................................................................................... 18
3.2. Continuous Flow Extraction [Paper II] .................................................................. 21
4. Continuous Dynamic Titration .......................................................................................... 23
4.1. New Titration Device [Paper III]............................................................................. 23
4.1.1. General Principle & Construction .................................................................... 24
4.1.2. End-Point Determination .................................................................................. 26
4.1.3. System Characteristics ........................................................................................ 28
4.2. Automation of Titration Device [Paper IV] ........................................................... 29
4.2.1. Fuzzy Logic Controller....................................................................................... 29
4.2.2. Continuous Titration .......................................................................................... 33
4.3. LabVIEW Program.................................................................................................. 34
5. Applications .......................................................................................................................... 35
5.1. Continuous Back Titration on a Paper Furnish [Paper V] ................................... 35
5.1.1. Polyelectrolyte titration ...................................................................................... 36
5.1.2. Experimental Results.......................................................................................... 39
6. Conclusions & Future Outlooks ........................................................................................ 43
7. Acknowledgements .............................................................................................................. 47
8. References ............................................................................................................................. 49
ix
List of Abbreviations
A-D
CFE
COD
DCS
FIA
FLC
GC
GUI
HPLC
HVIFE
IR
LED
LWC
m.w.
MSE
MTBE
NTU
oTB
P&B
PCMCIA
pDADMAC
PTFE
PVSA
SC
TOC
TMP
UV
Vdc
vis
analogue-digital
continuous flow extraction
chemical oxygen demand
dissolved and colloidal substances
flow injection analysis
fuzzy logic controller
gas chromatography
graphical user interface
high performance liquid chromatography
high velocity injection flow extraction
infra red
light emitting diode
lightweight coated
molecluar weight
mean squared error
methyl tert-butyl ether
nephelometric turbidity unit
o-toluidine blue
paper and board
personal computer memory card international association
poly-(diallyldimethylammonium chloride)
polytetrafluoroethylene (Teflon)
poly-(vinylsulfonic acid, sodium salt)
super-calendered
total organic carbon
thermomechanical pulp
ultra violet
volts (direct current)
visible (spectra)
List of Symbols
a0
a1
a2
A
e
i
k
K1
K2
N
t
T
V
V0
curve-fit coefficient
absorbance
error (end-point)
photocell number
cycle step
equilibrium constant
equilibrium constant
photocell calibration constant
time
transmittance
voltage (signal)
voltage (calibration constant)
wavelength
degree of membership
xi
xii
1.
Introduction
he origin of chemical analysis dates back to the advent of chemistry, the first
chemists requiring knowledge towards the identity and quantitative composition of
the materials with which they were working. In 1788, the Swedish chemist Torbern Olof
Bergman published his De Analysi Aquarum (On Water Analysis), a comprehensive
account introducing devised analytical methods for the analysis of mineral waters1-4.
This was generally accredited as the birth of Analytical chemistry as a discipline5.
Towards the end of the 19th century, new analytical techniques such as electrogravimetric
analysis and photometers were introduced to complement the wealth of classical assays
that were available at the time, however instrumental chemical analysis did not flourish
until well into the 20th century5. Since the advent of the microprocessor during the
1960s, analytical chemistry has undergone a rapid growth, strongly influenced by
advances in automation and miniaturization. The rapid transformation of classical to
instrumental analysis has overseen the automation of many laborious analytical
techniques, providing greater throughput, accuracy and reproducibility.
Parallel to the development of laboratory instrumental analysis, process analytical
chemistry developed in response to the needs of industry to obtain real-time
measurements. New analysis tools evolved to provide direct chemical and physical
information describing the composition of a process stream, enabling optimisation and
control to be implemented in real-time. Today, industrial processes ranging from
petrochemical to biotechnology often rely upon process analytical measurements for such
benefits as enhanced product and process quality management, environmental control
and monitoring, and crisis alerting6-9.
More recently, the pulp and paper industry has also realised the essential benefits gained
from a real-time monitoring of the wet-end chemistry. Primarily instigated from
strengthening environmental legalisation and increasing product demands stipulated by
the consumer, the past decades have seen substantial change with the chemistry of the
papermaking process10-19. In addition, the variety of papermaking chemical additives is
ever increasing to suit the specific requirements of the papermaker20-23. Such recent
changes have emphasised the urgent requirement for a better understanding of the
papermaking chemistry, and as a consequence, the necessity of more specific on-line
chemical sensors and monitoring devices24-34.
Prior to the mid 1980s, attempts to monitor and control the paper machine wet-end were
still scarce35. Although computer-based online process control systems have been widely
used in the pulp and paper industry, progress has been slow for wet-end chemistry system
development (currently only pH, thickness, consistency and additive flow rate are
routinely measured on-line)36-39. In order to develop computer based wet-end chemistry
process control systems, new robust on-line sensors must be developed. Concentrating
on the most important variables and their interrelationship is the key to improving
performance on a paper machine. A wet-end chemistry process control system would
reduce variability by detecting chemical parameters that influence paper quality at an early
stage. A stable papermaking process is the basis for higher quality, lower costs, higher
recycled content, substantially less waste, faster grade changes and the development of
higher value-added products.
This thesis presents some new techniques that were developed with the aim of dedicated
use in continuous real-time chemical analysis of a paper furnish. The dissolved and
colloidal components of the furnish were the key constituents chosen for analysis as
these materials are generally almost always detrimental in nature and it is clear that a
better understanding of the dynamic interactions of such substances and their impact on
the process is of great importance to the papermaker.
Initial work focuses on the development of suitable sample work-up procedures in order
to continuously remove extraneous materials from a bulk paper furnish that are not
required for subsequent analysis (Paper I), and to continuously extract colloidally
dispersed pitch from an analyte (Paper II). Subsequently, a continuous real-time
colorimetric titration apparatus was developed in order to allow a quantitative
determination of the amount of chemical substances present in an analyte (Paper III &
IV). The final work (Paper V) demonstrates a combination of the apparatus and
techniques developed in papers I, III and IV, in order to perform a continuous colloidal
titration directly on a paper furnish in real time. While the bulk of this work was carried
out with the objective to be able to monitor the wet-end of the papermachine, it should
also be possible to employ the apparatus and techniques developed for use in pulping and
bleaching plant, as well as for effluent monitoring.
2.
Papermaking
lthough modern papermaking is a highly mechanised process, the basic procedure

has remained essentially unchanged for nearly two thousand years. Fibres, most
commonly obtained from wood nowadays, are first separated and wetted to produce a
paper pulp or stock, then filtered on a woven screen to form a sheet, pressed to squeeze
out most of the water, and finally dried to evaporate the remaining water. The dry sheet
is often further compressed, coated and possibly impregnated with other substances to
obtain the desired properties for its intended use.
2.1.
A Historical Perspective40-48
From the dawn of civilization, the human race has had the need to communicate in the
form of writing, whatever the physical medium. The first records of written language
were clay pictographs used by the Sumerians as early as the fifth millennium BC. As
written languages developed throughout other civilizations, many different materials were
utilized to record the written word. Stone, clay, parchment, vellum, bark and tree leaves
have all filled this role at one time or another.
The ancient Egyptians, as discovered in tombs dating back to 3500 BC, made the written
word more portable with the advent of papyrus. Papyrus, the word paper is derived
from, consists of fibrous layers from the reedy plant papyrus placed side-by-side and
perpendicular in alternate layers. The structure was dampened, pressed and upon drying,
the glue-like sap of the plant fastened the layers together.
Complete defibring, a central requirement in modern papermaking, did not occur with
the manufacture of papyrus. The first account of papermaking was ca. AD 105 when
Tsai Lun, an official attached to the imperial court of China, created a sheet of paper
from the bark of the mulberry tree and other fibres made on a mold of bamboo strips.
However, the discovery and art of papermaking remained in China for over 500 years.
From China, trade caravans imported paper to Japan around AD 610, Central Asia and
Persia ca. 750. In its slow migration westward, the Moors brought paper to Europe with
the first papermaking mill established in Spain around 1150. During the subsequent
centuries, papermaking spread throughout most of the European countries.
However, it was not until the introduction of the printing press in 1450 by the German
ironworker Johann Gutenberg that papermaking experienced significant growth - for the
first time in history the written word could be mass-produced and paper was in demand.
The ever-increasing need for paper
resulted in shortages of raw materials
during the 17th and 18th centuries.
Up to this period, European
papermaking primarily utilized linen
and cotton rag as raw materials and it
was evident that a new and more
abundant substitute was required.
During the same period, attempts were
made to further reduce the cost of
paper by developing machinery to
replace the hand-molding process.
Nicholas-Louis Robert in France
introduced the first papermaking
machine in 1798 whereby a continuous
flow of stock was delivered to a
moving screen belt, delivering an
unbroken sheet of wet paper to a pair
of squeeze rolls. Robertss machine
was not realized however until the
British stationers Henry and Sealy Figure 2.1. Water paper mill circa 1662. From Georg
Fourdrinier developed an improved Andre Bckler, Theatrum Machinarum Novum
45
version in 1803, followed two years (Nuremberg 1662) .
later with a cylinder papermaking machine by the English Papermaker John Dickinson.
A cheap and abundant raw material substitute was first achieved by a German weaver,
Friedrich Gottlob Keller, in 1840 by the introduction of the groundwood pulp process
a mechanical method of defibring wood fibre. Hugh Bergess and Charles Watt
developed the first chemical defibring process, soda pulp, in England approximately 10
years later. From these crude beginnings, modern papermaking evolved.
Papermaking
2.2.
Modern Papermaking: A Global Industry
At the turn of the new millennium, there were 8873 paper and paperboard (P&B) mills
and 5946 wood pulp mills, producing a combined 316 million tons of P&B and 179
million tons of pulp annually, in over 103 countries spanning the globe49. Despite all the
hype of how new technologies such as the paperless office and the Internet would
strangle paper output, the last year of the 20th century saw a staggering increase of over
4.6 % in production on 1998 figures50-52. Figure 2.2 illustrates the production and
consumption statistics representing the global market.
Annual growth is projected at the average rate of ca. 1.8 % for P&B and 1.5 % for pulp,
with the most significant production increases expected for printing and writing
papers53-55. The major driving force behind this growth is the enormous population of
Asia. For example, the Peoples Republic of China, with a current population of over 1.2
billion has a per-capita consumption increase of ca. 1 kg per year56.
(1 000 000 tons)
Production/Consumption
(1 000 000 tons)
Production/Consumption
The past decades have also witnessed the introduction of huge and fast paper
machines57,58. The fastest newsprint machine today was recorded in June 1999 at the
Braviken paper mill (Sweden), with a
Global P&B Production/Consumption
record speed of 1 780 m.min-1 (107
(1999)
120
km.hr-1)59. Every day this machine
Capacity
100
produces a continuous 8 m wide web
Production
Consumption
80
long enough to cover a road from
60
Norrkoping in Sweden to Gibraltar.
40
An even faster machine has recently
20
been installed at the Golbey paper mill
in France, officially inaugurated on
0
a
a
ia
th ca
pe
sia
tin ric
ric
As
or ri
ro
la
60
La me
Af
N me
ra
April 30, 1999 . This newsprint
Eu
t
A
s
A
Au
machine is over 1.2 km in length, with
Global Pulp Production/Consumption
(1999)
a design speed of 1 800 m.min-1 and
100
The
capacity of 330 000 ton.yr-1.
Capacity
80
Production
fastest tissue machines today operate
Consumption
60
up to 2 200 m.min-1, the speed limited
by the drying capacity57.
40
Presently, over 400 specific types of
papers are produced, indicating the
diversity of the pulp and paper
industry61. Each grade is based upon
broad categories such as the type of
fibre used, the basis weight of the
20
0
pe
ro
u
E
th ca
or ri
N me
A
ia
As
a
si
la
rt a
s
Au
tin ric
La me
A
ric
Af
Figure 2.2. Global Paper & Board (P&B) and Pulp

manufacturing and consumption statistics for 199949.
material and specific properties62. Some descriptions of commodity type P&B grades are
provided in Table 2.1.
Table 2.1. Common paper and board grades with typical applications62.
Printing &
Writing Papers
Mechanical pulp
Newsprint - newspapers, telephone directories, inserts & flyers
SC papers - low-end magazines, catalogues
Coated - magazines, catalogues, inserts, commercial printing
Chemical pulp (fine papers)
Uncoated - magazines, catalogues, books, envelopes, business forms, bibles
Coated - magazines, catalogues, brochures, books and manuals, timetables
Special - copying, non-impact printing, low-volume paperbacks & hard cover books
Tissue
Hygene products
Bathroom - smooth or embossed, unprinted or patterned, pure white, off-white or tinted
Kitchen towels - as above however generally greater basis weight
Facial tissue - low-basis weight, smooth (calendered), generally two-ply
Table napkins - from small coffe cup napkins to large table napkins
Other
coffee filter paper, cigarette filters, padding for meat packaging
Paperboards
Cartonboards
Folding boxboard - packaging of cosmetics, cigarettes, pharmaceticals, food
White lined chipboard - as above except for food (due to recycled fibre content)
Solid bleached board - chocolate and cigarettes (no problems with odor or taint)
Solid unbleached board - beverage (can) packaging (high tear strength and stiffness)
Liquid Packaging board - milk and juice packaging
Container boards (cardboard boxes)
Linerboard - linear for corrugated board
Corrugating medium - used in corrugated board (the "wave" between the two liners)
Specialty
papers
Special boards
Core based - cores for paper rolls (such as toilet paper)
Wallpaper base - wallpapers
Plaster board- liners for gypsum board (a popular wall covering material)
Others - book binding board, beer mat board (used in restaurants under beer glasses)
Filter papers
Automotive - air and oil filters
Laboaratory & diagnosis - filters, test papers (impregnated with chemical reagents)
Household - coffee filters, tea bags, vacuum cleaner dust bag
Electrical papers
Cable paper - used for insulation between electrical cables
Transformer board - for uses where an insulation structure is required
Absorbant lamination papers
furniture, decoration panels, floors (normally laminated onto a particle- or fibreboard
to provide a good-looking resistant surface.
Other
strong papers (base paper for grinding belts and sandpaper), masking tape, photographic
paper, carbonless copy paper, map paper, security paper (banknotes), cigarette papers etc.
Papermaking
2.3.
Papermaking Chemistry63-71
One of the objectives of papermaking chemistry is to gain a better understanding of the

complex chemical and physio-chemical properties and interactions between the
papermaking process and raw materials. An understanding of papermaking chemistry
makes it possible to overcome a number of limitations and deficiencies inherent in the
raw materials in order to provide specific paper property specifications, to meet a
customers requirements more closely.
A paper furnish is the combination of all materials used to make paper, and generally
consists of fibres, fibre fines, functional additives, chemical process aids and a variety of
substances referred to as detrimental substances which interfere with the action of the
chemical additives in an adverse way. A typical paper furnish is schematically illustrated
in Figure 2.3.
2.3.1. Papermaking Fibres

Many different types of fibres have been used to make paper, including mineral, animal,
synthetic, and vegetable fibres. Vegetable fibres are by far the most important and, of
these, wood fibres find the greatest use.
Softwoods. Softwood fibres, which are approximately 3-7 mm long and 20-50 m in
diameter, have a high specific surface area and tend to flocculate when suspended in
water, providing an ideal matrix for papermaking. Typical softwoods include conifers or
cone bearing trees, such as pine, fur and cedar.
Polyelectrolytes
Cationic
Coagulant
Precipitated CaCO3
0.2 - 1m
Ti02
0,25m
Pitch
0.1-10 m
Figure 2.3. Typical components present in a paper furnish.
Softwood fiber
width = 36m
length = 3500m
Hardwood fiber
width = 22m
length = 1200m
Ground CaCO3
1 - 5m
Hardwoods. Hardwood fibres, which are approximately 1-2 mm long and 10-40 m in
diameter, while shorter than softwood fibres, still have a strong tendency to flocculate
when suspended in water. Unlike softwoods, hardwoods contain a large proportion of
non-fibrous elements, including vessel segments, ray cells and parenchyma cells. Typical
hardwoods include deciduous or annuals, such as birch and eucalyptus.
Other Fibres. Although virgin wood fibre is the foremost source of fibre for
papermaking today, increasing quantities of secondary fibres (recycled wastepaper) and
paperboard are being used to supplement the raw supply. Rag fibres are still used to
produce paper of maximum strength, durability and performance and are used
extensively for bank notes and security certificates. Other fibres include bagasse (residue
from crushed sugarcane), bamboo, esparto, flax, hemp, jute, kenaf and straw, while some
speciality papers are produced from synthetic fibres.
2.3.2. Wood Fibre Chemistry

Wood pulp fibres contain cellulose, hemicellulose, lignin as well as organic solventsoluble resins and fatty materials (extractives) that adversely contribute to the
papermaking process. The relative amounts of such materials are shown in Table 2.2.
Cellulose. Cellulose is the principal structural component of a wood fibre. Chemically,

it is a polysaccharide composed of glucose sugar units bonded end-to-end through
carbons 1 and 4 by an acetyl -linkage (Figure 2.4). In native cellulose, the chains are
typically 10 000 units long, however a shortening of the chains often occurs through
hydrolysis and oxidation during the pulping and bleaching processes. Cellulose chains at
the fibre surface contain hydroxyl groups that contribute to the fibre-to-fibre bonding in
paper.
Hemicelluloses. Hemicelluloses are also polysaccharides, but differ from cellulose in
that they contain a variety of sugars such as xylose, galactose, mannose and arabinose
(Figure 2.4). They are often branched and have a lower degree of polymerisation
compared to cellulose, typically containing 200-400 sugar units. Hemicelluloses interact
strongly with water and contribute greatly to the swelling of wood fibres during beating,
and promote the development of fibre-to-fibre bonding in paper. The carboxyl groups
on xylan glucuronic acid groups are the principal source of negative fibre surface charge.
Table 2.2. Chemical composition (typical) of wood69.
Cellulose
Hemicellulose
Lignin
Extractives
Softwood
42%
27%
28%
3%
Hardwood
44%
33%
20%
3%
Papermaking
9
Prominant structures of softwood lignin64
C
C
Two glucose molecules

H
OH
OH
C
CH2OH
O
CH2OH
H3CO
HC O[CH2OH]
OH
OH
CH
OH
OH
OH
O
OH
O
OH
OH
COOH
H2COH
O
HO
CH
H3CO
OCH3
HC
OH
HC
HC
OCH3
H2COH
H2COH
OH
H3CO
HC
OCH3
O
CH
CH2OH
HC
CH
CH
HC
CH2
O
HCOH
OCH3
HCOH
O
H3CO
OH
O
HC
OCH3
HCOH
H
C C
H
O O
H2C
HOH2C
CH 2OH
CH
H3CO
OCH3
H3CO
OH
CH 2OH
O
HCOH
Structure of softwood aribinoglucoronoxylan. The

structure is branced and contains xylose, glucuronic
acid, and arabinose sugars.
OH
HCOH
H3CO
H3CO
HCOH
CH2OH
CH
CH
HC
HCOH
HC
CH2OH
CH 2OH
HOH2C
OH
H2COH
O
CH
HCOH
H3CO
OH
H2COH
HC
C
H3CO
OCH3
OH[O C]
Figure 2.4. Chemical structures of primary materials present in a typical wood furnish.
Lignin. Lignin is concentrated in the cell walls of wood, holding the cellulose and
hemicellulose wood fibres together, providing mechanical strength. It is a mixture of
complex, polymeric compounds, phenylpropane units for the most part, containing many
inter-unit ether and carbon-carbon bonds (Figure 2.4). Lignin has a network structure
and a very high molecular weight. Residual lignin in papermaking fibres is detrimental to
both the papermaking process as well as the finished product. It inhibits interfibre
bonding, reduces swelling of the fibres in water, contributes to a rapid draining mat on
the paper machine and produces finished products with poor aging properties
(yellowing). The free phenolic groups on the surface contribute to fibre negative surface
charge when they ionise.
Extractives. Wood extractives include a wide range of non-polymeric organic
compounds that do not belong to the cell wall, typically fatty acids, resin acids, lignans,
sitoststerols, steryl esters and triglycerides (Figure 2.5). Extractives play important roles in
the life of a tree, providing food and energy storage and protection from microbial
attack, and offer valuable by-products in the kraft pulping process. However, their effects
on papermaking are always detrimental, contributing to such problems as foaming,
deposits, desizing, strength losses, and decreased paper quality.
10
Triglyceride:
1,2-dilinolen-3-linoleninglycerol
O
O
O
Resin acid:
abietic acid
O
O
Sterylester:
sitosteryllinolat
COOH
O
O
O
Sterol:
campesterol
HO
HO
O
O
OH
OH
Lignan:
hydroxymatairesinol
Fatty acid:
linoleic acid
COOH
Figure 2.5. Naturally occurring extractives present in a typical wood furnish.
2.3.3. Chemical Additives

Papermaking chemical additives are utilised to satisfy two primary objectives, namely
function and control, and are usually added to the stock at various locations prior to the
head-box. Functional additives are used to achieve desired paper properties and product
specifications, ultimately imposed by the customer, while control additives are used to
enhance paper machine runnability, a key factor for mill profitability.
Functional additives, such as dyes, internal sizing agents, wet and/or dry strength agents
and fillers etc. are often added to improve or impart certain properties to the finished
paper product. For such additives to be effective and the process to run efficiently, these
must be retained on the sheet. The majority of paper properties that are affected by wet
end chemistry can be summarised in the following five categories:
1. Structural properties (basis weight, porosity, roughness, directionality, twosidedness etc.);
2. Mechanical properties (tensile strength, bursting strength, tearing resistance,
stiffness, folding endurance, internal bonding strength etc.);
3. Appearance properties (opacity, brightness, colour, gloss etc.);
4. Permanence properties (durability, chemical stability, colour reversion etc.);
5. Barrier and resistance properties (sizing).
Control additives, such as biocides, drainage aids, retention aids, pitch control agents and
defoamers etc. are added to improve the papermaking process and do not directly affect
Papermaking
11
the finished paper product or are even necessarily retained on the finished product.
Some additives can also impart several effects at the same time, such as alum, which is
used for sizing under acid conditions as well as a drainage aid. Table 2.3 is a list of some
of the more common chemical additives used in papermaking with their intended effects.
Table 2.3. Common papermaking chemical additives71-72.
FUNCTIONAL ADDITIVES
fillers
dyes and brighteners
internal size
dry strength additives
wet strength resins
specialty chemicals
opacity, brightness and basis weight

- clay, calcium carbonate, talc, titanium dioxide
imparts colour/brightness
- basic/acid dyes, direct dyes, fluorescent brightening agents
resistance to water penetration
- rosin sizing with alum, alkylketone dimer (AKD), alkyl succinic anhydride (ASA)
increases hydrogen bonding
- polyacrylamides, starch, guar gum, (carboxy)methyl cellulose
promotes covalent fibre-fibre bonding
- urea formaldehyde (UF), melamine-formaldehyde (MF), glyoxal-polyacrylamide
copolymers, epoxidized polyamine-polyamide
flame retardants, anti-tarnish chemicals etc.
CONTROL ADDITIVES
retention &
drainage aids
formation aids
defoamers
deposit control agents
biocides
other additives
keeps material on the sheet & increases water removal on the wire
- high charge density polyelectrolytes (polyethylenimine, poly(diallyldimethyl
ammonium chloride)), high m.w. polyacrylamides, polyethyleneoxide, starches,
gums, alum, aluminium polymers
promotes dispersion of fibres
- water-soluble linear polyelectrolytes of ultra high m.w. (anionic polyacrylamides),
guar gum
used to control entrapped air
- alkylpolyesthers, polydimethylsiloxanes, oligomers of ethylene oxide (EO) or
polypropylene oxide (PO), hydrocarbon or polyethylene waxes, fatty alcohols,
fatty acids, fatty esters, ethylenebisstearamide (EBS)
used to control inorganic or organic deposits
- chelants (EDTA, NTA, DTPA), polyphosphates, polyacrylates, phosphonates,
non-ionic surfactants, polypropylene
reduces slime from microorganisms
- quaternary ammonium salts, methylene bis-thiocyanate, dibromonitrilepropionamide, glutaraldehyde, isothiazolin
PH control agents, corrosion inhibitors
12
2.3.4. Detrimental Substances

As the short circulation water system is closed, dissolved and colloidal substances (DCS)
accumulate within the white water system according to the degree of retention of such
material within the paper sheet itself73. These substances are introduced into the system
at various production locations by raw materials, broke, carryover from the pulping
process as well as hydrodynamic shear applied to the wood fibres during the various
pumping stages, which transfers residual material from the wood fibres e.g. lignins,
carbohydrates and extractives, to the water phase74-76. The organic materials with poor
solubility often form colloidally dispersed pitch droplets, which are anionic.
At high levels, DCS interfere with the action of chemical additives, such as retention aids
and wet strength resins, as well as effecting drainage, flocculation, and dryer
efficiency77-80. Additionally, DCS accumulation contributes to pitch deposition problems
on the papermaking machine and stock preparation equipment, which reduces
runnability by causing breaks, down-time for clean-ups, as well as paper defects, such
as holes, dirt and reduced paper strength81-83.
The increased use of recycled wastepaper, in combination with system closure and
neutral papermaking, has also resulted in other types of detrimental substances, which
originate from microbiological activity in the wet-end of a papermachine84-91.
Uncontrolled growth of freshwater microorganisms frequently results in a multitude of
undesired effects, such as biomass formation and slime deposition, which can impact
paper machine runnability and cause problems with heat transfer and equipment life
throughout the mill water system.
Papermaking
2.4.
13
Current Trends & Problems
For most of last century, the majority of papermaking advances were focused upon the
mechanics of the paper machines the demand for larger and faster machines required
challenging engineering solutions. Such advancements include high-speed papermaking
(efficient sheet threading and drying), twin wire forming and hydraulic head-boxes to
name just a few92-98. Surprisingly, the material the new machines were built around, the
paper furnish, remained essentially unchanged, uncontrolled, and poorly understood99-103.
Despite the significance wet-end chemistry (for this discussion, the wet end of a paper
machine extends from the pulp mill to the machine press section) has on many aspects
of paper production, this sector has suffered from poor understanding more than any
other area of the papermaking system104.
2.4.1. Recent Changes in the Papermaking Chemical Process

Over the past decades changes in the papermaking chemical process have become
necessary, primarily due to factors including environmental and associated legislative
issues (e.g. reduced effluent discharge and water intake), the increasing cost of raw
product (e.g. wood fibre) and the ever-increasing demands imposed by the customer10-19.
It is evident that the bottle neck of the papermaking process is slowly shifting towards
the wet-end of the paper machine. The most significant and recent papermaking trends
that have a bearing upon the wet-end chemistry include:
Benefits include
Conversion from acidic to neutral/alkaline conditions.
improved strength, energy conservation, decreased corrosion, less complex systems,
enhanced permanence, and decreased costs105-108. A major aspect of this conversion
is the replacement of alum109,110 and clay and titanium dioxide fillers to calcium
carbonate111-113. In addition, new retention aids114,115, sizing116-121 and wet strength
resins122,123 have become necessary. Problems reported include poor drainage,
decreased dryer efficiency and sheet quality, with an increase of holes, web breaks and
pitch deposit problems124-131.
Increased use of recycled wastepaper. Recycled fibre is a cheap and readily
available virgin fibre substitute132-134 - worldwide use is expected to reach 130 million
tons, or 40 % of total P&B fibre, by 2001 (ca. 75 million tons or 32 % was used in
1988)135. However, recycled fibre consists of increased amounts of short fibre lengths
(fines) and is often contaminated with de-inking chemicals, glue and other substances
that result in increased deposit problems, such as slime and stickies136-139. In addition,
the contaminants can lead to an increased consumption of chemical additives and
require the addition of retention aids to maintain stable paper quality140-142.
14
Closure of water systems. The advantages of closure include lower treatment costs,
more stable operating conditions, increased system temperature and lower losses of
fibres, fillers and chemicals143-146 the Canadian Pulp and Paper Association reported
that the amount of water required to make 1 ton of paper decreased by 50 % over the
last 20 years147. However, higher concentrations of dissolved and colloidal materials
accumulate within the system, leading to pitch deposit problems, as well as an increase
of suspended solids, thermal energy build-up, microbial activity and corrosion148-152.
Such problems have shown to affect both product quality and machine performance,
and can result in an increased consumption and/or poor utilisation of chemical
additives153-157.
Increased chemical additive use. In order to meet the requirements of improved
paper quality and higher productivity, taking into consideration the increased use of
recycled fibres, closed water systems and the conversion to neutral/alkaline
papermaking, new chemical strategies have become essential for efficient and effective
management of the wet-end process158-160. A variety of chemical products are being
increasingly used for such purposes as retention, distribution of fines, sizing,
microbiological and deposit control20-23. Wet end chemicals, namely processing aids
and functional additives, account for up to 20 % of world pulp and paper producers'
total raw material expenditures161.
Such process modifications have emphasised the urgent requirement for a more
fundamental understanding, control and optimisation of the wet-end chemistry in order
to achieve profitability and long-term viability24-34. In addition to the above-mentioned
problems, it is evident that the lack of wet-end monitoring also results in poor utilisation
of chemical additives with over-dosage a common scenario162. It is estimated that
between 3 % and 10 % of sub quality and up to 5 % of lost production, is directly
related to poor wet end chemistry control163.
2.4.2. Recent Developments of On-Line Instrumentation

The first dissolved solids, or true chemical measurement introduced to the
papermachine was pH, and today is by far the most frequent on-line chemical parameter
monitored164-171. During the 1970s, research focused upon the development of on-line
sensors for the pulping and bleaching plant, measuring such parameters as alkali, sulphur
and peroxide concentration172-180. Commercial devices soon became available (e.g. the
Technicon Auto-Analyzer181 and Kemotron Alkali Analyzer182) and were readily adopted
by the papermaker due to the ease of relating the on-line measurement data to the
chemistry of the process181-185. The 1980s saw the further development of on-line
Kappa number sensors (e.g. the Kajaani Kappa-Bright analyser186, STFI OPTI-
Papermaking
15
Kappa187-190 and Honeywell Pulpstar191) that measured the dissolved lignin content of
pulps and provided further control to the bleaching process172,186-193.
As far as the wet-end is concerned, the use of devices to monitor and control the
chemistry prior to the mid 1980s were very scarce162. The first wet-end analysers
developed were retention and stock consistency instrumentation although not directly
monitoring the wet-end chemistry, such sensors provide invaluable information on key
parameters reflecting wet-end variability24,31,194-214. Commercial devices include the
Chemtronics 4000 retention monitor211,212 and the Kajaani LC-100 and RM-200
consistency sensors201-208.
It was soon recognised that furnish charge determination in the wet-end of the
papermachine was one of the most critical on-line measurements required if the charge
of detrimental substances can be measured, then efficient neutralisation would be
possible, and the elimination of these substances is feasible215-221. Various charge
measurement techniques, such as zeta-potential222-224 using microelectrophoresis225-227 or
streaming potential228-233 detection and colloidal titration234-236 using streaming
current237-244 detection have been developed, however the implementation of such
devices for measurements on-line has not been straightforward245,246. Thus, besides
commercial devices such as the Paper Chemistry Laboratory Zeta Data System (zeta
potential)247-253, Mutek PCT10 (particle charge titrator)254-257 and the Innomatic Fibre
Charge Analyzer (based on streaming potential technique)258, there is still a considerable
need for further developments in this area.
The increase of microbiological activity in the wet-end of a papermachine has
necessitated more stringent preventive, treatment and control measures, resulting in a
demand for on-line sensors relating the microbiological pollution load of process-water
flows (parameters as oxygen consumption rate, total organic carbon and bacteria count
have been shown to be effective)259-263. Commercial on-line devices include the Nalco
Quick Count263 and the Nalco Optical Fouling Monitor262.
While sensor developments and techniques have advanced considerably in recent years,
due to the complexity of the wet-end system the number of devices that are readily
applicable to the papermaker still remain few35. In fact, the majority of papermachines
only utilise flow, pressure and temperature sensors for wet-end monitoring on a routine
basis; such parameters relating more to the physical state of the process than that of the
chemistry36-39. In an attempt to compensate for the lack of dedicated chemical sensors,
considerable effort has been spent to utilise computer-based diagnostic systems for
analysing wet-end control data using data from conventional sensors35,36.
Multivariate statistical time-series analysis and artificial neural networks are two
computer-based systems currently being developed264-274. Such systems utilize adaptive
16
algorithms to build non-linear process models based on enormous historical data sets, to
make use of all available wet-end data (both on-line and off-line), in order to find shortand long-term relationships between variations in process parameters275-277. The
chemometrics program WEDGE (Wet End Diagnostics Genius), developed by the
Finnish Pulp Paper Research Institute, is an example of such a system and results indicate
that significant cost savings and increased product consistencies may be achieved278-281.
Another approach to overcome the lack of wet-end chemical sensor development is the
recent introduction of the WIC (Wet-end Information Centre) developed by Rasio
Chemicals163,282-285. This system is an at-line robotic laboratory that utilises a
continuous sample work-up procedure and standard automated laboratory techniques,
such as titration, to determine charge, alkalinity or calcium etc. on discrete samples163,286.
It has been reported that the use of this system may help correlate wet-end parameters
with papermachine performance and improve runnability, however at the expense of a
substantial capital investment and installation procedure286,287.
In summary, it can be concluded that there still is a substantial need for improvements in
wet-end chemical monitoring. However, it must be considered that the implementation
of new sensor technology into the papermaking domain, a process that remains as much
of a craft as a science, may be met with a general reluctance from mill operators that
often have limited knowledge in papermaking chemistry. In an attempt to remove some
of the hysteria behind the use of complex chemical analysis systems (both in terms of
the apparatus itself and the derived results), the systems developed should be simple,
robust and most importantly, reliable. In addition, the results should either relate directly
to machine runnability or to the concentration of chemical substances that can be
controlled. The work presented in this thesis introduces some new techniques and ideas
that may help in achieving this goal.
17
3.
Sample Work-Up
n order to analyse a complex matrix, sample work-up techniques are often required in
order to remove, wherever possible, the materials that are not required to be analysed
and would otherwise interfere with the subsequent analysis and/or analysis equipment.
Manual laboratory sample work-up techniques have standardised procedures such as
sieving (separation based on particle size), filtration (complete solids removal),
centrifugation, extraction and distillation etc., but these are generally not applicable to
systems where continuous unattended operation is desired.
As depicted in Figure 2.3, a paper furnish is a heterogeneous mixture comprised of wood
fibres, filler materials (clay, calcium carbonate etc.), various dissolved and colloidal
substances (DCS) and chemical additives. As pointed out earlier (see section 2.3.4), it is of
particular interest to monitor the levels of DCS at the wet-end, since their contribution
to papermaking are generally detrimental in nature.
The sample work-up methodology developed in this study focuses on the separation of
the DCS in order to facilitate the use of further analysis techniques, such as
spectrophotometry, titration and/or gas chromatography etc.
3.1.
Primary Separation Techniques [Paper I]
The primary aim of the initial sample workup was to either utilise or design an apparatus
to produce a continuous stream of analytical sample not containing extraneous fibrous
materials, while containing a representative fraction of the DCS present within the bulk
furnish. The wood fibres do not contribute to the subsequent analysis of the DCS, and
could tend to hinder measurements or even damage sensitive analysis equipment.
Wood fibre can be separated from the bulk furnish either on the basis of density or size.
To exploit such physical properties, either centrifugation of filtration can be employed.
18
3.1.1. Centrifugation
Separation utilising centrifugation is achieved through differences in phase density
between the solids and the liquid matrix, providing an enhanced field force over that
provided by gravity to cause particle or liquid motion288. Batch operated centrifugal
separation for the separation of DCS has shown to be a successful approach, whereby a
laboratory centrifuge was utilised (1500 min-1, 30 min.)289,290.
For the development of a continuous on-line analytical system, several methods of
continuous centrifugation were investigated. Basket and disc-stack centrifuges were
found unsuitable due to the fact that these are solids retaining and have no cleaning
mechanism other than the manual removal of such materials (this would not be
acceptable in a mill environment). Hydrocyclones were also found unsuitable as the
g-values obtained were too low and the wood fibres tended to upset the vortex formed
within the apparatus, resulting in poor separation efficiency. A decanting centrifuge,
which utilises an archimedean screw within the centrifuge bowl to continuously remove
solids from the analyte, has shown to be successful for the removal of large wood fibres
from a paper furnish291, however commercial decanting centrifuges are large, expensive
and inconvenient.
3.1.2. Filtration
Separation utilising filtration is achieved
through differences in the particle size
of solids that are generally suspended
in a liquid matrix288,292. However,
traditional
filtration
techniques,
whereby the solid-liquid mixture is
directed towards a filter where the
solids are retained, has shown to
remove lipophilic droplets and colloidal
particles in the fibre mat (cake) formed
on the filter293.
Cross-flow filtration was initially
investigated, a filtration method
whereby the sample is usually pumped
at a high velocity, tangential to the
surface of a membrane filter, in order
to limit cake formation294-298. The
mechanism responsible for cake
formation in cross-flow filtration has
a)
a)
b)
b)
colloidal droplets
wood fibres
fines
filtration medium
Figure 3.1. Suggested mechanisms for filtration: (a)

Cross-flow filtration with cake formation. (b) High
shear turbulent flow filtration without cake formation
(from Paper I).
Sample Work-Up
19
been suggested as equilibrium between the forces acting tangential and across the
Cake formation reaches a stable thickness when the
filtration medium299,300.
hydrodynamic forces of the bulk flow acting tangential to the filter overcome the forces
acting to drag particles across the filtration medium (Figure 3.1(a)). It has been reported
that a critical condition exists whereupon zero cake formation can be achieved299,301,302.
Initial experiments investigated this possibility; utilizing a cylindrical filtration cartridge
containing a 22 m woven polyester cloth. The paper furnish was pumped through the
unit, tangential to the filtration medium, while the filtrate was withdrawn using a
peristaltic pump303. The pressure on the filtrate line was monitored, as the presence of a
vacuum, or a decrease in pressure from initial conditions, indicates a pressure drop across
the filtration medium that is indicative of cake formation298. Experiments showed that it
was possible to eliminate cake formation by significantly increasing the cross-flow
velocity relative to the filtrate velocity. As previously mentioned, these findings appear to
be in agreement with a balancing of the equilibrium between the shear forces acting at
the filter surface (cross-flow velocity) with respect to the drag forces pulling fibres into
the pores of the filter (filtrate flowrate)299,300. The filtration device was evaluated both in
the laboratory and at a paper mill, where NTU (Nephelometric turbidity unit)
measurements were routinely taken from the centrifuged filtrate and compared to the
corresponding centrifuged raw sample (such NTU measurements have been shown to
correlate well with the concentration of lipophilic extractives289). The filtration device
was operated continuously for several days with no signs of sample deterioration and
with good correlation between the NTU measurements (Figure 3.2), however final
inspection of the filtration cloth revealed a partial blockage, observed as a random
stapling304 of fibres between adjacent filter pores.
turbidity (NTU)
40
35
30
centrifuged raw pulp slurry

centrifuged filtrate
mill shutdown
25
20
0
10
20
30
40
50
60
70
80
90
100
time of experiment (h)

Figure 3.2. Turbidity measurement (NTU) vs. time for the 22 m cross-flow filter (from Paper I).
20
Alternative filtration mediums were

evaluated in an attempt to prevent
stapling and the possibility of eventual
1
filter blockage. A filtration medium
that was found most suitable for this
2
10
application was a track etched
9
3
polycarbonate membrane, notably
8
7
Whatman Cyclopore and Millipore
sample
inlet
Isopore filters295. These filters are
6
analytical
4
advantageous as they are very thin with
sample
5
no voids within the membrane for
attachment of fibre or filler materials,
and are available in a range of discrete
Figure 3.3.
Schematic of filtration device: (1)
pore sizes (12 0.05 m). A new
cylindrical tank; (2) baffle; (3) stirrer; (4) silicon rubber
design was constructed to house the
gasket; (5) base plate; (6) peristaltic pump; (7) vacuum
membrane, which were supplied as flat
gauge; (8) filter membrane; (9) filtrate chamber; (10)
discs, whereby an impeller was utilised
stirring device (from Paper I).
to generate a high shear turbulent flow
regime directly above the membrane which was glued to a flat perforated disc
(Figure 3.3). This filter/filtration-mode is referred to as a dynamic membrane filter or
high-shear cross-flow filtration respectively305-307 (Figure 3.1(b)).
sample
return
Using a 10 m membrane filter, laboratory experiments showed that continuous

filtration, without cake formation, was possible for a high fibre (5 w/w %) with CaCO3
filler material (5 w/w %) furnish over a one week period of constant operation. An
impeller speed fast enough to generate turbulence within the tank (ca. 750 rpm) in
combination with a low sample flowrate (ca. 4 L.h-1) were key factors required for the
prevention of a filter cake. Mill trials were also conducted and the samples analysed did
not indicate any pitch retention. Visual inspection of the membrane indicated no sign of
blockage, fibre stapling, or deterioration. Use of the same membrane for a period of
intermittent continuous operation over several months (subsequent to Paper I) also
showed no sign of blockage, fibre stapling or deterioration.
Unfortunately, utilising filtration for sample pre-treatment does not discriminate against
filler materials that may also hinder measurements. Various post-filtration methods of
filler removal were investigated, e.g. gravity settling. Some encouraging results were
obtained, however the problem needs to be addressed in more detail.
Sample Work-Up
3.2.
21
Continuous Flow Extraction [Paper II]
The primary aim of this work was to develop a system for continuous-flow extraction of
samples containing DCS present in an aqueous matrix. A laboratory procedure has been
reported for the analysis of the colloidally dispersed lipophilic and water-soluble
extractives present in a paper furnish, using a liquid-liquid extraction with methyl tertbutyl ether (MTBE) solvent of the centrifuged sample, followed by gas chromatography
(GC) analysis308. Extraction with a non-polar solvent, such as MTBE or hexane, is
required to transfer the hydrophobic colloidal material into the organic phase. In a
subsequent step the solvent is evaporated to concentrate the sample prior to GC analysis.
It was found that strong mechanical forces were required (i.e. vigorous shaking for several
minutes) to provide sufficient contact between the colloidal droplets and the solvent
during the extraction308.
Liquid-liquid extraction is a commonly used technique in the chemical laboratory to
achieve pre-concentration, cleanup, or matrix exchange in order to facilitate and/or
improve chemical analysis of a liquid sample. The principle and theory of liquid-liquid
extraction is based upon heterogeneous equilibrium309, influenced by the diffusion of
analyte through a phase boundary as well as concentration equalising within the
continuous phases310. The rate of diffusion can be enhanced by increasing the interfacial
surface area of the phases, such as
solvent
distributing the phases into small
droplets311 and/or by the addition
of mechanical energy312 e.g. vigorous
shaking.
Continuous flow extraction (CFE)
was the first method evaluated313-318,
whereby solvent was continuously
pumped into the aqueous sample
stream, forming a segmented flow,
followed by a length of PTFE
tubing (5 m) to provide a region of
substantial contact between the
segmented phases (Figure 3.4 (a)).
Dissolved components (such as
lignans) extracted well, however
poor
extraction
yields
were
experienced
for
the
more
hydrophobic
colloid-forming
a)
a)
sample
solvent
b)
b)
sample
Figure 3.4.
(a) Conventional continuous flow
extraction segmentor. (b) High-velocity injection flow
extraction unit (from Paper II).
22
components (Table 3.1). The poor

extraction
yield
of
such
components is likely to be related to
an insufficient contact between the
colloids and the extractant308,319.
Table 3.1. Average amount (mg.L-1), standard deviation

(% of average) and yield (compared to manual extraction
with vigorous shaking which is set at 100%) of the
component groups obtained by extraction of the sample
by manual extraction, CFE and HVIFE (10 m i.d. nozzle)
(from Paper II).
In order to increase the mechanical

fatty resin
sito- steryl triglycenergy added to the system and the
lignans
acids acids
sterols esters erides
interfacial surface area of the manual extraction
phases, the solvent was brought into
average
0.31 2.14 8.05 0.37 1.95 2.70
std dev
7
4
2
3
2
4
forced contact with the sample by
high-velocity injection through a CFE
average
0.29 1.05 8.34 0.40 0.50 0.25
10 m capillary nozzle (Figure
std dev
69
25
6
18
8
15
3.4 (b)).
Greatly
improved
yield (%)
94
49
104
108
26
9
extraction
yields
of
the
hydrophobic components were HVIFE
average
0.27 1.94 8.67 0.35 1.60 2.12
obtained over traditional CFE, with
std dev
14
3
2
7
2
3
an extraction enhancement of up to
yield (%)
87
91
108
95
82
79
9 times experienced with the
triglycerides (Table 3.1). This new mode of continuous extraction was paraphrased high
velocity injection flow extraction (HVIFE).
High-speed photographs were taken of the solvent inlet region to provide some insight
into the mechanism of extraction utilising HVIFE. The solvent jet remained continuous
until collision with the adjacent wall of the T-piece, after which the jet disintegrated
resulting in a high degree of turbulence with a large amount of solvent droplets that
varied considerably in size. Shortly after the solvent inlet region, coalescence of the
solvent droplets occurred forming a segmented flow similar to that observed in CFE.
Experiments were also undertaken whereby the downstream PTFE tube was omitted
(used for extraction in CFE), the results showing there was no significant variation in
extraction yields. From these findings, the conclusion is that HVIFE occurs almost
instantaneously due to the intense contact achieved within the T-piece.
Choice of nozzle diameter, providing some control over the interfacial area of the
resulting solvent droplets, was also investigated. The use of a 5 m nozzle, while
resulting in smaller solvent droplets, resulted in an excessive entrainment of solvent
within the water phase, with an emulsion-like appearance, and with a slight decrease in
extraction yields. The addition of chemicals to break this emulsion was also investigated,
with promising results using multi-valent salts, notably ammonium dihydrogen
phosphate, however the results from this approach remain inconclusive.
23
4.
Continuous Dynamic Titration
itration is one of the most accurate and selective wet chemical analytical methods
for the quantitative determination of soluble analytes320. Since the advent of the
microprocessor and the subsequent development of modern instrumental analysis,
automating the laborious procedure of titration has been a key topic, with a rapid
development of automatic titration devices321-323 and computerised data handling
procedures324-326.
Many automated titration devices are commercially available today, both for use in the
laboratory and apparatus for the semi-continuous monitoring of discrete samples and/or
industrial process streams327-331. Considering the advancements made, it is surprising that
there are only a few reported apparatus than can titrate continuously in real-time332,333.
The majority of methods presented, while reported as being continuous, require a
periodic sampling to provide a succession of discrete results. Continuous methods
should ideally provide a readout or indication of the state of a streaming sample in real
time.
4.1.
New Titration Device [Paper III]
The primary aim of this part of the work was to develop a simple and robust device that
could titrate a continuous stream of analytical sample in real time, based upon the wellestablished colorimetric neutralisation titration technique334-337. The titration apparatus
developed is referred to as a continuous dynamic titration device, in order to
distinguish the apparatus from other continuous titrators that do not titrate streaming
samples in real-time.
In titrimetry, substances are quantified by measuring the volume of known concentration
reagent solution that is required for a defined, complete chemical conversion with the
substance being analysed. The addition of a reagent, referred to as the titrant, until one
can recognise the end-point of the reaction (with the aid of an indicator that undergoes
an easily recognisable colour change at this point) is known as colorimetric neutralization
titration. Knowing the volume of sample and titrant added, the concentration of the
titrant, and the stoichiometric relationship between the sample and the titrant, the
concentration of the sample can be calculated.
24
Classical manual titrations are carried out using a burette to accurately deliver the titrant
to a known volume of sample with indicator. Titrant is added drop-wise to the sample,
mixing between additions, until a permanent colour change of the sample solution
occurs, at which point the volume of titrant consumed is read from the burette. As with
most analytical procedures, more than one titration is often required to reduce the chance
of error. Consecutive titrations can be carried out faster by the continuous addition of
titrant up to an amount just prior to the neutralisation volume (determined either by the
first titration or more commonly a rough titration), followed by precise drop-wise
additions of titrant up to the end-point.
4.1.1. General Principle & Construction

The general operating principle for the new titration apparatus presented here is, in a
sense, analogous to the manual titration procedure described above. An initial rough
titration, referred to as the pre-titration, is first performed by combining a continuous
stream of sample with a continuous stream of titrant up to an amount just prior to the
neutralisation volume, followed by further, considerably smaller, continuous stepwise
additions of titrant to accurately resolve the end-point. A simplified schematic of the
operating principle is given in Figure 4.1.
The experimental device developed in this work primarily consists of a machined
Plexiglas board with channels for the passage of the working fluids and integrated
electronic photometric detection cells for a monitoring of the end-point. Between each
successive titrant addition and subsequent detection cell, static mixing channels (zigzag
structures machined into the Plexiglas board) were employed to ensure a complete
10
11
11
12
Pump 1
sample
titrant +
indicator
waste
Pump 2
pre-titrant
Pump 3
titrant
Absorbance
sample
7
6
5
1
Figure 4.1 Operating principle for the continuous dynamic titration device.
10
11
12
11
25
reaction of sample, titrant and indicator338,339. The photometric cell construction was
simplified using solid-state electronic components (light emitting diodes (LEDs) and
photodiodes with on-chip amplifiers), mounted directly on the titration unit with no
lenses, mirrors or sophisticated optical or mechanically moving parts340-347. The light
paths were holes drilled through the Plexiglas plate (black Plexiglas was used), to provide
a fixed light path and to reduce interference from internal reflections348. The Plexiglas
board was sandwiched between two metal plates containing the electronic components
required for the photometric cells, threaded holes to facilitate convenient connection of
ancillary fluidics and gaskets to prevent leakage of the fluids. The titration unit was
comprised of a sample inlet, 11 titrant addition points and 12 mixing channels with
subsequent detection cells. The number of channels and addition points were arbitrarily
chosen.
Three HPLC pumps were utilized to accurately deliver the fluids to the titration device; a
sample pump (pump 1), pre-titrant pump (pump 2) and titrant pump (pump 3). To
provide 11 titrant addition points using one pump, capillary tubes were utilized to split
the titrant flow; the large pressure drop incurred across each narrow bore capillary
(50 m i.d.) ensured a consistent delivery of titrant with the same flowrate. The hardware
control and data acquisition was fully computer automated using a program written in the
LabVIEW graphical programming language349, utilizing an A-D converter to control
and acquire data from the detection cells and RS-232 communication to control the
pumps. A simplified schematic of the continuous dynamic titration device is given in
Figure 4.2.
plexiglas plate
zigzag mixing channel

LEDs
sample
pump 1
titrant
+
indicator
pump 2
photodetector
pump 3
computer
control &
data handling
4
10
11
12
capillary tube
waste
Figure 4.2. Simplified schematic of the continuous dynamic titration device (from Paper IV).
26
The total combined flowrate of the titration apparatus (waste flowrate) was set at a
constant value of 4.00 mL.min-1, as higher flowrates resulted in leakage of fluids (the
upper flowrate limit was ca. 6 mL.min-1). In addition, the titrant flowrate (pump 3) was
also kept constant, thus resulting in a constant combined flowrate of sample and pretitrant (pump 1 + pump 2 = 4.00 - pump 3 = const.). Control of the pre-titration was
established by varying the ratio of sample to pre-titrant, referred to as the pre-titration
ratio.
4.1.2. End-Point Determination

In order to monitor the end-point of the titration, an indicator is added to the titrant that
undergoes an easily recognisable colour change at this point. The titration unit was
evaluated using a standard acid-base titration, using bromothymol blue (sodium salt) as
the indicator which provides a distinct colour change from yellow (acidic) to blue (basic),
with an absorbance maximum around 615 nm when basic. The absorbance spectrum for
bromothymol blue is given in Figure 4.3.
Absorbance / Relative Intensity
615 nm
acidic (yellow)
200
300
basic (blue)
400
500
LED output
600
700
800
wavelength (nm)
Figure 4.3. Absorbance vs. wavelength spectra for the indicator dye bromothymol blue (sodium salt) in
both acid and basic form, and relative intensity vs. wavelength (spectral emission) of the 615 nm redorange LED light source.
Red-orange LEDs were utilized as the light source to monitor indicator colour change,
providing a spectral emission centring around 615 nm and a bandwidth of 17 nm (shown
in Figure 4.3). In addition, 950 nm LEDs were utilized as a reference light source since
the indicator does not adsorb at this wavelength and therefore could be used to monitor
changes in the samples turbidity350,351. Photodiodes were used to detect the intensity of
both the 615 and 950 nm incident light that passed through each light path, the
acquisition of the voltage outputs were synchronised with the LEDs which were
switched on and off alternatively, providing a sampling rate of ca. 20 Hz (for both
wavelengths).
27
After de-multiplexing the voltage signals (Vi) obtained from each photodiode (i) for the
wavelengths monitored (), transmittance ((Ti)) or absorbance ((Ai)) was calculated
according to equations 4.1 and 4.2 respectively321,335,348.
(Ti )
( Ai )
V
= i
(V0 ) i
N i
(V )
= log 0 i N i
Vi
Eqn. 4.1
Eqn. 4.2
Prior to operation, it was necessary to calibrate each photocell for the voltage
corresponding to maximum light transmittance (V0) and to standardise the photocell
output values (Ni) in order to accommodate for minor variations between optical path
length and/or LED/photodiode alignment321,348. The calibration procedure was
computer automated, achieved by making the flow regime entirely yellow/acidic (for
determining V0), or entirely blue/basic (for determining ki). For the present application
using bromothymol blue indicator, absorbance values were used to determine the end
point, producing a S-shaped set of data points.
To obtain a numerical value for the end-point, the twelve absorbance values
corresponding to the indicator colour change were fitted to an inverse hyperbolic sine
function, according to equation 4.3, where a0 = y scale offset (x-inflexion), a1 = x scale
offset (y-inflexion), a2 = height (max-min), and slope = slope of the curve.
f ( x,a) = a 2 asinh(( x a 0 ) slope) + a1
Eqn. 4.3
To fit the absorbance data to this function, the non-linear least-squares LevenbergMarquardt method was utilized350,351, requiring both initial guess coefficients and the
Jacobian to be specified. The initial guess coefficients were estimated using the following
approximations: a0 = 6.5 (mid point of the twelve photocells); a1 = 50 % of max.
absorbance; a2 = max. min. absorbance. The Jacobian function (/A) was specified
from the partial derivatives (equations 4.4 4.6).
slope
f ( x, a ) = a 2
a 0
(1 + ( x a 0 ) 2 slope 2 )
Eqn. 4.4
f ( x,a ) = 1
a1
Eqn. 4.5
f ( x , a ) = asinh(( x a 0 ) slope)
a 2
Eqn. 4.6
28
absorbance
Other methods of end-point determination were also evaluated, notably directly

processing the raw data using techniques such as first and second derivatives, Grans
plotting and Sevitsky-Golay curve smoothing etc., however the present method appeared
superior for very small data sets352-362. A further advantage of using a general nonimplicit mathematical expression to model the data is that different titration assays could
be readily adopted so long as the
100
general appearance of the end-point
80
region is S-shaped. The slope of the
60
curve (slope) was left as a variable in
40
order to tune the fit for different
20
titration conditions, while the model
directly yields an approximation for
0
the end-point (a0), reducing the
-20
1
2
3
4
5
6
7
8
9
10
11
12
requirement
of
further
data
photocell #
processing. Figure 4.4 demonstrates
absorbance data fitted with the asinh Figure 4.4. Typical strong acid-base titration data with
corresponding fit (slope = 2000) (from Paper III).
function.
4.1.3.
System Characteristics
The titrant and pre-titrant concentration, as well as the titrant flowrate, are three
parameters that must be chosen prior to operation. The concentration of pre-titrant
determines the titratable concentration range, while the concentration of titrant and the
titrant flowrate determines the sensitivity. To reduce the work of preparing standards,
the pre-titrant and titrant were taken from the same solution. Two fixed parameters that
effect the magnitude of the titratable concentration range is the maximum combined
flowrate (4.00 mL.min-1) and the flowrate precision (minimum adjustable flowrate) of the
pumps utilised. The effects of these parameters are discussed in detail in Paper IV.
From both theoretical and experimental work, it was shown that an acetic acid sample,
using sodium hydroxide (10 mM) as the pre-titrant/titrant, could be titrated from ca. 0.5
mM to 150 mM (titrant flowrate was 0.5 mL.min-1), by adjusting the pre-titration ratio
accordingly. At very low sample concentrations (<0.5 mM), insufficient absorbance data
was available for a good curve fit (S-curve was far left, end-point < 3), while at high
sample concentrations (>150 mM), minor flow instabilities, such as pulsed flow from the
pump heads, resulted in chaotic end-points (the concentration range of sequential titrant
addition was low compared to sample concentration fluctuations).
The accuracy and reproducibility of the titration apparatus was primarily dependent upon
the characteristics of the three pumps utilised. The flowrate accuracy of the pumps was
2 % or 0.002 mL.min-1 (whichever is greater), with a reproducibility of 0.3 % or
29
0.003 mL.min-1 (whichever is greater). Based on these specifications, it was calculated

that the determination of the sample concentration has a subsequent error of ca. 4 %
for pump flowrates > 0.1 mL.min-1 (lower flowrates introduces increased error as per the
pump specifications).
The error incurred from the curve fit appeared to be low for an acid/base system
where indicator colour change was abrupt, the end point could be estimated within 0.5
photocell/titrant addition points. Intermediate absorbance values helped assist with the
estimation of the end-point, however such points were not always present. In addition,
the mean squared error (MSE) between the fitted values and the observed values was
calculated in order to automatically monitor the goodness of fit. This was used to
reject poorly fitted data, sometimes resulting from transient flowrate fluctuations,
concentration spikes, or small air bubbles.
4.2.
Automation of Titration Device [Paper IV]
The primary objective of this work was to develop and implement a control
methodology in order to fully automate end-point detection and subsequent control.
This was achieved using a fuzzy logic controller (FLC) to automatically maintain the pretitration ratio based on the numerical value obtained for the end-point. A schematic of
the controller implementation is provided in Figure 4.5.
An FLC is a problem solving, control system methodology using rule-based decisionmaking, replicating the decision based thought process used by human beings363-365.
Linguistic control terms that would be used to manually describe how the system should
be controlled were directly translated into the rule base of the FLC366-368.
4.2.1. Fuzzy Logic Controller369-373

The FLC is comprised of three main decision making stages; fuzzification, fuzzy
inference and defuzzification. The input parameters used for the FLC are end-point
error (e) and change of end-point error (e). To simplify the programming of the FLC,
the input parameter error at each cycle step (k) is transformed into a range of 1 to 1
according to equation 4.7, where zero represents the centre point of the 12 photocells
(set point). The change of error is the difference between the error at cycle step k and
the previous step (k-1), according to equation 4.8.
30
Proposed Controller to Automate
End-Point / Pump Ratio Control
Existing Manual
Titrator Control Software
Observation
(ek= 0)
ek
Fuzzy
Logic
Controller
Fuzzy
Rule-Base
Error
Calculator
Set-Point
End-Point Determination
(1 end-point 12)
ek
(Vdc A/D card)
Process
Fuzzification
Module
Pump 1
Fuzzy Inference
Engine
Pump 2
Defuzzification
Module
(RS-232)
outk
Pump Ratio Control
Control Factor
(pump 1 + pump 2 = const.)
Response
Figure 4.5. Schematic of the fuzzy-logic controller implementation (from Paper IV).
The first stage of the FLC (fuzzification) is to translate the input parameters into
linguistic terms. The input parameters were modified by adjectives to describe both the
degree of error in relation to the set point (ek left full, left, left center, center, right
center, right, right full) and the change of error with time (e fast neg(ative), medium
neg, slow neg, zero, slow pos(itive), medium pos and fast pos). The input membership
functions that were used to translate the input parameters are shown in Figure 4.6 (a) and
(b). To avoid abrupt controller response, the membership functions were distributed
symmetrically and in such a way that the overlap between adjacent functions was 50%.
( EndPoint 1) 2
1
11
Eqn. 4.7
change of error (ek ) = ek ek 1
Eqn. 4.8
error (ek ) =
The second stage of the FLC (fuzzy inference) generates consequent linguistic variables
from a linguistic rule base that represents the control strategy, and imparts the most
significant and primary influence upon the function of the FLC. The complete rule base
is given in Table 4.1, and consists of 49 rules based on expert knowledge provided from
experience gained through prior manual operation and control of the titration apparatus.
A gradual variation was imposed to consecutive rules to ensure continuous and smooth
controller response, in addition to a region of no change around the set-point region
to allow minor changes in the sample concentration to be tolerated.
31
Degree of Membership (e)
1.00
a)
0.75
0.50 left
full
left
center
left
right
center
center
right
-0.5
0.0
+0.5
error (e)
+1.0
error (e)
Degree of Membership (e)
1.00
b)
0.75
fast
0.50 neg
medium
neg
slow
neg
slow
pos
zero
medium
pos
fast
pos
0.25
0.00
-1.0
-0.5
0.0
+0.5
+1.0
change of error (e)

1.00
medium
neg
small
neg
no
change
small
pos
medium
pos
large pos
0.50
large neg
c)
0.75
0.25
0.00
-1.0
-0.5
0.0
+0.5
+1.0
output (out)
Figure 4.6. Membership functions for FLC input

variables, a) error (e), b) change of error (e), and c) the
FLC output variable (out) (from Paper IV).
Table 4.1. Complete linguistic "IF-THEN" rule base (from Paper IV).
AND
right
full
0.25
0.00
-1.0
Degree of Membership (out)
Fuzzy inference consists of two

operations, firstly aggregation, an
evaluation of the IF condition to
each
rule,
and
secondly
composition, an evaluation of the
THEN conclusion of each rule.
Aggregation
determines
how
adequately each rule describes the
present situation, calculating a
degree of truth for each IF
condition specified in the rule base.
For each possible pair of antecedent
elements obtained from the fuzzy
input sets ((e) and (e)), there is a
corresponding output fuzzy set
((out)), defined by the rule base, and
logically related by the operator
AND. Since the linguistic terms
utilised by fuzzy logic impart partial
truth, the Boolean AND from
conventional dual logic cannot be
used. In the present work, the
membership degree of any output
fuzzy set is obtained from the
minimum of the two truth-values
for each rule premise, according to
equation 4.9.
change of error (
e)
fast neg
medium neg
slow neg
zero
slow pos
medium pos
fast pos
left full
large pos
large pos
medium pos
medium pos
small pos
small pos
no change
left
large pos
medium pos
medium pos
small pos
small pos
no change
small neg
left center
Medium pos
medium pos
small pos
no change
no change
small neg
small neg
center
Medium pos
small pos
no change
no change
no change
small neg
medium neg
right center
small pos
small pos
no change
no change
small neg
medium neg
medium neg
right
small pos
no change
small neg
small neg
medium neg
medium neg
large neg
right full
no change
small neg
small neg
medium neg
medium neg
large neg
large neg
32
( out k ) = min( ( ek ), ( ek ))
Eqn. 4.9
Composition determines what action should be taken for the THEN condition, taking
into consideration the differently weighted conclusions of the active rules. Since the
rules given in the rule base are defined separately and are logically related by the operator
OR, difficulties again arise, as the conventional Boolean OR operator cannot be used.
In the present work, if any output fuzzy set is activated more than once, its final (out) is
the maximum membership function of this element, according to equation 4.10, where i
denotes each unique output fuzzy set combination.
(out k (i ) ) = max ( (out k ), (out k ),..)
Eqn. 4.10
The third and final stage of the FLC (defuzzification) determines a crisp numerical value
from a fuzzy linguistic conclusion that best represent the control strategy to be
implemented.
The relationship between the output linguistic values and the
corresponding numerical value (out) is provided from a set of output membership
functions, shown in Figure 4.6 (c). In order to derive a crisp numerical value, a numerical
compromise is required to arrive at the best final conclusion as a result of combining
the individual inferences. In the present work, the centre of maximum (CoM)
defuzzification method is utilized, according to equation 4.11, where n is the number of
unique output linguistic terms activated.
n
out k =
median(out
i =1
k (i )
) (out k (i ) )
Eqn. 4.11
(out
i =1
k (i )
To transform the FLC output value (outk) into a real value suitable for controlling the
pump ratio, a control factor was utilised, according to equations 4.12 and 4.13. The
Control Factor corresponds to the maximum allowable pump flow-rate change per cycle
step (k), and affects the stability of the controller, especially at higher sample
concentrations. For the present application, a Control Factor of 0.05 was found suitable.
(pump 1) k = out k Control Factor + (pump 1) k 1
Eqn. 4.12
(pump 2) k = 4.00 (pump 3) (pump 1) k
Eqn. 4.13
A graphical example of how the FLC operates is provided in publication IV, Figure 8.
33
4.2.2. Continuous Titration

In order to evaluate the FLC, a continuous titration was performed on an acetic acid
sample with 0.01 M sodium hydroxide as the titrant/pre-titrant.
The sample
concentration could be either kept constant or varied, either gradually or suddenly, the
operator manually determining the rate and extent of the sample concentration change.
The result of the continuous titration, performed over three successive days of ca. 8 hr
continuous operation, is given in Figure 4.7. During this time interval, 49 297
consecutive titrations were logged.
Concentration (mM)
1000
100
10
0.1
0
10
12
14
16
18
20
22
24
time (hr)
Figure 4.7. Continuous dynamic titration of acetic acid over 24 hrs (from Paper IV).
The stability of the FLC and its ability to maintain accurate and fast control was
outstanding, even for large and abrupt changes in concentration where the end-point
suddenly shifted, requiring large changes in the pre-titration ratio in order to re-establish
control. The results showed that it was possible to automatically titrate from ca. 0.5 to
150 mM, with good stability of the end-point and subsequent FLC at both extremes.
The titration apparatus showed no apparent memory effects, such as leaching of sample
into the apparatus, possibly assisted by the fact the system operates at near neutral pH
conditions (around the end-point), whereby no extremes of sample or reagent are in
contact with the apparatus for extended periods of time. In addition, the sample and
reagents are completely sealed from the environment, minimising titration errors from
airborne contaminants such as CO2.
For the work undertaken with acid-base systems, the samples did not exhibit any turbidity
and the 950 nm wavelength was monitored only as a reference for flow instabilities such
as turbulence. Further work presented in Paper V does use dual wavelength detection to
compensate for turbidity.
34
4.3.
LabVIEW Program
Data acquisition, control and calibration of the titration apparatus was fully computer
automated using a program written in LabVIEW 5.0 graphical programming
language349, operated under Microsoft Windows 98. A 200 MHz Pentium II laptop
computer was used to run the program, using a 16 bit PCMCIA multifunction A-D
converter to control and acquire data from the detection cells and RS-232 serial
communication to control the pumps.
The sampling frequency was ca. 20 Hz (both LEDs) and was dependent upon the speed
of the computer processor. To reduce the overwhelming amount of titration data
collected, 25 absorbance data were collected and averaged prior to curve-fitting and
subsequent control, providing an effective titration rate of ca. 0.4 Hz or ca. 1400
sequential titrations per hour.
A graphical user interface (GUI) was developed to display the status of the pump
flowrates, curve-fit parameters (MSE Fit and inflexion), calibrated concentration, as well
as a graphical plot of the titration data (with corresponding fit and end-point), and a
concentration history profile. In addition, auxiliary parameters, such as temperature
(ambient and sample) and pH (sample), were also displayed. The GUI is shown in Figure
4.8. The required output data was automatically logged to the hard disk and/or sent
directly to other computers on a local network.
Figure 4.8. Graphical user interface of the titrator control program written in LabVIEW.
35
5.
Applications
he equipment and techniques presented thus far should be very suitable as a

foundation for a comprehensive wet chemical analysis system. The filtration unit
performs an initial sample work-up, allowing the possibility to analyse the filtrate using
analytical apparatus, such as a turbidity meter, or of particular interest to this work, the
continuous titration apparatus. In addition, the continuous liquid extraction apparatus
could be utilised to extract the colloidal components from the filtrate in order to perform
spectrophotometry or automated GC analysis.
The continuous titration apparatus, since it utilises the well established technique of
colorimetric titration, should have numerous possible applications for the pulp and paper
industry, such as determination of total alkalinity, peroxide, ion concentration (chloride,
magnesium, calcium), hydrogen sulphide and colloidal/furnish charge.
5.1. Continuous Back Titration on a Paper Furnish [Paper V]

The primary aim of the work described in paper V was to utilise the high shear cross
flow filtration apparatus in combination with the continuous dynamic titration apparatus,
in order to perform a continuous titrimetric analysis on a paper furnish.
Back titration involves adding excess reagent to a sample, e.g. a polyelectrolyte to a paper
furnish, and titrating the excess reagent. A sample clean-up stage is required prior to
analysis to remove extraneous material that would otherwise hinder or prevent the
subsequent analysis; in the present application the high shear cross flow filtration
apparatus was utilised to separate excess reagent from the wood fibres. Alternatively,
excess reagent could be added directly to the filtrate line containing the DCS in order to
specifically monitor these substances (see Figure 5.1). Using either strategy, it was
possible to directly titrate the excess reagent contained in the filtrate using the continuous
dynamic titration apparatus.
A paper furnish is a complex heterogeneous mixture of charged substances, that if out
of control, can result in a myriad of process disorders and reduced product quality (see
chapter 2). Complex chemical additives are often used to abate known problems, however
poor utilisation and over dosage is a common scenario experienced162,163. The
importance of furnish charge determination in the wet-end of a paper machine has been
recognised as one of the most critical on-line measurements required215. Of particular
36
interest is the continuous charge

determination
of
detrimental
substances; if monitored, a more
efficient neutralisation and subsequent
elimination could be undertaken216-221.
This work presents a method for a
continuous quantitative determination
of the total number of charges in a
volume of paper furnish. The method
utilised is colloidal titration, or
polyelectrolyte back tiration, using a
cationic dye to colorimetrically resolve
the end-point374,375.
a)
b)
5.1.1. Polyelectrolyte titration

Polyelectrolyte
titration
involves
titrating a sample with standard
fibre
cationic polyelectrolyte
anionic or cationic polyelectrolyte that
colloidal material
filter (10 m)
will react with the oppositely charged
counterpart in the sample, forming a Figure 5.1. Back titration procedure using the highone-to-one charge association. For shear turbulent flow filtration device. (a) Excess
polyelectrolyte added to the bulk furnish, containing
this work, the anionic polyelectrolyte
fibres and DCS. (b) Excess polyelectrolyte added to
used was poly(vinylsulfonic acid, the filtrate containing DCS only (from paper V).
sodium salt) (PVSA) with poly
(diallyldimethylammonium chloride) (pDADMAC) as the cationic polyelectrolyte374,376-378. The indicator used to resolve the end-point was the cationic dye
o-toluidine blue (oTB), which changes colour from blue with excess cationic
polyelectrolyte, to pink with excess anionic polyelectrolyte, according to relationship
below374.
anionic
cationic
+
polyelectrolyte
polyelectrolyte
K1*
anionic / cationic
polyelectrolyte
complex
anionic
polyelectrolyte +
K2*
anionic polyelectrolyte /
cationic indicator
complex
cationic
indicator
* where K1 >> K2
Applications
37
excess
pDADMAC
(back titrant)
o-toluidine blue
(indicator)
indicator
complex
indicator
complex
Indicator
Indicator
Indicator
Indicator
Indicator
Indicator
Indicator
PVSA
(titrant)
polyelectrolyte
complex
BLUE
polyelectrolyte
complex
excess
PVSA
PINK
Figure 5.2. Colorimetric polyelectrolyte titration mechanism. Continual addition of PVSA (titrant) to
pDADMAC (sample) using oTB as the end-point indicator (from Paper V).
A necessary prerequisite is that K1 should be significantly greater than K2 to ensure the

cationic polyelectrolyte complexes prior to the indicator and subsequent colour change.
As illustrated in Figure 5.2, the sample initially contains an excess of cationic pDADMAC
so the less charged oTB does not interact and the uncomplexed dye gives a blue colour to
the solution. As anionic PVSA is added, the free pDADMAC binds until fully
complexed, at which point oTB begins to complex. When oTB has fully complexed, the
dye gives a pink colour to the solution.
Since it is difficult to identify the exact end-point of titration due to the fact an unknown
amount of oTB must complex with PVSA prior to any significant colour change occurs,
the titration of oTB must be included within the calibration procedure377. A charge
balance on the polyelectrolyte/oTB system is given in equation 5.1.
volume
pDADMAC
pDADMAC
=
conc.
added
(mEq.L1 )
1
(mL.min )
volume PVSA volume PVSA

PVSA
to titrate
to titrate
conc.
sample
indicator
(mEq.L1 )
(mL.min 1 )
mL
(
.min 1 )
Eqn. 5.1
In order to use the continuous dynamic titration apparatus, the LED light source was
modified according to the absorbance spectrum of the oTB indicator (626 nm primary
and 525 nm reference), in addition to subtracting the reference from primary
transmittance values to compensate for turbidity. Transmittance values were used in
order to preserve the S-shape of the titration curve, preventing the requirement of
modifying the fitting algorithm. A further amendment was an additional pump for
dosing the indicator, since oTB participates in the titration. The filtrate stream from the
high shear turbulent flow filtration apparatus, after a further dilution or reagent addition
stage, was pumped to the sample inlet of the titration apparatus via a 7 m filter. This
filter was included to safeguard the titration apparatus from particulate material that
could cause a clogging within the mixing channels. A schematic of the experimental
configuration is given in Figure 5.3.
38
The system was calibrated by preparing a pDADMAC standard that was

used to determine the concentration
of the PVSA titrant/pre-titrant.
Rearranging equation 5.1, the slope of
the calibration curve
(known
concentration of pDADMAC plotted
against the corrected flowrate of
PVSA divided by the flowrate of
pDADMAC) provides the concentration of the unknown PVSA titrant,
according to equation 5.2. Figure 5.4
shows such a calibration, using 9
consecutive
concentrations
of
pDADMAC from 0.05 to 5 mEq.L-1.
The fitted calibration curve was linear
with a slope of 0.359 (mEq.L-1), the
proportion of variation in the data
(r2) was 0.99994.
high shear turbulent

flow filtration
apparatus
peristaltic
pump
pDADMAC
pH
waste
water / reagent
filter
analyte
PVSA
oTB
pH electrode
HPLC
pumps
pre-titrant
waste
indicator
titrant
continuous dynamic
titration apparatus
Figure 5.3. Simplified schematic of the back-titration

apparatus for the continuous charge determination of a
paper furnish (from Paper V).
volume PVSA volume PVSA

to titrate
to titrate
sample
indicator
PVSA
pDADMAC
1
mL
(
.min1 )
mL
min
(
.
)
=
conc.
conc.
volume
(mEq.L1 )
(mEq.L1 )
pDADMAC
added
(mL.min1 )
Eqn. 5.2
pDADMAC conc.
(mEq.L-1)
10
y = 0.35944x
R2 = 0.99994
0.1
0.01
0.01
0.1
10
[PVSA/pDADMAC] polyelectrolyte flowrates
Figure 5.4. Manual calibration using high m.w. pDADMAC. oTB conc. was ca. 6.2510-6 M. Solid line
represents corrected calibration taking oTB participation into account. The dashed line represents
uncorrected calibration (volume PVSA required to titrate oTB not included) (from Paper V).
Applications
39
5.1.2. Experimental Results

In order to demonstrate the usefulness of a continuous polyelectrolyte titration, three
selected examples from paper V are presented. The first two examples utilise the
filtration tank in batch mode (as a stirred tank only) in order to monitor polyelectrolyte
adsorption kinetics and phenomena. Such experiments are valuable for determining the
effectiveness of different polyelectrolytes for differing paper furnish conditions prior to
deployment in the actual process. The third example demonstrates an on-line monitoring
of polyelectrolyte/DCS content within a paper furnish. The experiment demonstrates
the potential of the apparatus for continuous charge or cationic demand determination
on a raw furnish, such as in a paper mill.
i) Polyelectrolyte adsorption: different molecular weight
Due to the porosity of cellulose fibres, polyelectrolyte m.w. has a significant effect upon
the amount of polyelectrolyte adsorbed. It is expected that low m.w. polyelectrolytes will
penetrate the fibre pores, essentially covering the entire surface both inside and out, while
higher m.w. polyelectrolytes may not significantly penetrate the fibre pores, providing a
better indication of the fibre surface charge378-381.
Figure 5.5 shows the results of the effect of polyelectrolyte adsorption, using the same
concentration although differing m.w. solutions of the same polyelectrolyte
(pDADMAC). pDADMAC was added to the tank containing a 0.5 wt % pulp furnish
while the filtrate was continuously titrated. Temperature, pH and salt concentration were
kept constant (same raw furnish used).
Absorbed pDADMAC (Eq.g-1)
20.0
(1)
18.0
16.0
14.0
(2)
12.0
(3)
(4)
10.0
8.0
6.0
10
15
20
25
30
35
40
45
50
time (min)
Figure 5.5. Polyelectrolyte adsorption isotherms for different m.w. pDADMAC. (1) very low (5 00020 000); (2) low (100 000-200 000); (3) medium (200 000-300 000); (4) high (400 000-500 000). 0.5 wt %
pulp furnish, pH = 6.00.1. Ca. 800 consecutive titrations (from Paper V).
40
From Figure 5.5, polyelectrolyte adsorption of very low m.w. pDADMAC was almost
twice that of high m.w. under the same conditions. In addition, the absorption of very
low m.w. pDADMAC showed a considerable time dependency, possibly related to the
kinetics of polyelectrolyte transport into the inner fibre pores. The initial time delay was
a result of both the system dead time (time for tank filtrate to reach the titration unit) and
controller lag (time taken for the FLC to establish the initial end-point location), neither
affecting the subsequent accuracy of the titrations.
ii) Polyelectrolyte adsorption: influence of pH
The pH of a paper furnish has profound influence upon the ionisation state of
functional groups on the fibre surface which directly influences fibre charge379,382. For
example, at pH values below ca. 2.75, most of the carboxyl groups are protonated and the
charge becomes essentially zero, while at more neutral pH conditions the majority of
carboxyl groups are ionised and the surface charge is more negative. Additionally, at pH
values above ca. 9, phenolic OH groups become ionised, further contributing to a greater
negative surface charge67.
12.0
150
11.0
125
10.0
100
9.0
75
8.0
50
Absorbed pDADMAC
7.0
6.0
25
NaOH added
4
NaOH 0.02M (mL)
Absorbed pDADMAC (Eq.g-1)
Figure 5.6 shows the results of the effect of polyelectrolyte adsorption while
continuously increasing the pH from 4 to 10 by a continuous addition of sodium
hydroxide. From Figure 5.6, the greatest change in the amount of absorbed
polyelectrolyte, or change in surface charge, was between pH 4-6, corresponding to the
ionisation of the carboxyl groups present on the fibres surface. The spikes in the titrated
values were related to the FLC, each corresponding to a change in the pre-titration ratio,
and were transient in nature
10
pH
Figure 5.6. Polyelectrolyte adsorption with respect to pH value. Constant addition of 0.02 M NaOH
(3 mL.min-1) to 5 L of a 0.5 wt % pulp furnish with high m.w. pDADMAC (0.250 mEq.L-1). Ca. 800
consecutive titrations (from Paper V).
Applications
41
iii) Continuous polyelectrolyte titration

The continuous on-line monitoring of furnish charge and/or cationic demand is of great
interest to the papermaker. The continuous filtration device was designed to operate on
a continuous stream of pulp and therefore should be ideally suited for direct
measurements in combination with the titration apparatus. However, it must be taken
into consideration that a furnish charge could range from both anionic (e.g. presence of
anionic colloidal components) to cationic (e.g. presence of cationic polyelectrolyte
additives), and this must be taken into consideration prior to configuring the backtitration apparatus.
To allow both anionic and cationic samples to be continuously monitored, additional
cationic polyelectrolyte (0.500 mEq.L-1 pDADMAC) was added continuously to the
filtrate line to ensure the combined flowrate remained cationic, even for anionic samples.
The additional pDADMAC is depicted in Figure 5.3 as the reagent stream, which was
added at the same flow-rate as the tank filtrate. Using this configuration, a neutral sample
(deionised water) titrated as 0.250 mEq.L-1. Adjusting for this zero offset, the system
could titrate from 0.250 mEq.L-1 (anionic) to ca. +0.250 mEq.L-1 (cationic) (the range of
the titration unit was calibrated from 0 - 0.500 mEq.L-1 pDADMAC, see publication V,
Figure 11(a) for details).
Figure 5.7 shows the results of a continuous titration performed over a ca. 9 hr period.
During this interval, various random concentrations and volumes of PVSA, pDADMAC
or water were either pumped or manually added to the filtration tank in order to provide
a sample with continuously varying charge characteristics (both positive and negative).
Concentration (mEq.L-1)
+0.25
0.00
-0.25
time (hr)
Figure 5.7. Continuous polyelectrolyte/DCS titration. Continuous run over 9hr period. Random
amounts of PVSA and pDADMAC were manually added (or pumped) into the tank (with a ca. 0.5 wt %
pulp furnish) during this period. Ca. 9 000 consecutive titrations (from Paper V).
42
While the actual charge in the filtration tank was unknown for the duration of the
experiment, the calibrated results from the titration apparatus followed the expected
trends.
The data presented in Figure 5.7 would hopefully never represent a real life situation in
a paper mill, however the sudden drastic changes demonstrate the robustness of the
titration apparatus and the fuzzy control used for determining the location of the endpoint. Such a charge monitoring could be useful in a mill environment for the control of
detrimental substances through the addition of polyelectrolyte as a charge neutralising
agent, and to help optimise the most efficient dosage of polyelectrolyte required.
43
6.
Conclusions & Future Outlooks
he work presented in this thesis can be considered as a possible platform for a

continuous wet chemical analysis system and was initiated from the clear demand
for process analytical instrumentation for use in the pulp and paper industry. The work
consists of two continuous sample work-up techniques; a continuous filtration apparatus
that was successful for removing extraneous wood fibres from the dissolved and colloidal
components required for subsequent analysis, and a liquid-extraction apparatus that
continuously extracts hydrophobic components from a centrifuged paper furnish sample,
providing a significantly greater yield than obtainable from conventional flow extraction
techniques (over nine times extraction yield for triglycerides). A continuous real-time
colorimetric titration apparatus was developed in order to automate the procedure of
titration providing virtually continuous and adaptive titrations with a greatly increased
dynamic titration range compared to existing titration techniques (can titrate over two
orders of magnitude of sample concentration). In order to demonstrate the potential for
a wet chemical analysis system, whereby a paper furnish could be directly chemically
monitored in real time, the filtration device was combined with the titration apparatus,
utilizing a back-titration approach. The example explored was continuous charge
titration (by choosing the relevant reagents and indicator for the titration apparatus), and
it was possible to continuously monitor either total charge or colloidal charge directly on
a paper furnish in real-time.
As mentioned previously, the work undertaken for this thesis forms a basic platform for
a wet chemical analysis system. As schematically depicted in Figure 6.1, by combining
some of the techniques and apparatus developed in this work with existing sensor and
automated laboratory techniques, it should be feasible to design a powerful analysis
system, that could be tailor made to the papermakers individual needs.
The filtration apparatus, or primary sample work-up, is an essential operation where the
presence of wood fibres does not contribute to subsequent analysis as the presence of
such extraneous material may result in hindrance or even fouling of sensitive analysis
equipment. Measurements that could be made directly on the filtrate include
electrochemical measurements such as pH and conductivity, which can be used for a
monitoring of effective alkali383,384, corrosion385,386 and foam control387. In addition,
direct spectrophotometic methods can be used to monitor turbidity (which has shown to
correlate well with the concentration of lipophilic extractives289) and for the
44
determination of Kappa number (measurements in the UV range have been shown

useful for determining the concentration of lignin388-393).
Paper mill process water
Sample clean-up
high shear cross
flow filtration
usefull for a monitoring of: effective alkali383,384,

corrosion385,386 and for foam control387
Electrochemical
pH, conductivity
Liquid extraction
high velocity injection
flow extraction
organic phase
gas chromatography: sulfur394-395, lignin396-398, volatile

organic compounds and extractives394,399-412
water phase
(not used)
Titrimetric analysis
continuous dynamic
titration
Spectrophotometric
methods
vis
UV
IR
alkalinty/acidity(Paper III&IV), ammonia413, calcium414,415,

chemical oxygen demand417,418, chlorine416, colloidal
charge(Paper V), Kappa # (lignin)172,428, magnesium419,
starch427, sulfur/sulfide172,420-426
direct
turbidity (correlates to lipophilic extractives)289

Kappa # (lignin absorbes in UV region)388-393
indirect
ammonia429, chemical oxygen demand430, chlorine431,

hydrogen peroxide432, nitrogen433, pitch434,
phosphates435, resin acids404, silicon436, sulfur437
addition of
a reagent
Ion selective
electrodes
aluminium443-450, ammonia451, calcium452, chlorine453-457,

nitrate451,458, sodium459-461 and sulfur454,462-469
Pitch droplet
counter
Colloidally dispersed pitch droplet size distribution

and relative amount438-441
Figure 6.1. A possible future platform for continuous analysis.
Conclusions & Future Outlooks
45
The continuous flow extraction apparatus provides a further sample work-up that has
potential for further development, particularly suited as a sample work-up for gas
chromatography (GC) or high-performance liquid chromatography (HPLC) systems. If
further sample manipulation is required (such as chemical derivatisation), a robotic
sample preparation station could be employed. GC has been a used in the laboratory to
determine such wood chemistry parameters as sulphur394,395, lignin396-398 (using pyrolysis),
volatile organic compounds and extractives394,399-412 (the more hydrophobic extractives,
such as triglycerides, have been shown to contribute to process disorders and poor
runnability). GC could be feasible in an on-line monitoring set-up where specific and
detailed analysis are sought, however the increased specificity obtainable must be
weighted against the often-greater complexity of the apparatus.
The continuous dynamic titration apparatus has the potential to perform numerous online measurements on the wet-end of the papermachine and bleaching plant by simply
choosing a suitable reagent (or reagents) and corresponding indicator required for the
colorimetric determination required. Other than the colorimetric measurements
presented in this thesis (alkalinity/acidity and colloidal charge), numerous laboratory
methods with applications for papermaking chemistry have been established and include
ammonia413, calcium414,415, chlorine416, chemical oxygen demand417,418, magnesium419,
sulphur/sulphide172,420-426, starch427 and lignin172,428 determinations. It should be possible
to adapt such methods to the continuous dynamic titration apparatus with only minor
modifications to the titrator hardware and control software.
Another continuous analytical technique is colorimetric determination using
spectrophotometic detection (after the addition of a chemical reagent that can be
colorimetrically determined similar to colorimetric titration although less sensitive).
Such measurements that have potential for papermaking chemistry include methods for
the determination of ammonia429, chemical oxygen demand430, chlorine431, hydrogen
peroxide432, nitrogen433, pitch434, phosphates435, resin acids404, silicon436 and sulphur437.
The filtration apparatus would also be particularly suited as a sample work-up stage in
conjunction with an optical particle counting device to determine the concentration and
size distribution of colloidally dispersed pitch438-441. Such a measurement would greatly
assist in developing cause and effect relationships between chemical parameters (such as
pH and colloidal charge) with pitch deposition problems, in addition to assisting the
implementation of effective pitch control strategies (e.g. addition of pitch scavengers
such as low m.w. polyelectrolytes).
A further area of sensor development for papermaking chemistry is the implementation
of ion-selective electrodes. Such electrodes are beneficial in that they are in-line and nonintrusive (they do not destroy the sample and introduce negligible contamination) and
46
can often be placed directly into the paper furnish. A good calibration is critical for
obtaining meaningful results, which is not a trivial issue with such sensors442. Possible
applications include the determination of aluminium443-450, ammonia451, calcium452,
chlorine453-457, nitrate451,458, sodium459-461 and sulphur454,462-469. Mainly due to the
mentioned calibration problems, in some instances, the use of the continuous titration
apparatus may be more reliable.
While the focus of this work deals with dissolved and colloidal substances in the wet-end
of the paper machine, the same techniques and apparatus could be also adopted for a
continuous monitoring of substances in the pulp and bleach plant, as well for effluent
and emission monitoring. The portability and ease of changing the sampling location for
the filtration unit is beneficial as one unit could be used to sequentially monitor various
locations on the papermachine e.g. machine chest, headbox, white water etc. or before and
after chemical addition points. This would provide an invaluable diagnostic tool for
tracking the source of process disorders and instabilities, as well as for optimising
chemical dosage. In addition, the apparatus can be utilised off-line in laboratory
environments for conducting dynamic batch experiments e.g. the experiments presented
in paper V on polyelectrolyte titration.
In summary, I believe that this thesis has presented a number of new approaches for the
on-line and continuous monitoring of chemical parameters with applications for the pulp
and paper industry. It is my hope that further development of such an analysis platform
will contribute significantly to a better understanding of the complex chemical and
physio-chemical properties and interactions between the papermaking process and raw
materials.
47
7.
Acknowledgements
his work has been carried out at the Department of Chemistry, Division of
Analytical Chemistry, Royal Institute of Technology, Stockholm, Sweden. This
thesis would not have come about if it were not for the help of the following people, to
whom I would like to express my deep gratitude.
Prof. Johan Roeraade my principal supervisor, for his support, guidance and
unparalleled enthusiasm. I appreciate the freedom he provided, allowing me to
develop and mature without (too many) constraints.
Prof. Bjarne Holmbom for his expertise and many good suggestions.
Prof. Per Claesson and Dr. Andra Ddinait, for their invaluable help and wealth of
enthusiasm with surface chemistry.
Dr. Johnny Gustafsson for his assistance with the laser fluorescence photography
I think we broke the world speed record in photography!
Jarl Hemming and Ralf Degerth for help with the GC analysis.
Dr. Agne Swerin for providing me with mill samples and kappa analysis.
Dr. James Crawford a true friend. Thanks for all your help and support, both
academic and otherwise.
Mark Tazewell, thanks for helping me out one long night with the titrator!
Dr. Paul Dickman, for his help with statistics and introducing me to his little bit
drunk but Ok Finnish colleague.
Mark Booth, for accompanying me on a voyage into the remote depths of the
Finnish forests - a mill trial I certainly will never forget.
Isabella Gruenauer my friend and chauffer on many an occasion.
All the people at the department, both present and past thanks for putting up
with me and listening to all my problems!
To all my friends thanks for all the laughs and good times!
My dear mother I know I was only supposed to be in Sweden for one and a half
years I love you very much and know you understand (although I am still not
sure you know what it is I am doing here!).
To my beloved Catha. Your love and kindness has brought out the best in me.
48
49
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8.
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New Techniques for Continuous

Chemical Analysis in the

New Techniques for Continuous Chemical

An expert is a man who has made all the mistakes

Niels Bohr (1885-1962)

This doctoral thesis is dedicated to the pursuit of a better

Rice, M., Roeraade, J. and Holmbom, B. High-shear turbulent flow filtration

Rice, M., Roeraade, J. and Holmbom, B. Continuous-flow extraction of

Rice, M. and Roeraade, J. Continuous titration device for process analytical

Rice, M. and Roeraade, J. Fuzzy-logic to fully automate end-point control of

lthough modern papermaking is a highly mechanised process, the basic procedure

Modern Papermaking: A Global Industry

(1 000 000 tons)

(1 000 000 tons)

Figure 2.2. Global Paper & Board (P&B) and Pulp

One of the objectives of papermaking chemistry is to gain a better understanding of the

2.3.1. Papermaking Fibres

Figure 2.3. Typical components present in a paper furnish.

2.3.2. Wood Fibre Chemistry

Cellulose. Cellulose is the principal structural component of a wood fibre. Chemically,

Two glucose molecules

Structure of softwood aribinoglucoronoxylan. The

Figure 2.5. Naturally occurring extractives present in a typical wood furnish.

2.3.3. Chemical Additives

Table 2.3. Common papermaking chemical additives71-72.

opacity, brightness and basis weight

deposit control agents

2.3.4. Detrimental Substances

Current Trends & Problems

2.4.1. Recent Changes in the Papermaking Chemical Process

2.4.2. Recent Developments of On-Line Instrumentation

Primary Separation Techniques [Paper I]

Figure 3.1. Suggested mechanisms for filtration: (a)

centrifuged raw pulp slurry

time of experiment (h)

Alternative filtration mediums were

Using a 10 m membrane filter, laboratory experiments showed that continuous

Continuous Flow Extraction [Paper II]

components (Table 3.1). The poor

Table 3.1. Average amount (mg.L-1), standard deviation

In order to increase the mechanical

Continuous Dynamic Titration

New Titration Device [Paper III]

4.1.1. General Principle & Construction

Continuous Dynamic Titration

zigzag mixing channel

4.1.2. End-Point Determination

Absorbance / Relative Intensity

Continuous Dynamic Titration

Other methods of end-point determination were also evaluated, notably directly

Continuous Dynamic Titration

0.003 mL.min-1 (whichever is greater). Based on these specifications, it was calculated

Automation of Titration Device [Paper IV]

4.2.1. Fuzzy Logic Controller369-373

(Vdc A/D card)

Pump Ratio Control

(pump 1 + pump 2 = const.)

change of error (ek ) = ek ek 1

Continuous Dynamic Titration

Degree of Membership (e)

Degree of Membership (e)

change of error (e)

Figure 4.6. Membership functions for FLC input

Degree of Membership (out)