GERMAN ATV-DVWK

RULES AND STANDARDS

Advisory Leaflet
ATV-DVWK-M 374E

Production specific wastewater

and waste from the glass and mineral
fibre industry

August 2004
ISBN 3-937758-76-3

Publisher/Distribution:
ATV-DVWK Deutsche Vereinigung für Wasserwirtschaft,
Abwasser und Abfall e. V.
Theodor-Heuss-Allee 17 y D-53773 Hennef
Tel. 0 22 42 / 8 72-120 y Fax: 0 22 42 / 8 72-100
E-Mail: vertrieb@atv.de y Internet: www.atv-dvwk.de
ATV-DVWK-M 374E

The German Association for Water, Wastewater and Waste, ATV-DVWK, is the spokesman in Germany for
all universal questions on water and is involved intensively in the development of secure and sustainable
water management. As politically and economically independent organisation it operates specifically in the
areas of water management, wastewater, waste and soil protection.

In Europe the ATV-DVWK is the association in this field with the greatest number of members and, due to
its specialist competence, it holds a special position with regard to standardisation, professional training
and information of the public. The ca. 15,000 members represent the experts and executive personnel from
municipalities, universities, engineer offices, authorities and business.

The emphasis of its activities is on the elaboration and updating of a common set of technical rules and
standards and with collaboration with the creation of technical standard specifications at the national and in-
ternational levels. To this belong not only the technical-scientific subjects but also economical and legal
demands of environmental protection of bodies of waters.

Imprint

Publisher/marketing: Setting and printing (German original):

ATV-DVWK German Association for DCM, Meckenheim

Water, Wastewater and Waste
Theodor-Heuss-Allee 17
D-53773 Hennef
Tel.: +49 (0) 22 42 / 8 72-120 ISBN:
Fax: +49 (0) 22 42 / 8 72-100 3-937758-76-3
E-Mail: vertrieb@atv.de
Internet: www.atv-dvwk.de Printed on 100 % recycling paper

© ATV-DVWK Deutsche Vereinigung für Wasserwirtschaft, Abwasser und Abfall e. V., Hennef 2004

All rights in particular the translation into other languages are reserved. No part of this Standard may be reproduced in any form – by
photocopy, microfilm or any other process – or transferred into a language usable in a machine, in particular data processing ma-
chines, without the written approval of the publisher.

The scientific correctness of the texts, diagrams and tables does not fall under the responsibility of the publisher.

2 August 2004
 ATV-DVWK-M 374E

Foreword
Virtually, regarding the topic of production specific waste from the glass industry, there is only the "Mus-
terverwaltungsvorschrift" (=administrative model regulation) of the "Länder" study group on emission pro-
tection (LAI) of 1995, which at that time could not have taken into account the current keys of the "Abfall-
verzeichnisverordnung (AVV)" (=regulation regarding waste inventory). Now this gap is closed by the
present Advisory leaflet which also covers the recent research results as well as the current state of the in-
dustrial development. It replaces the advisory leaflet ATV-M 763 „Wastewater occurring in the glass indus-
try“ of 1995.

As the range of production as well as the facility's size play a substantial role regarding the occurrence and
avoidance of wastewater and waste, also these factors are taken into consideration.

The advisory leaflet has been elaborated based on progressive procedures, equipment and operational ac-
tivities, as they could be taken into account for new constructions and re-equipment of existing facilities at
the time of the leaflet's publication.

The requirements to be met are stated in European Guidelines, e. g. the Guideline regarding the integrated
avoidance and reduction of pollution (IVU) and other regulations, in Germany in the "Bundesimmissions-
schutzgesetz (BImSchG)" (=law on emission protection) , "Wasserhaushaltsgesetz (WHG)" (=law on water
management), "Kreislaufwirtschafts- und Abfallgesetz (KrW-/AbfG)" (=law on recycling management and
waste) as well as all associated law-subordinated sets of rules.

Regarding the effects on costs and environment please refer to the reference document on the best avail-
able techniques in the glass industry (BREF document).

Authors
For the elaboration of the advisory leaflet a mutual working group (AG AK-4.1) was formed by the ATV-
DVWK expert committee IG-1 „Industry wastewater with inorganic contents“ and the ATV-DVWK expert
committee AK-4 „Production specific industry waste“, consisting of members of FA AK-4 and the working
group IG-1.14 „Glass industry“, in which die following members and guests participated:
Dr. rer. nat. Rainer Werthmann, Kassel (Chairman FA AK-4)
Dr.-Ing. Walter Schaefer-Rolffs, Essen (Spokesman AG IG-1.14 and AG AK-4.1)
Dipl.-Ing. Gerhard Borcherding, Emden
Dipl.-Ing. Johannes Martin Düngelhoff, Herne
Dipl.-Ing. Matthias Fraaß, Gelsenkirchen
Dipl.-Ing. Günter Höller, Gelsenkirchen
Dr.-Ing. Thomas Hünlich, Mainz
Dr.-Ing. Heinz-Eckhard Lennertz, Düsseldorf (until November 2002)
Dipl.-Ing. Rüdiger Lilie, Wedel
Dr. rer nat. Michael Kühnapfel, Herzogenrath
Dipl.-Ing. Klaus Neukirch, Herne
Dr. rer. nat. Johann Overath, Düsseldorf (from Januar 2003)
Dipl.-Ing. Franz Puder, Berlin
Dipl.-Ing. Johann Georg Schönberger, Riedlhütte
Dipl.-Ing. Jürgen Westrup, Ludwigshafen
For the main business site:
Dipl.-Ing. Anett Baum, Hennef
Dipl.-Biol. Almuth Spitzer, Hennef

August 2004 3
ATV-DVWK-M 374E

Contents

Foreword ............................................................................................................................................................3
Authors ............................................................................................................................................................3
User Notes ..........................................................................................................................................................7
1 Area of application...........................................................................................................................7
1.1 Objective................................................................................................................................... 7
1.2 Branch presentation ................................................................................................................. 7
2 Production and treatment procedures.........................................................................................8
2.1 Raw and additional materials ................................................................................................... 8
2.2 Melting ...................................................................................................................................... 13
2.3 Forming .................................................................................................................................... 13
2.3.1 Hollow glass (container glass, tableware, special glass) ......................................................... 13
2.3.2 Flat glass .................................................................................................................................. 13
2.3.3 Tubes........................................................................................................................................ 13
2.3.4 Glass and mineral fibres........................................................................................................... 14
2.4 Work and finish......................................................................................................................... 14
2.4.1 Mechanical work....................................................................................................................... 14
2.4.2 Chemical work.......................................................................................................................... 16
2.4.3 Coating ..................................................................................................................................... 16
2.4.4 PICVD process......................................................................................................................... 16
2.4.5 Chemical tempering of flat glass .............................................................................................. 16
2.4.6 Further treatment of glass and mineral fibres .......................................................................... 17
3 Wastewater .......................................................................................................................................17
3.1 Cooling water ........................................................................................................................... 17
3.2 Process water........................................................................................................................... 17
3.2.1 Shear cooling ........................................................................................................................... 18
3.2.2 Water in the forming process ................................................................................................... 18
3.2.3 Water in the further treatment .................................................................................................. 18
3.2.3.1 Washing and rinsing................................................................................................................. 18
3.2.3.2 Mechanical treatment ............................................................................................................... 18
3.2.3.3 Chemical work.......................................................................................................................... 18
3.2.3.4 Coating ..................................................................................................................................... 18
3.2.3.5 PICVD process......................................................................................................................... 19
3.2.3.6 Further treatment of mineral fibres........................................................................................... 19
3.3 Wastewater from side installations and exhaust gas washers................................................. 19
3.3.1 Side installations ...................................................................................................................... 19
3.3.2 Exhaust gas wash .................................................................................................................... 19
3.4 Measures for avoidance, reduction and recovery .................................................................... 20

4 August 2004
 ATV-DVWK-M 374E

4 Wastewater treatment......................................................................................................................22
4.1 Dissolved solids ........................................................................................................................22
4.1.1 Chemical precipitation and neutralisation .................................................................................22
4.1.2 Subsequent treatment...............................................................................................................23
4.2 Non-dissolved solids .................................................................................................................23
4.2.1 Sedimentation ...........................................................................................................................23
4.2.2 Separation by centrifugal force .................................................................................................24
4.2.3 Flotation ....................................................................................................................................24
4.2.4 Filtration ....................................................................................................................................24
4.2.5 Separation devices for light liquids ...........................................................................................24
4.2.6 Process integrated burning of wastewater................................................................................24
4.3 Heat load...................................................................................................................................25
4.4 External disposal.......................................................................................................................25
5 Waste .................................................................................................................................................25
5.1 Type of wastes ..........................................................................................................................25
5.2 Waste amounts .........................................................................................................................25
5.3 Characterisation, avoidance, re-use and disposal of waste .....................................................25
5.3.1 Batch residues ..........................................................................................................................25
5.3.2 Filter dust ..................................................................................................................................28
5.3.3 Glass cullet................................................................................................................................28
5.3.4 Furnace material .......................................................................................................................29
5.3.5 Mud from the wastewater treatment (wastewater treatment mud) ...........................................31
5.3.5.1 Mechanical surface treatment...................................................................................................32
5.3.5.2 Chemical surface treatment ......................................................................................................32
5.3.5.2.1 Etching slime.............................................................................................................................32
5.3.5.2.2 Neutralisation gypsum...............................................................................................................33
5.3.5.2.3 Neutralisation mud ....................................................................................................................33
5.3.5.3 Waste from the PICVD procecs ................................................................................................33
5.3.6 Salt melt from the chemical tempering of flat glass ..................................................................33
5.3.7 Glass fibre and mineral fibre waste...........................................................................................33
5.3.8 Mud from the treatment of production water with organic load.................................................34
5.4 Rules on dangerous goods regarding the transport of waste ...................................................34
Bibliography .......................................................................................................................................................35
Reference Sources....................................................................................................................................37

Liste of figures

Fig. 1: Substance streams in the glass production (Bundesverband Glas).......................................12

Fig. 2: Substance streams in the glass production: production of special glass,
for example production of TV cones .......................................................................................12
Fig. 3: Substance streams in the mechanical surface treatment.......................................................15
Fig. 4: Substance streams of acid in the special glass production ....................................................15
Fig. 5: Wastewater treatment in the special glass industry................................................................21

August 2004 5
ATV-DVWK-M 374E

List of tables

Table 1: Production values of the glass industry in 2002 .................................................................... 8

Table 2: Chemical composition of important glasses as mass content in % ....................................... 9
Table 3: Maximum use of refining agent, referring to a glass mass of 100 kg .................................... 10
Table 4: Cullet ratios (mass content in %) ........................................................................................... 10
Table 5: Selection of the most important colouring agent and the according glass colour.................. 11
Table 6: Selection of the most import decolourising agents ................................................................ 11
Table 7: Measures for wastewater treatment in the single production processes ............................... 21
Table 8: Types of waste in the glass industry, including mineral fibre industry ................................... 26
Table 9: Characteristic components of filter dust (mass content in %) ................................................ 27

6 August 2004
 ATV-DVWK-M 374E

User Notes
This Advisory Leaflet is the result of honorary, technical-scientific/economic collaboration which has
been achieved in accordance with the principles applicable therefore (statutes, rules of procedure of
the ATV-DVWK and the Standard ATV-DVWK-A 400). For this, according to precedents, there exists
an actual presumption that it is textually and technically correct and also generally recognised.

The application of this Advisory Leaflet is open to everyone. However, an obligation for application can
arise from legal or administrative regulations, a contract or other legal reason.

This Advisory Leaflet is an important, however, not the sole source of information for correct solutions.
With its application no one avoids responsibility for his own action or for the correct application in spe-
cific cases; this applies in particular to the correct handling of the margins described in the Advisory
Leaflet.

1 Area of application 1.2 Branch presentation

According to the standard DIN 1259-1 „Glass:

1.1 Objective
It is the aim of this leaflet to give process-
engineering instructions to industry and authorities
for measures regarding the area of wastewater
and waste which are both environment-appropriate
and economically efficient. This includes the de-
scription of the progressive state of the technical
development in the glass and mineral fibre industry
as well as the presentation of measures for the
treatment and avoidance of wastewater and for the
avoidance or re-use of waste and, if need be, its
disposal.
It also addresses establishments which are occu-
pied with the planning and operation of such facili-
ties as well as institutions offering education and
training in the field of industrial wastewater tech-
niques and the avoidance and disposal of waste.
Production specific wastewater within the meaning
of this Advisory leaflet contains mainly inorganic
components.
The scope of application covers the feeding into
waters (direct injection) as well as the feeding into
public wastewater systems (indirect injection).
terms for glass types and glass groups“, glass is
„an inorganic non-metallic substance that is
achieved by complete meting of a mixture of raw
materials at high temperature, in the course of
which a homogenous liquid develops that is then
cooled down to its solid status, usually without
crystallisation“.
Depending on the composition it is differentiated be-
tween soda-lime-silica glass (e.g. flat glass, con-
tainer glass), potash glasses (e.g. crystal glass),
lead silicate glasses (e.g. lead crystal glass) and
borosilicate glass (e.g. laboratory glass, E-glass1).
Beside glass wool and stone wool there is also a
multitude of special glasses, the amount of which
however does not achieve the meaning of the
glass types stated above.
In 2002, the glass and mineral fibre industry in
Germany employed approx. 64,000 people and
generated a production value of 7.7 billion €.
Table 1 shows the production values, divided in
main product groups.

Production specific waste is that what arises during

production and processing (including treatment) of
products.
1
Definition according to LOEWENSTEIN (1997)

August 2004 7
ATV-DVWK-M 374E

Table 1: Production values of the glass industry in 2002 (Bundesverband Glas)

Main product groups Production value in Mio. € Share in %

Container glass 1.430 18,4
Flat glass 759 9,8
Utility and special glass, 1.468 18,9
incl. hollow glass processing
Crystal glass and tableware 456 5,9
Glass and mineral fibre 961 12,4
Flat glass refinement 2.680 34,6
Total 7.754 100,0

2 Production and The demands for raw materials are very high.
Mainly a homogenous chemical composition over
treatment long supply periods and a very low contents of iron
are requested. By iron and chrome the glass is
procedures discoloured and reduced in its transmission. Fur-
thermore, raw materials are not allowed to contain
For the classification of the arising wastewater and minerals difficult to melt (corundum, disthene and
waste, below a short sketch of the raw and addi- others), because depending on the melting condi-
tional materials as well as of the production proce- tions, these, as larger minerals corns, cannot be
dures. melted and lead to disturbing residues. Sub-
stances that are used as refining agents split off
gases at the glass melting temperature (compare
2.1 Raw and additional materials table 3).

Table 2 shows the chemical composition of impor-
tant glasses.
The raw materials used for the production of the-
ses glasses are divided in natural and synthetic
products:
The natural raw materials are: quartz sand, partly
also quartz flour, lime, dolomite, feldspar,
nepheline syenite, phonolithe, anhydrite, chromic
oxides, barytes, sassoline (boric acid), tetraborax
and others. For the production of stone wool also
basalt and diabas are used.
Synthetic raw materials are: soda, potash, hy-
drated alumina, bor(III)-oxide, lead oxides, sodium
sulphate, sodium nitrate, barium carbonate, barium
nitrate and others. Also the used refining agents
are classified as synthetic raw materials (also refer
to table 3).
For the production of some special glasses – es-
pecially opal and pot-opal glasses – fluorine con-
taining raw materials are necessary. For lead crys-
tal glass, crystal glasses and optical glasses oxide
compounds of lead, barium and others are used to
increase their refractive index. Textile glasses and
glass wool contain boric oxide due to product spe-
cific reasons. The same applies for special glasses
(borosilicate glasses) which are characterised by
their high chemical resistance.
The role of recycling glass cullet (cullet recycling)
as a raw material for the melting of glass becomes
increasingly important. Own as well as foreign cul-
let is used; usually, the one arising at the produc-
tion site or in the associated further processing
comply with the respective batch composition
and after separation according to given criteria
and being free of foreign substances, can be
used without any problems (VDI 2578). Table 4
shows approx. values for cullet ratios.

8 August 2004
 Table 2: Chemical composition of important glasses2,3 as mass content in % [VDI 2578, Nov. 1999, p. 4; amended]

Sub- Flat glass Container Crystal glass Lead crystal- Lighting glass Picture tube glass Chem. tech. Opt. glass Glass Glass and mineral fibres Water glass
stance (float glass) glass (tableware) glass (fluorescent apparatus glass (boron crown) ceramics
tubes) screen cone E-glass Glass wool Stone wool
Endless Steam Steam Cascade
glass fibres centrifugal blowing centrifugal
blowing procedure procedure
procedure
SiO2 72,6 73,0 69 – 74 58 – 62 67,5 60 – 63 53,5 – 55,3 80,4 61,7 60,0 – 63,5 52 – 56 56 – 67 50 – 61,5 34,5 – 43 68 – 77
Al2O3 0,7 1,4 0,2 – 1,2 0–1 5 2 – 3,4 1 – 5,2 2,27 03,3 – 3 10 – 20 12 – 16 0 – 2,5 0 – 4,5 17,5 – 22,5 0,1 –
Fe2O3 0,1 0,1 0,015 – 0,02 0,01 – 0,015 0,15 – – 0,03 – 0,1 – 0,3 0–1 0–7 2 – 8,5 0,03
CaO 8,6 10,5 4–7 0–4 9,4 0 – 3,2 0,9 – 3,8 – up to 3 0,5 – 7,0 16 – 25 5,5 – 9,5 17 – 32 14 – 22 0,008
PbO – – 0–5 24 – 32 – – 21,6 – 23,5 – – – – – – <0,0002
MgO 4,1 1,6 – – – 0 – 1,2 0,6 – 2,2 – – 0,5 – 1,0 0,1 – 1,0 1–6 7 – 11,5 7 – 14 0,008
Na2O 13,3 12,8 4 – 10 3–5 13,6 6,6 – 9,4 5,8 – 6,7 3,8 up to 5 0,5 – 10,0 0,1 – 1,04 14,5 – 20,5 2 – 6,5 0–3 22,5 – 24
(Soda
water glass)
K2O 0,31 0,4 8 – 12 9 – 11 1,8 6,6 – 8,4 7,8 – 8,1 0,6 12 – 18 – 0,1 – 1,0[4] 0 – 1,5 0–2 0 – 2,5 27 – 32
(potash water
glass)
SO3 0,2 0,2 – – 0,2 – – – – – 0,01 – 0,10 – – – 0,015
F – – – – 4,0 – – – – – 0,005 – 0,050 – – – –
B2O3 – – 0–2 0–2 – – – 12,9 6 – 20 – 5 – 10 4,5 – 13 – – –
BaO – – 0–7 – – 8,3 – 13 0 – 2,5 – up to 10 1–2 – – – – –
ZnO – – – 0–2 – – – – – 0,5 – 6,0 – – – – –
SrO – – – – – 2,2 – 8,8 0 – 0,5 – – 0,05 – 0,20 – – – –
ZrO2 – – – – – 0 – 2,3 0 – 0,2 – – 1 – 2,0 0,01 – 0,10 – – 1 – 2,0 –
P2O5 – – – – – – – – – – – 0–1 – 0 – 1,5 –
TiO2 – – – – – – – – – – – – 0–1 0–3 –
Cr2O3 – – – – – – – – – – 0,001 – 0,020 – – – –

ATV-DVWK-M 374E
August 2004

2
The glasses' composition is very manifold, so the data stated do only serve as an example. Especially broad is the variety of optical glasses. Therefore only the scope can be stated.
3
This table does not contain batch material related pollution (e.g. PbO from recycling cullet).
4
The sum of Na2O and K2O has to be smaller or equal to 1% !
9
10

Table 3: Maximum use of refining agent, referring to a glass mass of 100 kg [VDI 2578, p. 8]

ATV-DVWK-M 374E
5
Mass of refining agent in kg/100 kg glass mass
Kind of refining agent 6 Use e. g. for
made of batch
August 2004

CaSO4 or Na2SO4 from filter dust 1,2 soda-lime glasses

Sulphates e.g. Na2SO4) and sulphides 1,2 soda-lime glasses
Chlorides (e.g. NaCl) 1,5 borate glasses
Nitrates (e.g. NaNO3) 1,7
Oxides (e.g. As2O3, Sb2O3, NaSbO3 or CeO2) 0,3 tableware and special glasses in different combinations
Oxides (e.g. Mn2O3) 1,0

Table 4: Cullet ratios (mass content in %)7

Cullet Flat glass Container glass Crystal glass Lead crystal glass Lighting glass Picture tube glass
(float glass) flint amber green (tableware) (fluorescent tubes) screen cone
own share
65 – 85 65 – 85
furnace melt 5 – 15 5 – 15 5 – 15 5 – 15 25 – 45 30 – 50 20 – 50
25 – 35 25 – 35
pot melt
8
foreign share 10 – 25 35 – 70 35 – 70 45 – 75 0 0 2–5 0 – 30 0 – 50
total 30 – 70 20 – 80
15 – 30 40 – 85 40 – 85 50 – 90 25 – 85 25 – 85 25 – 50
cullet ratio

Cullet Chem.-tech. appara- Opt. glass Glass ceramics Glass and mineral fibres Water glass
tus glass (boron crown) E-glass glass wool stone wool
endless steam centrifugal blow- steam blowing cascade centrifugal procedure
glass fibres ing procedure procedure
9
own share 50 – 80 0 – 15 30 – 70 0 – 18 0 – 15 0 – 20 10 – 40 0
9
foreign share 0 0 0 0 > 50 – 75 ca. 30 0 – 20 0
total 50 – 80 0 – 15 30 – 70 0 – 18 > 50 – 80 30 – 45 10 – 60 0
cullet ratio

Several compounds, mainly metal oxides, serve as colouring or decolourising agent. A small selection of possible compounds is shown in tables 5 and 6.

5
The numbers stated are only rough values. Typ and amount of the refining agent, solely or in combination with other, is depending on the glass type, the melting device, its size, the capacity,
the furnace atmosphere, the temperature, the furnace material etc.
6
Also other reference and code sizes are used, e. g.: „kg refining agent/t glass made of batch“ or „kg SO3/t glass“ (e. g. when using filter dust).
7
The cullet ratios can be very different. The stated ranges are for orientation purposes only. The total cullet ratio does not necessarily have to be the addition of own and foreign share.
8
Limited by the mercury content of the recycling cullet, which can contain depending on the pre-treatment (shredded only) 30 – 40 mg mercury per kg, with post-cleaning in a cullet cleaning de-
vice with water up to 5 mg mercury per kg.
9
Water glass is produced in so-called „glass pieces“ with a size of approx. a palm of a hand, with waste cullet; no foreign cullet material.
 ATV-DVWK-M 374E

Table 5: Selection of the most important colouring agents and the according glass colour [VDI
2578, p. 8]

Colouring agent Glass colour Colouring type

chromic oxides green to yellow-green Ion colouring
ferric oxides blue-green to yellow-green Ion colouring
cobalt oxide blue Ion colouring
copper oxide, oxidising greenish blue Ion colouring
manganese oxide violet Ion colouring
nickel oxide grey-red to blue-red Ion colouring
selenium pink Ion colouring
sulphides with Fe yellow to amber-red Ion colouring
cadmium sulphide + ZnO yellow colloid colouring
gold ruby red colloid colouring
copper oxide, deep red colloid colouring
reducing
silver yellow colloid colouring

Table 6: Selection of the most import decolourising agents [VDI 2578, p. 9]

Mass of decolourising agent

Type in g/100 kg
glass mass made of batch
nickel oxide 0,5 – 1,0
manganese oxide 5,0 – 25,0
cobalt oxide 0,04 – 0,1
selenium, e.g. zinc selenite 3,0 – 20,0
neodym oxide 5,0 – 15,0
erbium oxide 10,0 – 20,0

August 2004 11
ATV-DVWK-M 374E

Raw and
Glass production facility Waste / wastewater
additional materials

Sand
Soda Batch dust
Lime Batch
Dolomite composition
Cullet Faulty batch
Others

Waste glass
Furnace demolition material

Ca(OH)2 Clean gas

Exhaust gas
Na2CO3 Glass melt
NaHCO3 cleaning
Filter dust

Energy
Glazed melting mass
Water

Wastewater
Wastewater
preparation

Filter cake
Compressor oils
Hot treatment
Lubrication oils Forming Waste glass, waste glass wool
Hager process
Waste oil
Water
Oil water mixes

Products

*depending on production process

Fig. 1: Substance streams in the glass production

Raw and
Special glass production facility Waste / wastewater
additional materials

Lead oxide
Quartz sand
Soda Batch Batch dust
Potash composition Faulty batch
Cullet
Other additives

Waste glass
Oxygen Glass melt Furnace demolition material
Natural gas

Exhaust gas Clean gas

Ammonia cleaning Filter dust

Hot
Forming

Neck
Natural gas Waste glass
Sealing

Water Grinding
Cooling lubricant
Wastewater Wastewater
Precipitation and treatment Slime
flaking agents

Product
cone

Fig 2: Substance streams in the glass production:

production of special glass, for example production of TV cones

12 August 2004

2.2 Melting
The glass melting occurs at temperatures up to
1700 °C in continuously operated furnaces or non-
continuous pots and daily furnaces. The continuos
furnaces are continuously charged with batch and
melted and refined glass is continuously taken out
for the forming process.
Fig. 1 shows the substance streams in the glass
production10 and Fig. 2 the substance streams in
the production of special glass, as an example the
production of TV cones.
For the production of stone wool diabas and basalt
are also melting in water cooled shaft furnaces, in
which the raw materials are stacked in layers al-
ternately with coke.
Different types of fuel oil, natural gas, liquid gas
and electricity are used as energy source. Coke is
used in shaft furnaces.
Regenerators or recuperators are used for the re-
covery of a part of the waste gas heat. The melting
ovens as well as their additional facilities and
equipment are cooled by air or water.
The melting ovens' waste gases are treated with
filters, sorption or other procedures according to
the rules of the TA Luft. The waste arising from
these procedures is discussed in 5.3.2.
2.3 Forming
2.3.1 Hollow glass (container glass,
tableware, special glass)
The forming of the glass is carried out both in
automatic and manual procedures.
Substantial areas of container glass, tableware
and special glasses are produced according to the
gob feeding process, working in single gob as well
as in multiple gob procedures. With these proce-
dures, the hot glass gob is cut by shears from the
remaining glass mass. For the shear blades' and
10
For parts of the mineral fibre industry, Fig. 1 differs in re-
spect to the use of other raw materials as well as their
preparation and charging.
ATV-DVWK-M 374E
the gob funnel's cooling normally cooling lubricants
are added to the water.
The further forming is carried out either by quickly
operating multiple-section machines or manually
by pressing, blowing, centrifugation or combination
of theses procedures.
Faulty gobs or posts are often granulated in a wa-
ter tank.
Usually, the mould material is made of metal, coal
or wood. For the mould cooling air and/or water is
used.
Literature: SCHAEFFER (1990), PFÄNDER (1997)
2.3.2 Flat glass
Mainly, flat glass is produced according to the so-
called float process. From the furnace the glass is
flowing through a spout channel to a following tin
bath (float bath). The arriving glass mass stretches
on the liquid tin (800 °C) which is under bath at-
mosphere in the float bath. Carried by the density
difference between tin and glass, the glass swims
(floats) – guided as an endless ribbon – to the spe-
cial rollers outside the float bath. These rollers lift
the glass ribbon and guide to into a following cool-
ing channel, in which the glass is slowly cooled
down from 600 °C to 60 °C under controlled cir-
cumstances.
Furthermore, sporadically flat glass is produced
according to some older drawing processes (Four-
cault, Libby-Owens and others) and according to
the machine flow process (rolled glass).
Literature: SCHAEFFER (1990)
2.3.3 Tubes
The main part of glass tubes is produced auto-
matically. The most common process is the one
according to DANNER. From the furnace the
melted glass flows in a continuous string on a slop-
ing, conical, and rotating tube („Danner blowpipe“)
and is separated by drawing at its lower end. By
feeding air into the hollow space the forming hol-
low glass body is maintained until its setting. The
August 2004 13
ATV-DVWK-M 374E
desired pipe sizes are defined among other things
by the drawing machine's speed.
Also the VELLO process is important, in which the
hot glass exits from a debiteuse and is separated
by drawing in a similar way.
Literature: PFÄNDER (1997), GIEGERICH, W.
And TRIER, W. (1964) , SCHUMANN, D. et al.
(1979)
2.3.4 Glass and mineral fibres
The following processes are used for the produc-
tion of endless glass fibres (also refer to VDI
3457):
Drawing from a bushing: the glass is fed to the
bushing either directly from the glass melting fur-
nace (direct melting procedure) or as re-melted
balls or pellets (ball melting procedure). In the
bushings' bottom there are spinning holes from
which the liquid glass gets out and is drawn to fi-
bres.
Drawing process for optical purposes: Pre-
manufactured canes and/or tubes are melted at
one end, from which then fibres are drawn, which
is especially used for optical fibres.
For the production of mineral fibres (glass wool
and stone wool) the following processes are used
(also refer to VDI 3457):
Centrifugal drawing: by centrifugal force and the
assistance of an air-stream the vertically fed melt
is split into mineral fibres, which are collected as
uncured mat in forming hoods, forming sections or
similar. The most common process is the steam
centrifugal blowing procedure (TEL process).
Steam blowing procedure: The melt flowing from
a bushing is split by a parallel directed air-stream.
Like in the centrifugal drawing process, the mineral
fibre is either sucked or blown and collected.
14 August 2004
Cascade centrifugal process: The melt is falling
freely on the circumference of a horizontal rotor
which distributes it on the surface of two or three
additional rotors; by that the melt is drawn to fibres
under assistance of the air friction. The mineral fi-
bres are sucked or blown and collected
(ULLMANN, 1988).
2.4 Work and finish
2.4.1 Mechanical work
In many cases, the formed rough glass has to be
worked mechanically to achieve the requested
geometrical, decorative and optical characteristics.
For that purpose it is made use of techniques re-
ferring to cutting, grinding, drilling, milling and pol-
ishing. This leads to abrasions from grinding agent
and glass which either can be re-used in the proc-
ess or have to be disposed.
Usually the rough work (cutting, drilling, milling) is
carry out with diamond tools. For the fine work, be-
side diamond tools there are also several auxiliary
inorganic substances like oxides (e. g. corundum,
ferric oxide, ceria), carbides (e. g. silicon carbide,
boric carbide), quartz sand, garnet, pumice flour
and others, for which usually water is used as ve-
hicle medium.
The work is mainly carried out automatically. After
the work the glasses are mostly washed.
Usually the cooling agent during the mechanical
work and the washing water is completely salt-free
water, with or without additives (cooling and lubri-
cation agents). They are guided in circles (see Fig.
3). Exceptions are only possible for certain cases
(refer to annex 41 of the Abwasserverordnung
(AbwV) part D, part 1 item 1).
 ATV-DVWK-M 374E

Raw and
Work process Waste / wastewater
additional materials

Fresh water
Cooling agent
Grinding water-
Flaking agent Glass grinding slime
Carbon dioxide treatment

dirty cleaned
grinding water grinding water

mechanical
Rough glass surface
treatment

Splash water
Cleaning water

Glass grinding slime

Slaked lime
(Wastewater slime)
Wastewater
Flaking agent
treatment
Ferric-III- Wastewater
chloride

finished product
finished or semi-finished

Fig. 3: Substance streams in the mechanical surface treatment

Raw and
Acid polishing process Wastel / wastewater
additional materials

Fresh water Exhaust air

Absorption
Fluorine hydrogen acid Hexa fluoronic silicic acid

Vapors Vapors

Rough glass Used acid Vaporiser

Acid
Fluorine hydrogen acid
polishing
Sulphuric acid Etching slime
Concentrate Distillate
Glass
Fresh water
rinsing

Acetous rinsing water

Used acid

Neutralisation Neutralisation gypsum

Slaked lime

Neutralised water

Slaked lime
Neutralisation mud
Precipitation agent Final (Wastewater mud)
wastewater
Flaking agent treatment
Wastewater
Ferric-III-
chloride

Product

Fig. 4: Substance streams of acid in the special glass production

August 2004 15
ATV-DVWK-M 374E
2.4.2 Chemical work
The acid polishing of lead crystal glass, crystal
glass and special glass is carried out with different
procedures, using a mixture of fluorine hydrogen
acid (1 % to 5 %), sulphuric acid (50 % to 70 %)
and water at a temperature of 50 °C to 70 °C.
The glass to be worked is placed in baskets or
drums and gets polished in a dipping procedure.
Depending on the number of acid baths, it is differ-
entiated between the single-bath procedure (pol-
ishing bath) and the multiple-bath procedures (pol-
ishing bath and washing bath). Before the
polishing bath a cleaning bath takes place, which
can be either acetous or basic. Following the pol-
ishing baths, there are always one or more rinsing
baths. Fig. 4 shows the substance streams of acid
in the special glass production.
Similar to the acid polishing, the frosting with
aqueous fluorine hydrogen acid and sulphuric acid
with additional alkali and ammonium compounds is
carried out. Afterwards the glasses are rinsed with
water.
In another finishing procedure the glass achieves
different mechanical and optical characteristics
(pressure, breakage strength, refractive index) by
ion exchanges in the surface. Usually this process
is carried out in hydrochloric melts at temperatures
between 200 °C and max. 800 °C.
2.4.3 Coating
Usually the decoration of glass (screen printing,
painting, golden rims) is made in an application
procedure with suitable colours. Depending on
type and glass composition these colours are fired
on at 400 °C to 600 °C.
The silvering is achieved by application of thin
metal layers (e. g. silver, copper) after a prelimi-
nary cleaning of the glass surface. The desired
metal deposit arises either from the liquid phase by
chemical reduction or dry by vacuum evaporation.
The metal cover is protected against damages by
one or two varnish layers.
For surface coating container glass in hot status
can be subject to a vapour deposition with metal
16 August 2004
chloride (TiCl4, SnCl4) or metal organic compounds
(e. g. mono butyl tin triple chloride), and, if need
be, be sprayed with lubricant after annealing.
These latter substances stick only on glass and do
not occur in any wastewater or waste stream. For
special purposes, glass can be coated with plastics
or other substances in a liquid procedure.
2.4.4 PICVD process
The PICVD (Plasma Impulse Chemical Vapour
Deposition) process which was developed by
Schott is especially suited for the coating of three-
dimensioned subjects. In this process the two sin-
gle components – titanium tetra chloride and
HMDSO (hexa methyl disiloxan) – are brought to a
reaction with oxygen in a vacuum by plasma crea-
tion via a magnetron, so that finest and highly pure
particles of titanium and silicon dioxide from the
gas phase can deposit on a surface. Initially devel-
oped for the finish of glass fibres for optical pur-
poses, this method now is used for the coating of
spectacle glasses (de-mirroring and improvement
of scratch resistance of glass and plastic spectacle
glasses), as well as for the coating of energy sav-
ing halogen lamps and high end lamp reflectors.
Here up to 100 high temperature resistant layers
with thickness between 20 nm and 300 nm care for
the required lamp reflectors' characteristics. They
are the layers of titanium oxide and silicon dioxide
mentioned above.
Literature: GLÄSER (1994), KRAUSE (2003).
2.4.5 Chemical tempering of flat glass
This procedure is characterised by the fact that a
pressure tempering of the glass surface is
achieved by creating a difference compared to the
glass inside by changing the surface's composi-
tion. The method of chemical tempering is based
on ion exchange. The ions of the single chemical
elements have different radiuses and are arranged
with different distances related to each other. If for
instance a sodium containing glass is heated
slowly in a potassium hydrochloric melt close to
the transformation temperature, the sodium ions
migrate form the glass into the hydrochloric melt
and the potash ions from the hydrochloric melt into
the glass surface. As the potash ions entering the
glass surface have an ion radius which is approx.

30 % larger, a kind of "shortage of space" is cre-
ated in the glass surface, which causes the com-
pression. The exchange zone has to have a mini-
mum thickness of 0.1 mm to achieve a strength
improvement of factor 5 to 8. Glasses tempered by
ion exchange are required for special demands, e.
g. in the air plane industry, for centrifuge glasses
and in the lighting branch as well as for the tem-
pering of spectacle glasses.
2.4.6 Further treatment of glass and
mineral fibres
With glass fibres for textile applications as well as
for plastics reinforcement the endless fibres have
to be coated due to the sensibility of the untreated
surface. For that purpose organic substances
(size; see 3.2.2) are applied on the fibres. By that
the friction effect of glass-on-glass and the risk of
mechanical damage during the further treatment is
reduced to a minimum. With fibres for plastics rein-
forcement the coating serves to achieve the com-
patibility with the plastic of the respective use. The
filaments are bundled and wound up on packages.
The wound up fibres can be further treated to be-
come e. g. thread, mats, rovings (cylindrical pack-
ages with precision winding) or short fibres. In the
production of mats the fibres are cut, split and treated
with a binding agent.
With glass fibres for optical application the fibres
wound up on drums after the drawing process are
equipped with a protective coat, either as single fi-
bre or as fibre bundle. Usually, this consists of
plastic (e. g. polyethylene) or, to a lesser extent, a
flexible metal hose. The end of the fibre has to be
cut plain and polished for a defined front area. For
that purpose the fibres, either as single fibre or as
bundles, are fixed in a metal shell and glued in ad-
vance.
Usually mineral fibres are worked by coating, im-
pregnation or soaking with binding agent and/or
lubricants and, if need be, with the assistance of
subsequent hardening procedures, to become dif-
ferent finished products. The work comprises be-
sides others: cutting, pressing, stamping, sawing,
milling, grinding, and facing (compare VDI 3457).
ATV-DVWK-M 374E
3 Wastewater
This section deals with the water consumption in
the glass and mineral fibre industry, irrespective of
the question, if in the single case wastewater oc-
curs or not.
3.1 Cooling water
It is differentiated between direct and indirect cool-
ing circuits with and without product contact.
Cooling water with product contact arises if due to
standstills, job changes, trouble or other opera-
tional reasons hot glass is chilled with water. Usu-
ally the generated granule is taken out with a
scraper conveyor and in general is re-entered in
the production process again. The generated
wastewater (so-called scraper water) is warm and
possibly slightly polluted with glass components
(depositable substances, alkalis, earth alkalis) and
oils.
Cooling water without product contact comprises:
boiler water systems, cooling circuits for compres-
sors, cooling circuits for other cooling purposes like
e. g. cooling of certain parts of the furnace or the
inside cooling of the forming tools.
Cooling water circuit are either closed or work as
open systems with de-mudding. In these cases
wastewater occurs, which is slightly charged with
common conditioning agents.
The rules stated in annex 31 AbwV and possible
requirements of the local drainage/wastewater
statutes are valid for the injection of wastewater
from open and closed cooling circuits. Especially a
possible charge of the cooling water with biocides
has to be checked.
Further literature: ATV-DVWK-M 706 „Kraftwerke
und Energieversorgungsbetriebe“, Parts 1 to 3.
3.2 Process water
According to annex 41 AbwV part B „the wastewa-
ter is not allowed to contain any halogen hydrocar-
bons originating from additional substances like
cooling lubricants. The proof that there are no
August 2004 17
ATV-DVWK-M 374E
halogen hydrocarbons in the wastewater can be
achieved by a manufacturers' statement that the
used additional substances do not contain halogen
hydrocarbons.“ Also annex 41 AbwV part E has to
be paid attention to, according to which the re-
quirements for wastewater are defined at the place
of occurrence.
3.2.1 Shear cooling
Like described in 2.3.1, in the gob feeder process
the hot glass gob is cut by a shear from the re-
maining glass mass. For improvement of the shear
blades' lubrication and cooling effect, water mix-
able cooling lubricants can be used, which have
been developed for this purpose. Usually they are
biologically decomposable and contain e. g. alca-
nol amines, polyoles, tensides. Referring to the
"Technische Regeln für Gefahrstoffe (TRGS 611)"
the cooling lubricants are not allowed to contain
neither nitrosating agents or their preliminary
stages (like nitrites) nor secondary amines.
3.2.2 Water in the forming process
In the production of hollow glass water is used in
the forming process for cooling and lubrication,
when a glass article's turn or movement in the
mould takes places. This can lead to a slight
wastewater charge with mineral oil carbohydrates.
Endless glass fibres are coated with a size during
drawing. In that context losses of the used sizes
occur. Depending on the purpose of the produced
fibres either "textile sizes“ or „plastic sizes“ are
used. Textile sizes are substances like potato or
corn starch as glue and film shaper as well as
vegetable fat as lubricant. The plastics sizes con-
tain besides others: polyester resins, epoxid resins
(few), polyvinyl alcohol (few), polyurethane, film
shaper, sticking agents like silanes, rinsing agents
and emulsifier. These lead to increased CSB val-
ues in the wastewater (see 5.3.8).
18 August 2004
3.2.3 Water in the further treatment
3.2.3.1 Washing and rinsing
Washing procedures are used for a preliminary
cleaning of glass for a subsequent finishing proc-
ess. Usually, common detergents (surface active
substances) are added to the wash water manually
or automatically. In special cases acids and lye are
used. After the rinsing process the wastewater
may contain substances from preceding treatment
steps.
3.2.3.2 Mechanical treatment
According to 2.4.1 usually during the treatment of
glass water is used as cooling or transport medium
for substances mentioned in that section. Further-
more biologically decomposable cooling lubricants
are used. Besides others they contain e. g. alcanol
amines, polyoles, tensides. During the mechanical
treatment the cooling water gets charged with
glass friction, possible also contents of the glass
matrix can dissolve to a small extent.
3.2.3.3 Chemical work
All work and finishing processes being carried out
in a liquid, mainly aqueous phase may generate
wastewater in the subsequent rinsing which is
charged with components of the glass matrix.
Usually acid polishing and frosting happen in ace-
tous solution. Besides the acids (e. g.: sulphuric
acid, fluorine hydrogen acid, hydrochloric acid)
also ions from the glass can occur in the wastewa-
ter.
In other cases, e. g. at the ion exchange both basic
and acetous wastewater shares can arise.
3.2.3.4 Coating
Usually the decoration and surface coating are car-
ried out without wastewater (also refer to 2.4.3 and
3.3.2).

During the mirror production after preliminary
treatment with tin (II) chloride a silver solution con-
sisting of silver nitrate, ammonia and sodium or
potash oxide in completely salt-free water as well
as a reducing solution containing mainly glucose is
splashed on the glass surface for silvering. After-
wards a copper layer is applied in a similar way.
After respective cleaning, the surplus solution is
guided into the wastewater.
Literature: Gläser (1994), Kempf (1959).
3.2.3.5 PICVD process
The exhaust air components from the coating
process have to be washed out of the exhaust gas
stream with a moist washer (in principle also dry
sorption is possible, however not yet tested) on al-
kaline basis (soda lye respectively sodium bisul-
phite solution). After de-mudding the wash water of
the exhaust gas washer can be injected into the
sewers, if it complies with the state of the art ac-
cording to annex 41 AbwV and the injection condi-
tions of the rules for direct injections issued by the
Länder respectively with the requirements of the
local drainage/wastewater statutes.
3.2.3.6 Further treatment of mineral
fibres
Usually binding agents and lubricants are added
during the production of the different glass and
mineral wool products. This is carried out by spray-
ing an aqueous solution, emulsion or suspension.
For this purpose are mainly used: duromere syn-
thetic resins (based on phenol, urea or melamine
formaldehyde), mineral oil, vegetable fat, silanes
and silicon oils.
Usually water is consumed in the production of
mineral fibres. Substantial amounts of steam
evaporate from the area of splitting, lesser
amounts from the area of the curing ovens in the
surrounding air. Apart from that no more water is
drained. The process water is guided in a closed
circuit. Fresh water is added to the system as cool-
ing or washing water. Usually washer water is in-
jected in the process water circuit (VDI 3457).
ATV-DVWK-M 374E
3.3 Wastewater from side installations
and exhaust gas washers
3.3.1 Side installations
Usually the cleaning of machines, machine parts,
mould parts and tools complies with the standard
procedures for cleaning and de-greasing com-
monly used in engineering works. The detergents
in normal commercial use can contain sodium hy-
droxide, soda, tri sodium phosphate, polyphos-
phate, alkali silicates, alkali borates and tensides.
They enrich with oils, fats, tinder and dirty sub-
stances and have to be transferred to an appropri-
ate external disposal or a waste water treatment.
3.3.2 Exhaust gas wash
Exhaust gas wash can be used in different areas:
• Glass melt: for deposit of acetous gaseous ex-
haust gas components like sulphur oxides, fluo-
rine and chloride carbohydrates usually dry or
nearly-dry sorption procedures are used. These
procedures are free of wastewater. In some
cases also exhaust gas washers are used (whirl
washers, Venturi washers and others).
• Chemical work: during the glasses' treatment
with sulphuric and fluorine hydrogen acid (acid
polishing, frosting) gaseous silicon tetra fluoride
is generated. In multiple-step washers equipped
with filling bodies this gas is washed out and
concentrated as hexa fluoronic silicic acid. This
can be transferred to recycling. According to
annex 41 AbwV part E no wastewater is allowed
to be generated from the exhaust gas wash.
• Surface coating: like described in 2.4.3 con-
tainer glass in hot status is subject to vapour
deposition with metal chlorides, e. g. titanium or
tin tetra chloride. Usually the sucked exhaust
gases are cleaned together with the furnace ex-
haust gases.
• In single cases the suction devices are
equipped with moist washers instead. This can
lead to slight loads of the wastewater with the
respective metal oxides and hydrochloric acid,
which has to be disposed appropriately. Metal
organic coating agents are usually sucked, col-
lected and used again after re-working by the
manufacturer.
August 2004 19
ATV-DVWK-M 374E
• With the online coating occur exhaust gases;
they consist of gases of an inorganic chloride
compound (e. g. tin chloride) that have already
reacted completely and gases, which have not
completed their reaction yet. For to complete
the reaction, the coating gases can react in total
in a reactor, that means, they change into the
oxide form. The hot gases are guided over an
exhaust gas cooler, which decreases the ex-
haust gas temperature by sprayed-in water, and
then they are transferred to the electric filter. in
the electric filter the metal oxides e. g. of the tin
are deposited and collected. These metal ox-
ides are recycled. The exhaust gases leaving
the filter are neutralised in a soda lye washer.
The cleaned air is released over a stacker. The
arising salt-containing water is collected in tanks
for a later transfer to the wastewater cleaning,
where they are injected in a spray dryer. The
spray dryer evaporates the water and the dry
salt is taken out over a cell wheel sluice. The
spray dryer's hot air can consist of the waste
heat of the roller annealing lehr which is guided
over an after-heater. Usually the salts are used
in mine filling.
• Further treatment of mineral fibres: during im-
pregnation, hardening and final work exhaust
gas streams occur which are cleaned. This is
carried out with moist or dry working devices for
exhaust gas treatment, like e. g. moist washer,
moist electric filter, hose filter, thermal after-burn
(combined with heat re-transfer systems). Wash
water from these exhaust gas treatment devices
contains as main components residues of min-
eral fibres as well as organic parts (phenol for-
maldehyde resin in different condensation
stages). After mechanical separation of the
mineral fibre residues the washer water is re-
transferred to the process water circuit.
20 August 2004
3.4 Measures for avoidance, reduction
and recovery
Multiple water use
depending on its further use, slightly charged
process water can be used for further purposes in
the plant, either with or without treatment. This
saves water and the amount of wastewater is sub-
stantially reduced. Attention has to be paid to a
possible enrichment of contents.
The multiple use can be different:
• in the first phase of use taking up heat, in the
second taking up dissolved solids or vice versa.
• in two or more steps taking up of different or
same substances (cascade rinsing system).
Examples of application:
• use as consumption water in vaporisation sys-
tems,
• use as consumption water for moistening raw
materials,
• multiple use as cooling water,
• cascade rinsing in washing procedures.
In contrast to the multiple use without intermediate
treatment, in the rinsing water circuit with ion ex-
changer a nearly permanent use of the same water
is aimed.
The regenerates arising after treatment of the ex-
changer resins represent a wastewater charged
with pollutant which has to be treated according to
section 4. In this context lot treatment units have
proven good.
Completely closed water circuits do not exist. Sub-
stances that enrich, either solid or dissolved, have
to be extracted, continuously or non-continuously.
For the treatment of such wastewater the proce-
dures described in section 4 have proven good.
 ATV-DVWK-M 374E

Table 7: Measures for wastewater treatment in the single production processes

Ref. Sedimen- Centrifugal Floating Filtering Deposit of Precipi- Ion Neutra- Burning
section tation force de- light sub- tation exchange lisation
Flaking posit stances
3.2.1 – – – – (X) – – – (X)
Shear cooling
3.2.2 – – (X) – (X) (X) – (X) (X)
Forming process
3.2.3.1 X – (X) X – – – X –
Washing and rinsing
3.2.3.2 X (X) (X) (X) (X) – – – –
Mechan. treatment
3.2.3.3 X (X) (X) X – X – X –
Chemical work
3.2.3.4 X – – X – X X X –
Coating
3.3.1 – – – X X X – X (X)
Side installations
3.3.2 (X) X (X) X – X – X –
Exhaust gas wash
X ... usual; (X) ... done sometimes

K polymere FeCl3 A polymere FeCl3 H2SO4

Wastewater CHLORINE
DIOXIDE
DEVICE

SEDIMENTATION
FLAKING - COURSE
PUMP CONTAINER
BUFFER-
SUMP CONTAINER

Sand filter

MUD
THICKE- CHAMBER FILTER PRESS
NER
BUFFER
CONTAI-
NER

MUD PLANT NET

Filtrate WASTEWATER SEWER

Fig. 5: Wastewater treatment in the special glass industry

August 2004 21
ATV-DVWK-M 374E

4 Wastewater • Lot treatment devices do not have lingering time

characteristics and so do present the disadvan-
treatment tages connected with it.
• The single process steps can be tested and de-
The measures' type and scope are based on pro- fined in the laboratory and afterwards trans-
cedures which have been tested for the respective ferred to the lot treatment device.
cleaning problems (see table 7).
• Use of treatment methods with long-term reac-
tions.
Fig. 5 shows the possible steps in wastewater
treatment at the example of the special glass in- • Realisation of several necessary reactions one
dustry. after the other in one container.
• Treatment of concentrated solutions.
Direct and indirect injectors have to pay attention
to the rules stated in annex 41 of the Ab-
Mostly wastewater treatment is a series of single
wasserverordnung. In due case, indirect injectors
steps (e. g. filling – reaction – deposit – filtering).
have to carry out preliminary treatment measures,
The slowest process sets the frame for the capac-
especially for the reduction of concentration and/or
ity. With larger amounts of wastewater it is efficient
load of heavy metals, for being allowed to inject
to use several smaller reactors which are filled al-
the wastewater in the public sewer system. The
ternately instead of one big reactor. By that the ca-
rules of the municipality statutes have to be re-
pacity can be increased in a nearly continuous op-
spected, which regarding the limitation values for
eration. Usually the reactor sizes are limited to
heavy metals mostly refer to e. g. annex 41 AbwV
max. 20 m³ – 30 m³ due to the occurrence of reac-
or ATV-DVWK-M 115-2 „Indirekteinleitungen nicht
tion technical trouble, especially the quick and effi-
häuslichen Abwassers, Teil 2 Anforderungen“.
cient mixture of the reactors content with the
treatment chemicals (HARTINGER, 1991).
The main tasks of wastewater treatment are
• the elimination of sedimentable substances, However, it should be decided individually for
every wastewater problem which type of wastewa-
• the separation of organic light liquids,
ter treatment – lot by lot or continuously – is effi-
• the neutralisation of acetous and basic waste- cient and by that appropriate.
water,
• the precipitation and retention of dissolved
heavy metals. 4.1 Dissolved solids
The lot procedures is recommend due to the water
With the treatment of glass in aqueous media, es-
saving by the multiple use of rinsing water (see
pecially by chemical procedures, dissolve actions
3.4) and for to be able to keep after-reactions un-
take place. For the treatment of the arising waste-
der control.
water the same treatment processes like in other
industrial branches are applied.
Lot treatment devices should be used in such
cases where the arising wastewater amounts can
be stored and treated in containers with efficient
size. Therefore it is important to minimise the 4.1.1 Chemical precipitation and
wastewater arising from the production. This can neutralisation
be achieved e. g. by cascade rinsing, rinsing water
circuits or multiple use of the wastewater. One of the widest spread treatment methods is the
transformation from the dissolved to the hard to
In general, the lot procedure is the most safe dissolve detachable status by precipitation with
method of wastewater treatment because every suitable reagents.
step is controllable and in due case it can be
started manually at important points. Further ad- The most important precipitation reaction in this
vantages of lot treatment devices are: context is the formation of hard to dissolve calcium

22 August 2004

fluoride (CaF2) and anhydrous gypsum (CaSO4)
with slaked lime in the treatment of wastewater of
the chemical surface treatment (see 3.2.2.3) con-
taining fluorine hydrogen and sulphuric acid.
During monitoring fluoride is often determined as
fluoride in total. However, if it is present in waste-
water in complex-bound type, e. g. as tetra fluorine
borate (e. g. from acetous metal electrolytes), its
precipitation is not possible.
The same conditions like for fluoride are valid for
the precipitation of anhydrous gypsum by neutrali-
sation with slaked lime.
Some metals can be precipitated not only as hy-
droxides with lye but also as carbonates or sul-
phites, e. g. lead as lead carbonate and arsenic
and antimony as according sulphites. These pro-
cedures can be applied for treatments according to
3.2.3.2 (Mechan. treatment), 3.2.3.3 (Chem. work),
3.2.3.4 (Coating), 3.3.2 (Exhaust gas wash).
The precipitation of free fluoride is carried out with
calcium compounds, usually with slaked lime in
combination with the neutralisation. Here it has to
be considered that the fluoride precipitation can
only be successful if per equivalent fluoride also an
equivalent calcium is present. Otherwise additional
calcium ions have to be added in form of dissolv-
able calcium compounds.
According to DIN 4030-1 sulphate in concentra-
tions between 200 mg/l and 600 mg/l has slightly
concrete aggressive characteristics. Therefore it is
usually limited in the indirect injection. In most fa-
vourite case, concentrations around 1400 mg/l SO4
(equilibrium concentration) can be achieved, depend-
ing on the concentration of neutral salt and tempera-
ture. However, with higher neutral salt concentra-
tions this can be exceeded by far. Because of that
reason annex 41 of the Abwasserverordnung
states a limitation value for sulphate of 3000 mg/l.
The value of 1000 mg/l mentioned in the BREF
document for the glass industry can not be
achieved with slaked lime precipitation. Another
possibility could be to precipitate the sulphate as
ettringite (calcium sulphate aluminate), which en-
ables sulphate concentrations of less than 400
mg/l (HARTINGER, 1991). However, this proce-
dure causes a substantially big amount of waste-
water mud and is hard to control. The forming of
ettringite happens spontaneously and can lead to
ATV-DVWK-M 374E
the blocking of piping. So from both economical
and also ecological point of view this procedure
can not be recommed.
The requirements regarding the admissible sul-
phate concentration at the transfer point for the in-
jection into public sewer systems are defined on
the basis of the municipality statutes. Usually the
drainage statutes of cities and towns contain a
generally applicable monitoring value for sulphate.
In most cities and towns however, under certain
circumstances (sewer system material, dilution
conditions) a higher sulphate concentration may be
allowed after checking each single case.
Usually acetous or basic and metal containing
wastewater, especially from the finishing sector,
has to be transferred into a pH value scope be-
tween 6,5 and 9,5 (up to 10). This occurs in reac-
tors, either continuously or in lot procedures, using
acetous or basic reagents (e. g. hydrochloric acid,
slaked lime, soda lye and others). Arising mud is
separated (see 4.2.1.), more to mud see section 5.
4.1.2 Subsequent treatment
The most frequent reasons for a possible excess
of the requirements of annex 41 AbwV respectively
the local drainage/wastewater statutes for rest
concentrations of metals are very small amounts of
solid particles which despite of sedimentation or
flotation (see 4.2.1 and 4.2.3) remain in the
wastewater. In this case a final filtration is neces-
sary. Usually it is carried out with sand or flint fil-
ters. It is also possible to use candle or membrane
filters.
If after the treatment the waster water still contains
small amounts of cat-ioncally dissolved metals or if
the requirements can not be kept under guarantee
at all times, a selectively working cat-ion ex-
changer can be installed after the final filter.
4.2 Non-dissolved solids
4.2.1 Sedimentation
The treatment residues in the glass industry are
substances that can be fairly easy separated by
sedimentation, possibly under preliminary use of a
August 2004 23
ATV-DVWK-M 374E
sieve for the bigger fraction. For to accelerate the
phase separation solid - liquid and for the separa-
tion of colloids often auxiliary substances (flaking
agents e. g. aluminium or ferric sulphate or chlo-
rides and flaking auxiliary substances, e. g. poly-
acrylic amides) are added in small amounts to in-
crease the sinking speed of small parts.
The separation process is carried out in suitable
devices in which the cleared wastewater can over-
flow and the sediment can be extracted as mud.
Subsequently the mud has to be partly drained
(see section 5).
4.2.2 Separation by centrifugal force
With the separation by centrifugal force the sinking
speed of the parts to be separated can be substan-
tially increased in comparison with the separation
by force of gravity. Therefore, depending on the
device's construction, also such particles which in
separators using force of gravity would not deposit,
can be separated. The procedures depend on size
and density of the parts.
As separators working with centrifugal force are
used:
Hydrocyclones, that means devices without mov-
ing parts in which the centrifugal force is created
by tangential feeding of the suspension. This is
separated into one liquid stream which is richer of
solid substances and one that is poorer.
Centrifuges, in which the centrifugal force is cre-
ated by quickly rotating machine parts. Sedimenta-
tion, decanter and filter centrifuges as well as
separators are used.
4.2.3 Flotation
Flotation means the separation of non-colloid dis-
perse particles from liquids by provoking the
swimming up using fine gas bubbles and subse-
quent taking out of the generated foam. Emulsion
containing wastewater can be cleaned by flotation
by way of preliminary breaking of the emulsion and
coagulation of the organic substances with flaking
agents. In the waster water technique, the gas
bubbles' docking necessary for the swimming up
usually is realised by release of air previously un-
24 August 2004
der pressure dissolved in the wastewater (release
flotation) or by electrolytic water disintegration
(electric flotation).
4.2.4 Filtration
Filtering devices in form of belt filters and chamber
filter presses are used where due to process-
related reasons larger amounts of solid substances
to be separated have to be taken out and drained
e. g. thin mud from the sedimentation.
4.2.5 Separation devices for light liquids
Substances that can not or only to a small extent
be mixed with water and which are not emulsified
in a stable way, separate from water by creation of
an own phase. So due to the density difference
they can be extensively separated from the water
with suitable devices. Separators for light liquids
according to DIN 1999-2 are especially used for
the separation of oils. In the glass industry a
wastewater pollution with oils occurs mainly in the
machine area.
In cases where the separation capacity of oil sepa-
rators is insufficient (according to annex 49 AbwV
„Mineralölhaltiges Abwasser“ the monitoring value
for carbohydrates is 20 mg/l), coalescence separa-
tors according to DIN 1999-6 can be used.
4.2.6 Process integrated burning of
wastewater
Cleaning water from the under-floor heating or
cleaning and washing water from the cleaning of
machines or machine parts as well as collected
leaking and splashing water. e. g. from the trough
cooling or other cooling systems for machines for
the production of hollow glass are collected in a
central reception container. From here, depending
on the amount, the water is fed to the single burn-
ers in a controlled manner and injected into the
burner area of the furnace parallel to the fuel-air-
mix. It has to be paid attention that no quality im-
pairment occurs.

4.3 Heat load
Usually high specific heat loads at devices for
glass production require water as cooling agent for
heat discharge. In normal operation the cooling
water heats up to 30 °C to 40 °C. Mainly the cool-
ing down is carried out in open systems (evapora-
tion cooler) in which depending on the surround-
ing's conditions the cooling water is cooled down in
an amount of up to 10 Kelvin.
4.4 External disposal
In case certain highly charged plant wastewater
can not be treated with cost-efficient method within
the plant, this wastewater has to be collected and
disposed externally.
5 Waste
5.1 Type of wastes
Table 8 shows the type of waste in the glass indus-
try, including mineral fibre industry, according to
the Abfallverzeichnisverordnung (AVV).
Dangerous waste is marked with asterisks and has
to be monitored in a special way in Germany ac-
cording to § 41 par. 1 sentence 1 and par. 3 No. 1
KrW-/AbfG. In due case, it is subject to bringing
duties according to § 13 par. 4 sentece 1 KrW-
/AbfG in case these have been stated by local law
(e. g. in Berlin, Brandenburg, Baden-Württemberg,
Niedersachsen, Rheinland-Pfalz, Sachsen-Anhalt
and Thüringen).
Dangerous waste is supposed to have one or more
dangerous characteristics mentioned in annex II of
the European Guideline regarding dangerous
waste (EU, 91/689/EWG).
ATV-DVWK-M 374E
5.2 Waste amounts
With the production of the different glass types and
products waste arises in every production step.
However, it has to be taken into consideration that
glass raw materials, glass compositions, recycling
ratios, melting methods, procedures for further
treatment, environmental rules and quality re-
quirements are subjects to permanent changes.
Therefore the waste amounts of a production unit
as well as comparable productions of different
manufacturers and plants can differ considerably
over the time.
So it is not possible to state common waste
amounts.
5.3 Characterisation, avoidance, re-
use and disposal of waste
5.3.1 Batch residues
Usually batch residues occur with faulty weighing
during batch preparation. Faulty weighing happens
due to trouble in the steering procedures or by
malfunction of the dosing devices in the batch
preparation. This happens only very rarely.
Another form of batch residues is the dust that de-
posits in the batch house or within the transport
devices and the batch charger.
Place of occurrence: batch house, transport de-
vices, batch charging area
Composition: general batch composition with one
component in excess or mixture with sweepings.
August 2004 25
ATV-DVWK-M 374E

Table 8: Types of waste in the glass industry, including mineral fibre industry

Waste code Waste description

01 04 07* Waste arising from the physical and chemical treatment of non-metallic mineral re-
sources, containing dangerous substance
01 04 10 Dusty and powdery waste without such being subject to 01 04 07
01 04 13 Waste arising from stone-mason and stone sawing work without such being subject
to 01 04 07
06 01 06 Other acidsa
06 04 04* Waste containing mercury
06 04 05* Waste containing other heavy metalsb
10 01 21 Mud from the plant-owned wastewater treatment without such being subject to
10 01 20
10 02 02 Non-processed slag
10 11 03 Glass fibre waste
10 11 05 Parts and dust
10 11 09* Batch waste before melting with dangerous substances
10 11 10 Batch waste before melting without such being subject to 10 11 09
10 11 11* Glass waste in small parts and glass dust containing heavy metals (e. g. from elec-
tron probe tubes)
10 11 12 Glass waste without such being subject to 10 11 11
10 11 13* Glass polishing and glass grinding slimes containing dangerous substances
10 11 14 Glass polishing and glass grinding slimes without such being subject to 10 11 13
10 11 15* solid waste from the exhaust gas treatment containing dangerous substances
10 11 16 solid waste from the exhaust gas treatment without such being subject to 10 11 15
10 11 17* Mud and filter cakes from the exhaust gas treatment containing dangerous sub-
stances
10 11 18 Mud and filter cakes from the exhaust gas treatment without such being subject to
10 11 17
10 11 19* solid waste from the plant-owned wastewater treatment containing dangerous sub-
stances
10 11 20 solid waste from the plant-owned wastewater treatment without such being subject
to 10 11 19*
10 11 99 Waste a. n. g.c
16 11 05* Linings and refractory materials from non-metallurgic processes containing dan-
gerous substances
16 11 06 Linings and refractory materials from non-metallurgic processes without such being
subject to 16 11 05
17 04 05 Iron and steel
17 06 03* Other isolation material consisting of dangerous substances or containing such
substances
17 06 04 Isolation material without such being subject to 17 06 01 and 17 06 03
19 02 05* Mud from physical - chemical treatment containing dangerous substancesd
* dangerous type of waste according to the Abfallverzeichnisverordnung
a in the glass industry e. g. hexa fluoronic silicic acid
b Etching mud from the acid polishing
c a. n. g. = not mentioned anywhere else
d Neutralisation gypsum form the acid polishing

26 August 2004
 Table 9: Characteristic components of filter dust (mass content in %)11

Sub- Flat glass Container Crystal glass Lead crystal Picture tube glass Glass and mineral fibres
stance (float glass (tableware) glass E-glass Glass wool Stone wool
glass) screen cone endless Steam Steam blowing Cascade centrifugal
glass fibres centrifugal blowing procedure procedure
procedure
Al2O3 – 0,07 0,02 – 0,11 0,05 – 0,11 0,25 – 0,35 0,05 – 0,15 0,5 – 10 0–3 0–2 1 – 27
As2O3 0,01 0,02 0,05 – 5,0 0,1 – 3,0 – – 0 – 0,1 – – –
B2O3 – – 0,5 – 2,0 0,5 – 4,0 – – 17 – 65 5 – 45 – –
BaO – – < 0,01 – 2,0 0,01 0,20 – 0,25 0,1 – 0,2 – < 0,5 – < 0,5
CaO 35 – 37 34,9 0,50 – 1,2 0,01 – 0,15 30 – 40 0,05 – 0,15 2 – 33 < 1 – 50 15 – 25 1 – 18
Cl – 2,3 – – 0,8 – 1,5 0,5 – 1,0 0 – 0,5 – – –
CoO – – 0,003 0,003 – – – – – –
Cr2O3 0,03 0,04 0,001 – 0,003 0,003 0,01 – 0,03 < 0,005 0 – 0,3 < 0,5 – –
CuO – – – – – – 0 – 0,1 – – –
F – 0,44 0,1 – 0,7 0,04 8 – 10 0,5 – 1,5 2–3 0 – 10 – –
Fe2O3 0,12 0,10 0,02 – 0,8 0,04 – 05 0,05 0,005 0 – 0,2 0–1 0–5 2–7
K2O – 0,40 10,0 – 20,0 5,0 – 18,0 10 – 13 2–4 8 – 22 0–5 0–3 6 – 14
MgO 0,47 0,31 0,01 – 0,02 < 0,01 0,2 – 0,3 0,01 0,2 – 1 < 30 0 – 10 1–6
Na2O 2,2 12,8 2,0 – 20,0 3,0 – 10,0 0,01 0,01 3–8 5 – 35 0–5 5 – 20
NiO 0,01 – 0,003 0,003 4–5 0,8 – 1,2 – – – –
P2O5 – 0,05 – – – – 0 – 0,6 < 0,5 – <1
PbO – 0,33 0,2 – 30,012 25,0 – 40,0 0,2 – 0,3 80 – 90 0,5 – 0,7 – – –
Sb2O3 – – 3,0 – 10,0 0,1 – 0,5 2,0 – 3,0 0,5 – 1,0 – – – –
Se – 0,23 – – – – – – – –
SiO2 0,15 0,36 2,0 – 8,0 25,0 – 50,0 2,0 – 3,0 0,5 – 1,0 2 – 30 < 0,5 – 25 20 – 45 10 – 40

ATV-DVWK-M 374E
SnO 0,05 0,10 – – – – – – – –
SO3 52 – 54 30,9 0,5 – 7,0 0,05 – 2,0 9,0 – 12,0 1,0 – 1,5 2 – 28 1 – 30 0–2 –
SrO 0,01 0,01 – – 0,3 – 0,6 0,05 0 – 0,2 – – < 0,5
TiO2 0,41 0,64 0,01 – 0,07 0,03 0,02 0,01 0 – 0,1 < 0,5 – <1
August 2004

V2O5 – 0,03 – – – – – – – –
ZnO – 0,02 0,01 – 1,5 < 0,01 – 1,0 0,8 – 1,0 0,04 – < 0,5 – –
ZrO2 – – 0,01 – 0,03 0,01 – 0,09 0,01 0,01 – – – –

11
The filter dust's composition is very manifold. The data stated here do only serve for orientation purposes. The composition largely varies with exhaust gas cleaning process' steering and type.
12
Lead free crystal glass usually has got only lead emissions close to zero in the exhaust gas due to raw material pollution. However, with common lead contents of 5 % to 8 % in the batch the fil-
27

ter dust can enrich with lead oxide up to 30 %.

ATV-DVWK-M 374E
Avoidance: Faulty batch can only be reduced if
the device's general reliability can be further in-
creased. At the moment these devices' capacity is
already at 98 % to nearly 100 %.
The occurrence of dust can be minimised or
avoided by closed systems. Closed systems are
mostly installed at the places of occurrence.
Re-use and disposal: Batch residues are re-used
in the container glass industry, in the flat and spe-
cial glass industry usually rejected due to quality
reasons. Mixtures with sweepings also have to be re-
jected. Given suitable composition or suitable pre-
liminary treatment, rejected batch residues can be
re-used e. g. in mine filling (also refer to 5.3.2 and
5.3.4). Due to the small and non-continuously aris-
ing amount as well as individual quality require-
ments regarding raw material and product a use in
other glass plants can not be realised. If re-use is
not possible, the disposal is carried out on a dump
licensed for such substances.
5.3.2 Filter dust
Glass plants in Germany are equipped with exhaust
gas cleaning and filtering devices for generated dust.
With the exhaust gas cleaning and the suction of
glass and batch dust different filter dust arises de-
pending on glass type, production conditions and
exhaust gas cleaning procedure.
Depending on the exhaust gas composition and
exhaust gas temperatures electric filters or filtering
separators, in due case with preliminary dry or
nearly dry sorption procedure for separation of
acetous waste gas components are used. The fil-
ters are automatically cleaned in regular intervals.
The filter dust is collected in bunkers or transport
containers.
Place of occurrence: exhaust gas cleaning de-
vices, batch houses, hot end, cold end
Composition: See following table 9.
Avoidance: By an appropriate selection of raw
and additional materials as well as an optimised
way of operation the amount of filter dust can be
reduced, as far as this it technically and economi-
cally tenable. This minimises the expenses for
secondary measures (e. g. filter dimension).
28 August 2004
The complete re-transfer of filter dust e. g. in facili-
ties for the production of flat glass, container glass
and glass fibres is explicitly appreciated according
to the TA Luft. Taking into consideration other
conditions, the TA Luft enables the assertion of a
higher emission values regarding sulphur dioxide
in comparison to other plants in which the filter
dust is not completely re-entered in the production.
Re-use and disposal: In the container glass, flat
glass and mineral fibre industry filter dust is mainly
re-used again.
With special glasses, pollution e. g. by colour-
donating metal oxides can limit a re-use,
Dust which can not be re-entered in the process,
can be used externally (e. g. non-ferric metal plant,
mine filling) or disposed (surface dump, under-
ground dump).
5.3.3 Glass cullet
Usually non-soiled glass cullet is immediately re-
entered in the melting process and so does not
represent waste.
Glass cullet with dirt from the melting process is
cullet that is miss-coloured or interspersed with
metallic, mineral oder glassy inconsistencies or
glass cullet that after the forming process, espe-
cially during further treatment has become dirty
due to e. g. lubricants, foil residues (flat glass
laminated screens), grinding agents and/or sweep-
ings.
Usually the separation of the cullet from it's pollu-
tion is carried out at a place different from the
place of glass production.
Place of occurrence: glass melt, glass forming,
glass treatment, sorting, packing, warehouse
Composition: the glass cullet composition is equal
to the product composition. In general, the pollu-
tion (as stated above) is insignificant in regard to
weight and volume.
Avoidance: avoidance is achieved by a reduction
of defects in the production process, a reduction of
inconsistencies in glass by optimisation of batch

production and melting process (e. g. by keeping
the minimum times for homogenisation and refin-
ing), use of more resistant refractory materials.
The amounts of miss-coloured glass arising during
colour changes can be reduced by an optimised
management of job and melting changes.
Under certain circumstances also the cullet with
pollution can be melted in the production of glass
products of different quality. A respective melting
unit has to be on hand. The products have to be
saleable on the market.
Re-use: The transfer to other glass plants for melt-
ing is limited due to the pollution and/or different
chemical compositions.
Suitable cullet, e. g. lead-containing, can also be re-
used in non-ferric metal plants.
The re-use of lighting glass in the melt has to be
limited due to the sticking mercury parts. Usually
shredded fluorescent tubes have got mercury
shares of 30 mg/kg to 40 mg/kg. By an subsequent
cleaning in a cullet cleaning device with water, the
mercury share can be reduced to 5 mg/kg. A fur-
ther reduction is technically impossible. Therefore
the cullet ratio in the existing technical production
facilities is limited 2 to 5 mass % for to keep the re-
spective exhaust gas values of the TA-Luft.
Before being used as construction material or addi-
tive an aptitude test has to be carried out. The re-
use has to be carried out properly and without
causing any damage. For underground mining re-
use the "Verordnung über den Versatz von Abfäl-
len unter Tage (VersatzV)" has to be respected.
Disposal: In case neither avoidance nor re-use of
the polluted cullet is possible, it has to be disposed ac-
cording to its composition and its leaching character-
istics on an appropriate dump. Usually for container
and flat glass settlement waste dumps can be con-
sidered. For other glass it has to be decided from
case to case depending on the glass composition's
type and condition.
Literature: GREULICH und HÜNLICH (1996),
LARMS et. al. (1999)
ATV-DVWK-M 374E
5.3.4 Furnace material
Furnace material arises with repairs and recon-
struction (approx. all 4 to 14 years) of the furnaces.
It mainly consists of refractory materials and dust
products of glass melt, chamber and exhaust gas
channel deposits.
Shaft furnaces for the production of stone wool are
constructed approx. weekly, during which small
amounts of fire-light bricks arise which are inter-
nally re-used as melting raw material.
By targeted measures during the demolition and
subsequent careful sorting, the part of furnace ma-
terial that hat to be disposed can be substantially
reduced.
Place of occurrence: furnace, feeder (glass
channel), recuperator, regenerator and exhaust
gas channels.
Composition: Refractory materials are non-
metallic materials with a pyrometric cone equiva-
lent (PCE)13 of minimum 1500 °C. Refractory ma-
terials consist of high melting oxides (Al2O3, MgO,
Cr2O3, ZrO2), fire-proof silicates and other materi-
als (see table 10).
A priori, refractory materials do only contain small
amounts of water-soluble contents. However, glass
melting furnaces are subject to a strong mechani-
cal, thermal, and chemical permanent stress. Be-
sides the components of the refractory materials,
the composition of the processed batch (raw mate-
rials and additives) and the type of heating are im-
portant for the furnace material's chemical compo-
sition.
13
The PCE is an auxiliary tool for monitoring and control of the
burning operation. Not only the temperature is determined
with the PCE, but also the influence of temperature and time
which both are conditions for the achieved burning degree.
Details are stated in DIN EN 993-12 and -13.
August 2004 29
ATV-DVWK-M 374E

Table 10: Main components of refractory materials (ISO 1109)

Products Limit content of main components

High alumina containing products Al2O3 > 56 %
group 1
High alumina containing products 45 % < Al2O3 < 56 %
group 2
Fire-clays 30 % < Al2O3 < 45 %
Fire-clays low in alumina 10 % < Al2O3 < 30 %; SiO2 < 85 %
Half silica products 85 % < SiO2 < 93 %
Silica products SiO2 > 93 %
Basic products:
Magnesite MgO > 80 % (main component magnesite)
Magnesiumchromite 55 % < MgO < 80 % (main component magnesite and chromite)
Chromitemagnesite 25 % < MgO < 55 % (main components chromite and magnesite)
Chromite Cr2O3 > 25 %; MgO < 25 % (main component chromite)
Forsterite main component forsterite = Mg2SiO4
Dolomite main component colomite = CaMg(CO3)2
Special products On the basis of:
carbon
graphite,
zirconium,
zirconia (ZrO2),
silicon carbide,
carbide (others than SiC),
nitride
borides, spinels (other than chromite),
products of different oxides (others than basic products)
products of pure oxides including aluminium, silicon, magnesium,
zirconium

Avoidance: Waste avoidance is possible by opti-
misation of the furnace campaign. Furthermore in
some application cases new technologies (e. g.
fuel-oxygen heating instead of fuel-air-heating)
which make regenerators obsolete, offer the pos-
sibility to avoid refractory material waste.
Re-use: Re-use possibilities depend on material
composition, pollutant content and material status.
Primary recycling: primary recycling is possible if
after selective demolition undamaged refractory
bricks can be directly re-used.
With handing back lesser stressed material to the
refractory material's manufacturer, maybe a direct
re-use (with or without preparative treatment) is
possible.
Secondary recycling: material's use after transfor-
mation into a new product in other production
branches and conditions of use (secondary con-
struction material, depending on the classification
values of the LAGA rules e. g. for the installation in
free areas and for use in road construction as well
as intermediate or filling layer in dumps). The
harmlessness has to be checked in every single
case as long as no federal unitary standard values
are available.
Mining technological re-use: Here in particularly
the mechanical and the construction material char-
acteristics of waste are used to achieve a mining
technological target. The set of rules to be applied
for this purpose is the VersatzV. Apart from the limi-
tation values for heavy metals between 1 % (Cu)

30 August 2004
 ATV-DVWK-M 374E

and 50 % (Fe), above which the metal recovery is
emphasised, and the classification values in the
TOC (Total Organic Carbon) and glow loss, further
limitation values depend on the specific geological
situation of the mine. These could be e. g. obsolete
if „in plants in salt stone“ „a long-term safety proof
was given to the authorities in charge“. For details
refer also to Advisory leaflet ATV-DVWK-M 358
(2003).
Re-use as additive to the batch: under certain cir-
cumstances the deposit from the chambers and
channel, which have arisen in the container glass
industry in connection with a furnace material, can
be used after preliminary treatment as batch com-
ponent.
Disposal: Is neither avoidance nor re-use of the
furnace materials and the deposits possible, only
disposal remains.
According to the material's analytical characteris-
tics it has to be disposed at underground dumps,
special waste dumps, settlement waste dumps or
class 0 dumps according to the "Deponieverord-
nung (DepV)".
5.3.5 Mud from the wastewater
treatment (wastewater treatment
mud)
Place of occurrence: mud from the wastewater
treatment arise in context with:
1. the mechanical surface treatment of glass,
2. the chemical surface treatment of glass,
3. aqueous exhaust gas cleaning systems (e. g.
PICVD process),
4. special procedures (e. g. chemical tempering of
glass).
Composition: The wastewater treatment mud's
composition depends on the places of occurrence
which are described below.

Table 11: Examples for the composition of dried glass grinding slimes
(mass content in %)

Parameter Lead crystal Crystal glass Flat glass Picture tube glass
SiO2 55,7 62,0 72,9 48,0
PbO 24,8 <0,01 <0,01 0,24
As2O3 0,16 <0,01 – < 0,01
Sb2O3 0,41 <0,01 – 0,21
K2O 7,4 1,1 0,07 4,1
Na2O 3,6 11,7 11,9 4,1
Al2O3 2,7 7,2 0,3 20,6
CaO 0,86 11,5 8,9 1,1
BaO – 0,2 – 5,9
B2O3 0,82 <5 – –
Fe2O3 0,40 0,7 0,08 3,75
MgO 0,32 0,1 4,4 0,22
CuO 0,19 0,5 – –
CoO 0,08 0,01 – –
Glow loss 2,56 8,4 – 2,51

August 2004 31
ATV-DVWK-M 374E
5.3.5.1 Mechanical surface treatment
The main source for wastewater treatment mud is the
mechanical surface treatment of glass. Usually the
grinding process is carried out automatically, how-
ever partly still manually. The composition of mud
arising during the preparation of the grinding water
(table 11) mainly reflects the composition of the
glass being treated, enriched with the natural fric-
tion of the grinding tools (iron), the grinding agents
(pumice flour, corundum, diamond) as well as usu-
ally biologically decomposable cooling lubricants
(common cooling lubricant share 3 % to 5 % in the
grinding water).
For to improve the separation also of dissolved
heavy metals, in due case possibly acid treatment
steps (barium sulphate precipitation) have to be
foreseen, and further precipitation and flaking
agents (e. g. aluminium sulphate, ferric-(III)-
chloride, cat-ionic and an-ionic polymeres) have to
be added.
Another feature of this mud is it's fine grain size
(99 % < 30 µm). Despite of the fine grain size and
so the quite big material's surface the leaching val-
ues mentioned below are quite low due to the sur-
face's passive state (re-carbonisation).
Avoidance: In most cases the occurrence of glass
grinding slime is directly proportionate to the
amount of glass to be disengaged during grinding.
By the growing improvement of melting technology
with subsequent forming procedures which are
close to the product's final shape, the necessity for
a following grinding process is reduced more and
more, so that the amount of glass grinding slime
decreases automatically.
Re-use: Only after having checked every single
case, glass grinding slime can be re-used inter-
nally. Even if the main composition of the glass
grinding slime reflects the initial glass matrix, the
small mass parts of:
• flaking agents,
• grinding tools' friction and grinding agents,
• organic components from the cooling lubricants
mentioned above can make a re-use impossible
due to the high requirements regarding product
32 August 2004
quality. Because of this reason in most cases the
glass grinding slime is re-used externally. After ac-
cording aptitude tests, there are ways of re-use e. g.
in the earthenware industry (additive to brick-clay
for back wall bricks), in the construction material
industry (additive to concrete stones for paving
stones and bottom plates), covering materials for
dumps or for mine filling in suitable mines.
Disposal: The ways of disposal depend on the
glass grinding slime's composition and not on its
place of occurrence. The mud's leaching charac-
teristic is the main criterion as well as the dry sub-
stance contents of the heavy metals and organic
components in question.
5.3.5.2 Chemical surface treatment
With the chemical surface treatment, several kinds
of wastewater treatment mud arise:
5.3.5.2.1 Etching slime
Etching slime occurs during the chemical polishing
(finishing) of lead crystal and crystal glass with
fluorine hydrogen and sulphuric acid. In the prepa-
ration of the polishing acid, the etching slime is
separated by chamber filter presses. Besides lead
sulphate as „main product” also small amounts of
lead fluoride, alkali silicon fluoride and alkali sul-
phate are generated.
Avoidance: In most cases the amount of etching
slime is directly proportionate to the amount of
glass to be disengaged during the chemical polish-
ing. By the growing improvement of melting tech-
nology with subsequent forming procedures which
are close the product's final shape, the necessity
for a following grinding process that requires a
subsequent acid polishing is reduced more and
more. So the amount of etching slime decreases
automatically.
Re-use: The high fluorine content makes the pyro-
metallurgic re-work in a lead plant practically im-
possible. Other re-use procedures are yet un-
known.
Disposal: Due to its high fluorine content and the
incorporated acid residues, the etching slime is

disposed at special waste dumps, possibly after
preliminary treatment.
5.3.5.2.2 Neutralisation gypsum
The second waste arising in the acid polishing
area is neutralisation gypsum. It occurs during the
neutralisation of the sulphate containing wastewa-
ter with slaked lime. In small amounts also calcium
fluoride is generated. Lead, arsenic and antimony
are present as trace elements. The neutralised
suspension is drained e. g. with a chamber filter
press.
Avoidance: By re-transfer of rinsing water concen-
trates and used acids, the occurrence of neutrali-
sation gypsum can be avoided. For that purpose
the mixtures of used acids are concentrated up by
an evaporator, so that they can be completely re-
entered in the polishing process again. This can
decrease the amount of neutralisation gypsum
substantially.
Re-use: There are external re-use possibilities for
neutralisation gypsum in mine filling and as addi-
tive in the dump construction.
Disposal: In case a re-use is not possible, the
neutralisation gypsum has to be disposed on spe-
cial waste dumps or settlement waste dumps, de-
pending on its composition and its leaching
characteristics.
5.3.5.2.3 Neutralisation mud
This wastewater treatment mud occurs during the
final treatment of neutralised acid water. Lead, ar-
senic and antimony are separated by adding flak-
ing agent, slaked lime, ferric-(III)-chloride. The
complex-bound heavy metals and antimony are
precipitated with a specific precipitation agent. The
neutralisation mud is drained by either a belt filter
or a chamber filter press.
Avoidance: By re-transfer of the neutralised acid
wastewater, e. g. into the rinsing circuits, the
wastewater to be treated and the arising wastewa-
ter treatment mud can be minimised.
ATV-DVWK-M 374E
Re-use: The neutralisation mud can be externally
re-used in the same way like neutralisation gyp-
sum or glass grinding slime.
Disposal: In case a re-use is not possible the neu-
tralisation mud has to be disposed on a dump of
appropriate classification depending on its compo-
sition and its leaching characteristics.
5.3.5.3 Waste from the PICVD procecs
At the moment, the solid residues (titanium dioxide
with components of silicon dioxide) which occur in
the exhaust gas washers of the PICVD process, are
disposed as waste to be monitored. Research
work is necessary to enable titanium preparation
for re-use in the future.
5.3.6 Salt melt from the chemical
tempering of flat glass
The procedure is operated free of wastewater. The
potash containing salt melt can be re-used in mine
filling. In general, a use as fertiliser in farming is
possible, however necessitates an approval ac-
cording to the law on fertilisers.
5.3.7 Glass fibre and mineral fibre waste
Glass fibre and mineral fibre waste occurs during
product changes, production interruptions, faulty
product lots and when edge cuts arise. Moreover,
mineral fibre waste occurs in the area of process
water filtration, and in the stone wool production,
waste from stone wool filter material can arise.
Place of occurrence: drawing device, splitting and
further treatment, process water preparation, filtering
devices.
Composition: Usually the composition of glass fi-
bre and mineral fibre waste corresponds to the one
of the products.
August 2004 33
ATV-DVWK-M 374E
Avoidance: Waste avoidance can be achieved by
improvement of the material's efficiency.
Re-use:
Primary recycling:
primary recycling is possible in the mineral fibre
production (glass wool and stone wool) if the min-
eral fibre waste can be re-entered into the produc-
tion process after mechanical preparation.
Mineral fibre waste from the process water filtration
and stone wool waste from the filtering devices is
usually re-used over the melting process.
In general waste from endless glass fibres is not
re-used again because it disturbs the production
process substantially.
Secondary recycling:
In single cases it is possible to use mineral fibre
waste as additive in the brick industry after me-
chanical preparation of the material.
Glass fibre waste arising from E-glass can be used
as additive to construction materials.
Before the use as construction material or additive
a preliminary aptitude test is necessary. The re-use
has to be carried out properly and without causing
any damage.
Drawn fibres can be worked to simples products
made of glass fibres, e. g. quilted mats.
Disposal: In case neither avoidance nor re-use of
the glass fibre and mineral fibre waste is possible,
only disposal remains.
According to the material's analytical characteris-
tics, a disposal on appropriate dumps of class 0 or
on settlement waste dumps has to be foreseen.
5.3.8 Mud from the treatment of
production water with organic load
Place of occurrence: For the production of end-
less fibres made of E-glass it is necessary to coat
the drawn fibres with a so-called size (see 3.2.2).
34 August 2004
A part of the size does not stick to the fibres and
washes away with the water used for the drawing
process.
In the wastewater treatment device, the organic
components are separated with the addition of
flaking agents, slaked lime, ferric chlorides and a
precipitation agent. The organic mud is drained e.
g. by a chamber filter press.
Avoidance: At the moment it is not possible to
avoid these solid residues in the production
wastewater. A reduction should be aimed to de-
crease the use of size in the production.
Re-use: A re-use as additive in re-cultivation
measures or in dump construction could be possi-
ble, as far as the organic pollution does not bar it.
The rules of the KrW-/AbfG (§ 8) and the
BBodSchV (§ 12) have to be respected.
Disposal: Usually a disposal is not necessary.
5.4 Rules on dangerous goods
regarding the transport of waste
Most waste arising during the production of glass
and mineral fibres is not subject to marking duties
according to the rules of the European Guideline
regarding dangerous goods (ADR). However, in
single cases, especially with waste form the spe-
cial glass or lead crystal glass production, danger-
ous goods can be present, for which the rules on
dangerous goods have to be respected.
Dangerous goods are defined in chapter 3.2 of
ADR in the list of dangerous goods. They are clas-
sified with UN numbers (substance numbers).
The according national rules can be found besides
others in the "Gefahrgutverordnung Straße und
Eisenbahn (GGVSE)". The GGVSE regulates the
classification of substances as dangerous trans-
port goods = dangerous goods, their packaging for
the transport, the requirements regarding the vehi-
cle, the driver's training and further aspects and is
generally valid above certain volume thresholds.
For the transport of different dangerous goods in
the same transport unit part 1 of annex A to the
GGVSE has to be respected.

There are simplified rules for smaller and minor
amounts.
The application of the rules regarding dangerous
goods has to be monitored by an appropriately
trained representative with valid training certificate,
who has been appointed in writing. Exceptions are
regulated by the "Gefahrgutbeauftragtenverord-
nung (GbV)".
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August 2004 37