Professional Documents
Culture Documents
Advisory Leaflet
ATV-DVWK-M 374E
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
© 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
August 2004 5
ATV-DVWK-M 374E
List of tables
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.
August 2004 7
ATV-DVWK-M 374E
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- For the production of some special glasses – es-
tant glasses. pecially opal and pot-opal glasses – fluorine con-
taining raw materials are necessary. For lead crys-
The raw materials used for the production of the- tal glass, crystal glasses and optical glasses oxide
ses glasses are divided in natural and synthetic compounds of lead, barium and others are used to
products: increase their refractive index. Textile glasses and
glass wool contain boric oxide due to product spe-
The natural raw materials are: quartz sand, partly cific reasons. The same applies for special glasses
also quartz flour, lime, dolomite, feldspar, (borosilicate glasses) which are characterised by
nepheline syenite, phonolithe, anhydrite, chromic their high chemical resistance.
oxides, barytes, sassoline (boric acid), tetraborax
and others. For the production of stone wool also The role of recycling glass cullet (cullet recycling)
basalt and diabas are used. as a raw material for the melting of glass becomes
increasingly important. Own as well as foreign cul-
Synthetic raw materials are: soda, potash, hy- let is used; usually, the one arising at the produc-
drated alumina, bor(III)-oxide, lead oxides, sodium tion site or in the associated further processing
sulphate, sodium nitrate, barium carbonate, barium comply with the respective batch composition
nitrate and others. Also the used refining agents and after separation according to given criteria
are classified as synthetic raw materials (also refer and being free of foreign substances, can be
to table 3). 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
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]
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
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
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
Hot
Forming
Neck
Natural gas Waste glass
Sealing
Water Grinding
Cooling lubricant
Wastewater Wastewater
Precipitation and treatment Slime
flaking agents
Product
cone
12 August 2004
ATV-DVWK-M 374E
The forming of the glass is carried out both in Literature: SCHAEFFER (1990)
automatic and manual procedures.
August 2004 13
ATV-DVWK-M 374E
desired pipe sizes are defined among other things Cascade centrifugal process: The melt is falling
by the drawing machine's speed. freely on the circumference of a horizontal rotor
which distributes it on the surface of two or three
Also the VELLO process is important, in which the additional rotors; by that the melt is drawn to fibres
hot glass exits from a debiteuse and is separated under assistance of the air friction. The mineral fi-
by drawing in a similar way. bres are sucked or blown and collected
(ULLMANN, 1988).
Literature: PFÄNDER (1997), GIEGERICH, W.
And TRIER, W. (1964) , SCHUMANN, D. et al.
(1979)
2.4 Work and finish
The following processes are used for the produc- In many cases, the formed rough glass has to be
tion of endless glass fibres (also refer to VDI worked mechanically to achieve the requested
3457): geometrical, decorative and optical characteristics.
For that purpose it is made use of techniques re-
Drawing from a bushing: the glass is fed to the ferring to cutting, grinding, drilling, milling and pol-
bushing either directly from the glass melting fur- ishing. This leads to abrasions from grinding agent
nace (direct melting procedure) or as re-melted and glass which either can be re-used in the proc-
balls or pellets (ball melting procedure). In the ess or have to be disposed.
bushings' bottom there are spinning holes from
which the liquid glass gets out and is drawn to fi- Usually the rough work (cutting, drilling, milling) is
bres. carry out with diamond tools. For the fine work, be-
side diamond tools there are also several auxiliary
Drawing process for optical purposes: Pre- inorganic substances like oxides (e. g. corundum,
manufactured canes and/or tubes are melted at ferric oxide, ceria), carbides (e. g. silicon carbide,
one end, from which then fibres are drawn, which boric carbide), quartz sand, garnet, pumice flour
is especially used for optical fibres. and others, for which usually water is used as ve-
hicle medium.
For the production of mineral fibres (glass wool
and stone wool) the following processes are used The work is mainly carried out automatically. After
(also refer to VDI 3457): the work the glasses are mostly washed.
Centrifugal drawing: by centrifugal force and the Usually the cooling agent during the mechanical
assistance of an air-stream the vertically fed melt work and the washing water is completely salt-free
is split into mineral fibres, which are collected as water, with or without additives (cooling and lubri-
uncured mat in forming hoods, forming sections or cation agents). They are guided in circles (see Fig.
similar. The most common process is the steam 3). Exceptions are only possible for certain cases
centrifugal blowing procedure (TEL process). (refer to annex 41 of the Abwasserverordnung
(AbwV) part D, part 1 item 1).
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
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
finished product
finished or semi-finished
Raw and
Acid polishing process Wastel / wastewater
additional materials
Vapors Vapors
Neutralised water
Slaked lime
Neutralisation mud
Precipitation agent Final (Wastewater mud)
wastewater
Flaking agent treatment
Wastewater
Ferric-III-
chloride
Product
August 2004 15
ATV-DVWK-M 374E
2.4.3 Coating
2.4.5 Chemical tempering of flat glass
Usually the decoration of glass (screen printing,
painting, golden rims) is made in an application This procedure is characterised by the fact that a
procedure with suitable colours. Depending on pressure tempering of the glass surface is
type and glass composition these colours are fired achieved by creating a difference compared to the
on at 400 °C to 600 °C. glass inside by changing the surface's composi-
tion. The method of chemical tempering is based
The silvering is achieved by application of thin on ion exchange. The ions of the single chemical
metal layers (e. g. silver, copper) after a prelimi- elements have different radiuses and are arranged
nary cleaning of the glass surface. The desired with different distances related to each other. If for
metal deposit arises either from the liquid phase by instance a sodium containing glass is heated
chemical reduction or dry by vacuum evaporation. slowly in a potassium hydrochloric melt close to
The metal cover is protected against damages by the transformation temperature, the sodium ions
one or two varnish layers. migrate form the glass into the hydrochloric melt
and the potash ions from the hydrochloric melt into
For surface coating container glass in hot status the glass surface. As the potash ions entering the
can be subject to a vapour deposition with metal glass surface have an ion radius which is approx.
16 August 2004
ATV-DVWK-M 374E
Usually mineral fibres are worked by coating, im- Further literature: ATV-DVWK-M 706 „Kraftwerke
pregnation or soaking with binding agent and/or und Energieversorgungsbetriebe“, Parts 1 to 3.
lubricants and, if need be, with the assistance of
subsequent hardening procedures, to become dif-
ferent finished products. The work comprises be- 3.2 Process water
sides others: cutting, pressing, stamping, sawing,
milling, grinding, and facing (compare VDI 3457). 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 3.2.3 Water in the further treatment
achieved by a manufacturers' statement that the
used additional substances do not contain halogen 3.2.3.1 Washing and rinsing
hydrocarbons.“ Also annex 41 AbwV part E has to
be paid attention to, according to which the re- Washing procedures are used for a preliminary
quirements for wastewater are defined at the place cleaning of glass for a subsequent finishing proc-
of occurrence. ess. Usually, common detergents (surface active
substances) are added to the wash water manually
or automatically. In special cases acids and lye are
3.2.1 Shear cooling used. After the rinsing process the wastewater
may contain substances from preceding treatment
Like described in 2.3.1, in the gob feeder process steps.
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- 3.2.3.2 Mechanical treatment
able cooling lubricants can be used, which have
been developed for this purpose. Usually they are According to 2.4.1 usually during the treatment of
biologically decomposable and contain e. g. alca- glass water is used as cooling or transport medium
nol amines, polyoles, tensides. Referring to the for substances mentioned in that section. Further-
"Technische Regeln für Gefahrstoffe (TRGS 611)" more biologically decomposable cooling lubricants
the cooling lubricants are not allowed to contain are used. Besides others they contain e. g. alcanol
neither nitrosating agents or their preliminary amines, polyoles, tensides. During the mechanical
stages (like nitrites) nor secondary amines. treatment the cooling water gets charged with
glass friction, possible also contents of the glass
matrix can dissolve to a small extent.
Endless glass fibres are coated with a size during Usually acid polishing and frosting happen in ace-
drawing. In that context losses of the used sizes
tous solution. Besides the acids (e. g.: sulphuric
occur. Depending on the purpose of the produced acid, fluorine hydrogen acid, hydrochloric acid)
fibres either "textile sizes“ or „plastic sizes“ are also ions from the glass can occur in the wastewa-
used. Textile sizes are substances like potato or
ter.
corn starch as glue and film shaper as well as
vegetable fat as lubricant. The plastics sizes con- In other cases, e. g. at the ion exchange both basic
tain besides others: polyester resins, epoxid resins
and acetous wastewater shares can arise.
(few), polyvinyl alcohol (few), polyurethane, film
shaper, sticking agents like silanes, rinsing agents
and emulsifier. These lead to increased CSB val-
3.2.3.4 Coating
ues in the wastewater (see 5.3.8).
Usually the decoration and surface coating are car-
ried out without wastewater (also refer to 2.4.3 and
3.3.2).
18 August 2004
ATV-DVWK-M 374E
During the mirror production after preliminary 3.3 Wastewater from side installations
treatment with tin (II) chloride a silver solution con- and exhaust gas washers
sisting of silver nitrate, ammonia and sodium or
potash oxide in completely salt-free water as well 3.3.1 Side installations
as a reducing solution containing mainly glucose is
splashed on the glass surface for silvering. After- Usually the cleaning of machines, machine parts,
wards a copper layer is applied in a similar way. mould parts and tools complies with the standard
After respective cleaning, the surplus solution is procedures for cleaning and de-greasing com-
guided into the wastewater. monly used in engineering works. The detergents
in normal commercial use can contain sodium hy-
Literature: Gläser (1994), Kempf (1959). droxide, soda, tri sodium phosphate, polyphos-
phate, alkali silicates, alkali borates and tensides.
They enrich with oils, fats, tinder and dirty sub-
3.2.3.5 PICVD process stances and have to be transferred to an appropri-
ate external disposal or a waste water treatment.
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 3.3.2 Exhaust gas wash
sorption is possible, however not yet tested) on al-
kaline basis (soda lye respectively sodium bisul- Exhaust gas wash can be used in different areas:
phite solution). After de-mudding the wash water of
the exhaust gas washer can be injected into the • Glass melt: for deposit of acetous gaseous ex-
sewers, if it complies with the state of the art ac- haust gas components like sulphur oxides, fluo-
cording to annex 41 AbwV and the injection condi- rine and chloride carbohydrates usually dry or
tions of the rules for direct injections issued by the nearly-dry sorption procedures are used. These
Länder respectively with the requirements of the procedures are free of wastewater. In some
local drainage/wastewater statutes. cases also exhaust gas washers are used (whirl
washers, Venturi washers and others).
August 2004 19
ATV-DVWK-M 374E
• With the online coating occur exhaust gases; 3.4 Measures for avoidance, reduction
they consist of gases of an inorganic chloride and recovery
compound (e. g. tin chloride) that have already
reacted completely and gases, which have not Multiple water use
completed their reaction yet. For to complete depending on its further use, slightly charged
the reaction, the coating gases can react in total process water can be used for further purposes in
in a reactor, that means, they change into the the plant, either with or without treatment. This
oxide form. The hot gases are guided over an saves water and the amount of wastewater is sub-
exhaust gas cooler, which decreases the ex- stantially reduced. Attention has to be paid to a
haust gas temperature by sprayed-in water, and possible enrichment of contents.
then they are transferred to the electric filter. in
the electric filter the metal oxides e. g. of the tin The multiple use can be different:
are deposited and collected. These metal ox- • in the first phase of use taking up heat, in the
ides are recycled. The exhaust gases leaving second taking up dissolved solids or vice versa.
the filter are neutralised in a soda lye washer.
The cleaned air is released over a stacker. The • in two or more steps taking up of different or
arising salt-containing water is collected in tanks same substances (cascade rinsing system).
for a later transfer to the wastewater cleaning, Examples of application:
where they are injected in a spray dryer. The • use as consumption water in vaporisation sys-
spray dryer evaporates the water and the dry tems,
salt is taken out over a cell wheel sluice. The
• use as consumption water for moistening raw
spray dryer's hot air can consist of the waste
materials,
heat of the roller annealing lehr which is guided
• multiple use as cooling water,
over an after-heater. Usually the salts are used
in mine filling. • cascade rinsing in washing procedures.
• Further treatment of mineral fibres: during im- In contrast to the multiple use without intermediate
pregnation, hardening and final work exhaust treatment, in the rinsing water circuit with ion ex-
gas streams occur which are cleaned. This is changer a nearly permanent use of the same water
carried out with moist or dry working devices for is aimed.
exhaust gas treatment, like e. g. moist washer, The regenerates arising after treatment of the ex-
moist electric filter, hose filter, thermal after-burn changer resins represent a wastewater charged
(combined with heat re-transfer systems). Wash with pollutant which has to be treated according to
water from these exhaust gas treatment devices section 4. In this context lot treatment units have
contains as main components residues of min- proven good.
eral fibres as well as organic parts (phenol for-
maldehyde resin in different condensation Completely closed water circuits do not exist. Sub-
stages). After mechanical separation of the stances that enrich, either solid or dissolved, have
mineral fibre residues the washer water is re- to be extracted, continuously or non-continuously.
transferred to the process water circuit. For the treatment of such wastewater the proce-
dures described in section 4 have proven good.
20 August 2004
ATV-DVWK-M 374E
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
SEDIMENTATION
FLAKING - COURSE
PUMP CONTAINER
BUFFER-
SUMP CONTAINER
Sand filter
MUD
THICKE- CHAMBER FILTER PRESS
NER
BUFFER
CONTAI-
NER
August 2004 21
ATV-DVWK-M 374E
22 August 2004
ATV-DVWK-M 374E
fluoride (CaF2) and anhydrous gypsum (CaSO4) the blocking of piping. So from both economical
with slaked lime in the treatment of wastewater of and also ecological point of view this procedure
the chemical surface treatment (see 3.2.2.3) con- can not be recommed.
taining fluorine hydrogen and sulphuric acid.
The requirements regarding the admissible sul-
During monitoring fluoride is often determined as phate concentration at the transfer point for the in-
fluoride in total. However, if it is present in waste- jection into public sewer systems are defined on
water in complex-bound type, e. g. as tetra fluorine the basis of the municipality statutes. Usually the
borate (e. g. from acetous metal electrolytes), its drainage statutes of cities and towns contain a
precipitation is not possible. generally applicable monitoring value for sulphate.
In most cities and towns however, under certain
The same conditions like for fluoride are valid for circumstances (sewer system material, dilution
the precipitation of anhydrous gypsum by neutrali- conditions) a higher sulphate concentration may be
sation with slaked lime. allowed after checking each single case.
Some metals can be precipitated not only as hy- Usually acetous or basic and metal containing
droxides with lye but also as carbonates or sul- wastewater, especially from the finishing sector,
phites, e. g. lead as lead carbonate and arsenic has to be transferred into a pH value scope be-
and antimony as according sulphites. These pro- tween 6,5 and 9,5 (up to 10). This occurs in reac-
cedures can be applied for treatments according to tors, either continuously or in lot procedures, using
3.2.3.2 (Mechan. treatment), 3.2.3.3 (Chem. work), acetous or basic reagents (e. g. hydrochloric acid,
3.2.3.4 (Coating), 3.3.2 (Exhaust gas wash). slaked lime, soda lye and others). Arising mud is
separated (see 4.2.1.), more to mud see section 5.
The precipitation of free fluoride is carried out with
calcium compounds, usually with slaked lime in
combination with the neutralisation. Here it has to 4.1.2 Subsequent treatment
be considered that the fluoride precipitation can
only be successful if per equivalent fluoride also an The most frequent reasons for a possible excess
equivalent calcium is present. Otherwise additional of the requirements of annex 41 AbwV respectively
calcium ions have to be added in form of dissolv- the local drainage/wastewater statutes for rest
able calcium compounds. concentrations of metals are very small amounts of
solid particles which despite of sedimentation or
According to DIN 4030-1 sulphate in concentra- flotation (see 4.2.1 and 4.2.3) remain in the
tions between 200 mg/l and 600 mg/l has slightly wastewater. In this case a final filtration is neces-
concrete aggressive characteristics. Therefore it is sary. Usually it is carried out with sand or flint fil-
usually limited in the indirect injection. In most fa- ters. It is also possible to use candle or membrane
vourite case, concentrations around 1400 mg/l SO4 filters.
(equilibrium concentration) can be achieved, depend-
ing on the concentration of neutral salt and tempera- If after the treatment the waster water still contains
ture. However, with higher neutral salt concentra- small amounts of cat-ioncally dissolved metals or if
tions this can be exceeded by far. Because of that the requirements can not be kept under guarantee
reason annex 41 of the Abwasserverordnung at all times, a selectively working cat-ion ex-
states a limitation value for sulphate of 3000 mg/l. changer can be installed after the final filter.
The value of 1000 mg/l mentioned in the BREF
document for the glass industry can not be
achieved with slaked lime precipitation. Another 4.2 Non-dissolved solids
possibility could be to precipitate the sulphate as
ettringite (calcium sulphate aluminate), which en-
4.2.1 Sedimentation
ables sulphate concentrations of less than 400
mg/l (HARTINGER, 1991). However, this proce-
The treatment residues in the glass industry are
dure causes a substantially big amount of waste-
substances that can be fairly easy separated by
water mud and is hard to control. The forming of
sedimentation, possibly under preliminary use of a
ettringite happens spontaneously and can lead to
August 2004 23
ATV-DVWK-M 374E
sieve for the bigger fraction. For to accelerate the der pressure dissolved in the wastewater (release
phase separation solid - liquid and for the separa- flotation) or by electrolytic water disintegration
tion of colloids often auxiliary substances (flaking (electric flotation).
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- 4.2.4 Filtration
crease the sinking speed of small parts.
Filtering devices in form of belt filters and chamber
The separation process is carried out in suitable filter presses are used where due to process-
devices in which the cleared wastewater can over- related reasons larger amounts of solid substances
flow and the sediment can be extracted as mud. to be separated have to be taken out and drained
Subsequently the mud has to be partly drained e. g. thin mud from the sedimentation.
(see section 5).
24 August 2004
ATV-DVWK-M 374E
Usually high specific heat loads at devices for With the production of the different glass types and
glass production require water as cooling agent for products waste arises in every production step.
heat discharge. In normal operation the cooling However, it has to be taken into consideration that
water heats up to 30 °C to 40 °C. Mainly the cool- glass raw materials, glass compositions, recycling
ing down is carried out in open systems (evapora- ratios, melting methods, procedures for further
tion cooler) in which depending on the surround- treatment, environmental rules and quality re-
ing's conditions the cooling water is cooled down in quirements are subjects to permanent changes.
an amount of up to 10 Kelvin.
Therefore the waste amounts of a production unit
as well as comparable productions of different
4.4 External disposal manufacturers and plants can differ considerably
over the time.
In case certain highly charged plant wastewater
can not be treated with cost-efficient method within So it is not possible to state common waste
the plant, this wastewater has to be collected and amounts.
disposed externally.
August 2004 25
ATV-DVWK-M 374E
Table 8: Types of waste in the glass industry, including mineral fibre industry
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
Avoidance: Faulty batch can only be reduced if The complete re-transfer of filter dust e. g. in facili-
the device's general reliability can be further in- ties for the production of flat glass, container glass
creased. At the moment these devices' capacity is and glass fibres is explicitly appreciated according
already at 98 % to nearly 100 %. to the TA Luft. Taking into consideration other
conditions, the TA Luft enables the assertion of a
The occurrence of dust can be minimised or higher emission values regarding sulphur dioxide
avoided by closed systems. Closed systems are in comparison to other plants in which the filter
mostly installed at the places of occurrence. dust is not completely re-entered in the production.
Re-use and disposal: Batch residues are re-used Re-use and disposal: In the container glass, flat
in the container glass industry, in the flat and spe- glass and mineral fibre industry filter dust is mainly
cial glass industry usually rejected due to quality re-used again.
reasons. Mixtures with sweepings also have to be re-
jected. Given suitable composition or suitable pre- With special glasses, pollution e. g. by colour-
liminary treatment, rejected batch residues can be donating metal oxides can limit a re-use,
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- Dust which can not be re-entered in the process,
ing amount as well as individual quality require- can be used externally (e. g. non-ferric metal plant,
ments regarding raw material and product a use in mine filling) or disposed (surface dump, under-
other glass plants can not be realised. If re-use is ground dump).
not possible, the disposal is carried out on a dump
licensed for such substances.
Place of occurrence: exhaust gas cleaning de- Place of occurrence: glass melt, glass forming,
vices, batch houses, hot end, cold end glass treatment, sorting, packing, warehouse
Composition: See following table 9. Composition: the glass cullet composition is equal
to the product composition. In general, the pollu-
Avoidance: By an appropriate selection of raw tion (as stated above) is insignificant in regard to
and additional materials as well as an optimised weight and volume.
way of operation the amount of filter dust can be
reduced, as far as this it technically and economi- Avoidance: avoidance is achieved by a reduction
cally tenable. This minimises the expenses for of defects in the production process, a reduction of
secondary measures (e. g. filter dimension). inconsistencies in glass by optimisation of batch
28 August 2004
ATV-DVWK-M 374E
Under certain circumstances also the cullet with Shaft furnaces for the production of stone wool are
pollution can be melted in the production of glass constructed approx. weekly, during which small
products of different quality. A respective melting amounts of fire-light bricks arise which are inter-
unit has to be on hand. The products have to be nally re-used as melting raw material.
saleable on the market.
By targeted measures during the demolition and
Re-use: The transfer to other glass plants for melt- subsequent careful sorting, the part of furnace ma-
ing is limited due to the pollution and/or different terial that hat to be disposed can be substantially
chemical compositions. reduced.
Suitable cullet, e. g. lead-containing, can also be re- Place of occurrence: furnace, feeder (glass
used in non-ferric metal plants. channel), recuperator, regenerator and exhaust
gas channels.
The re-use of lighting glass in the melt has to be
limited due to the sticking mercury parts. Usually Composition: Refractory materials are non-
shredded fluorescent tubes have got mercury metallic materials with a pyrometric cone equiva-
shares of 30 mg/kg to 40 mg/kg. By an subsequent lent (PCE)13 of minimum 1500 °C. Refractory ma-
cleaning in a cullet cleaning device with water, the terials consist of high melting oxides (Al2O3, MgO,
mercury share can be reduced to 5 mg/kg. A fur- Cr2O3, ZrO2), fire-proof silicates and other materi-
ther reduction is technically impossible. Therefore als (see table 10).
the cullet ratio in the existing technical production
facilities is limited 2 to 5 mass % for to keep the re- A priori, refractory materials do only contain small
spective exhaust gas values of the TA-Luft. amounts of water-soluble contents. However, glass
melting furnaces are subject to a strong mechani-
Before being used as construction material or addi- cal, thermal, and chemical permanent stress. Be-
tive an aptitude test has to be carried out. The re- sides the components of the refractory materials,
use has to be carried out properly and without the composition of the processed batch (raw mate-
causing any damage. For underground mining re- rials and additives) and the type of heating are im-
use the "Verordnung über den Versatz von Abfäl- portant for the furnace material's chemical compo-
len unter Tage (VersatzV)" has to be respected. sition.
August 2004 29
ATV-DVWK-M 374E
Avoidance: Waste avoidance is possible by opti- Secondary recycling: material's use after transfor-
misation of the furnace campaign. Furthermore in mation into a new product in other production
some application cases new technologies (e. g. branches and conditions of use (secondary con-
fuel-oxygen heating instead of fuel-air-heating) struction material, depending on the classification
which make regenerators obsolete, offer the pos- values of the LAGA rules e. g. for the installation in
sibility to avoid refractory material waste. free areas and for use in road construction as well
as intermediate or filling layer in dumps). The
Re-use: Re-use possibilities depend on material harmlessness has to be checked in every single
composition, pollutant content and material status. case as long as no federal unitary standard values
are available.
Primary recycling: primary recycling is possible if
after selective demolition undamaged refractory Mining technological re-use: Here in particularly
bricks can be directly re-used. the mechanical and the construction material char-
acteristics of waste are used to achieve a mining
With handing back lesser stressed material to the technological target. The set of rules to be applied
refractory material's manufacturer, maybe a direct for this purpose is the VersatzV. Apart from the limi-
re-use (with or without preparative treatment) is tation values for heavy metals between 1 % (Cu)
possible.
30 August 2004
ATV-DVWK-M 374E
and 50 % (Fe), above which the metal recovery is class 0 dumps according to the "Deponieverord-
emphasised, and the classification values in the nung (DepV)".
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 5.3.5 Mud from the wastewater
refer also to Advisory leaflet ATV-DVWK-M 358 treatment (wastewater treatment
(2003). mud)
Re-use as additive to the batch: under certain cir- Place of occurrence: mud from the wastewater
cumstances the deposit from the chambers and treatment arise in context with:
channel, which have arisen in the container glass
1. the mechanical surface treatment of glass,
industry in connection with a furnace material, can
2. the chemical surface treatment of glass,
be used after preliminary treatment as batch com- 3. aqueous exhaust gas cleaning systems (e. g.
ponent. PICVD process),
4. special procedures (e. g. chemical tempering of
Disposal: Is neither avoidance nor re-use of the glass).
furnace materials and the deposits possible, only
disposal remains. Composition: The wastewater treatment mud's
composition depends on the places of occurrence
According to the material's analytical characteris- which are described below.
tics it has to be disposed at underground dumps,
special waste dumps, settlement waste dumps or
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 quality. Because of this reason in most cases the
glass grinding slime is re-used externally. After ac-
The main source for wastewater treatment mud is the cording aptitude tests, there are ways of re-use e. g.
mechanical surface treatment of glass. Usually the in the earthenware industry (additive to brick-clay
grinding process is carried out automatically, how- for back wall bricks), in the construction material
ever partly still manually. The composition of mud industry (additive to concrete stones for paving
arising during the preparation of the grinding water stones and bottom plates), covering materials for
(table 11) mainly reflects the composition of the dumps or for mine filling in suitable mines.
glass being treated, enriched with the natural fric-
tion of the grinding tools (iron), the grinding agents Disposal: The ways of disposal depend on the
(pumice flour, corundum, diamond) as well as usu- glass grinding slime's composition and not on its
ally biologically decomposable cooling lubricants place of occurrence. The mud's leaching charac-
(common cooling lubricant share 3 % to 5 % in the teristic is the main criterion as well as the dry sub-
grinding water). stance contents of the heavy metals and organic
components in question.
For to improve the separation also of dissolved
heavy metals, in due case possibly acid treatment
steps (barium sulphate precipitation) have to be 5.3.5.2 Chemical surface treatment
foreseen, and further precipitation and flaking
agents (e. g. aluminium sulphate, ferric-(III)- With the chemical surface treatment, several kinds
chloride, cat-ionic and an-ionic polymeres) have to of wastewater treatment mud arise:
be added.
Another feature of this mud is it's fine grain size 5.3.5.2.1 Etching slime
(99 % < 30 µm). Despite of the fine grain size and
so the quite big material's surface the leaching val- Etching slime occurs during the chemical polishing
ues mentioned below are quite low due to the sur- (finishing) of lead crystal and crystal glass with
face's passive state (re-carbonisation). fluorine hydrogen and sulphuric acid. In the prepa-
ration of the polishing acid, the etching slime is
Avoidance: In most cases the occurrence of glass separated by chamber filter presses. Besides lead
grinding slime is directly proportionate to the sulphate as „main product” also small amounts of
lead fluoride, alkali silicon fluoride and alkali sul-
amount of glass to be disengaged during grinding.
By the growing improvement of melting technology phate are generated.
with subsequent forming procedures which are
Avoidance: In most cases the amount of etching
close to the product's final shape, the necessity for
a following grinding process is reduced more and slime is directly proportionate to the amount of
more, so that the amount of glass grinding slime glass to be disengaged during the chemical polish-
ing. By the growing improvement of melting tech-
decreases automatically.
nology with subsequent forming procedures which
are close the product's final shape, the necessity
Re-use: Only after having checked every single
for a following grinding process that requires a
case, glass grinding slime can be re-used inter-
subsequent acid polishing is reduced more and
nally. Even if the main composition of the glass
more. So the amount of etching slime decreases
grinding slime reflects the initial glass matrix, the
automatically.
small mass parts of:
• flaking agents, Re-use: The high fluorine content makes the pyro-
metallurgic re-work in a lead plant practically im-
• grinding tools' friction and grinding agents,
possible. Other re-use procedures are yet un-
• organic components from the cooling lubricants known.
mentioned above can make a re-use impossible Disposal: Due to its high fluorine content and the
due to the high requirements regarding product incorporated acid residues, the etching slime is
32 August 2004
ATV-DVWK-M 374E
disposed at special waste dumps, possibly after Re-use: The neutralisation mud can be externally
preliminary treatment. re-used in the same way like neutralisation gyp-
sum or glass grinding slime.
5.3.5.2.2 Neutralisation gypsum Disposal: In case a re-use is not possible the neu-
tralisation mud has to be disposed on a dump of
The second waste arising in the acid polishing appropriate classification depending on its compo-
area is neutralisation gypsum. It occurs during the sition and its leaching characteristics.
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 5.3.5.3 Waste from the PICVD procecs
suspension is drained e. g. with a chamber filter
press. At the moment, the solid residues (titanium dioxide
with components of silicon dioxide) which occur in
Avoidance: By re-transfer of rinsing water concen- the exhaust gas washers of the PICVD process, are
trates and used acids, the occurrence of neutrali- disposed as waste to be monitored. Research
sation gypsum can be avoided. For that purpose work is necessary to enable titanium preparation
the mixtures of used acids are concentrated up by for re-use in the future.
an evaporator, so that they can be completely re-
entered in the polishing process again. This can
decrease the amount of neutralisation gypsum
substantially.
5.3.6 Salt melt from the chemical
tempering of flat glass
Re-use: There are external re-use possibilities for
neutralisation gypsum in mine filling and as addi-
The procedure is operated free of wastewater. The
tive in the dump construction.
potash containing salt melt can be re-used in mine
filling. In general, a use as fertiliser in farming is
Disposal: In case a re-use is not possible, the
possible, however necessitates an approval ac-
neutralisation gypsum has to be disposed on spe-
cording to the law on fertilisers.
cial waste dumps or settlement waste dumps, de-
pending on its composition and its leaching
characteristics.
August 2004 33
ATV-DVWK-M 374E
Avoidance: Waste avoidance can be achieved by A part of the size does not stick to the fibres and
improvement of the material's efficiency. washes away with the water used for the drawing
process.
Re-use:
Primary recycling: In the wastewater treatment device, the organic
primary recycling is possible in the mineral fibre components are separated with the addition of
production (glass wool and stone wool) if the min- flaking agents, slaked lime, ferric chlorides and a
eral fibre waste can be re-entered into the produc- precipitation agent. The organic mud is drained e.
tion process after mechanical preparation. g. by a chamber filter press.
Mineral fibre waste from the process water filtration Avoidance: At the moment it is not possible to
and stone wool waste from the filtering devices is avoid these solid residues in the production
usually re-used over the melting process. wastewater. A reduction should be aimed to de-
crease the use of size in the production.
In general waste from endless glass fibres is not
re-used again because it disturbs the production Re-use: A re-use as additive in re-cultivation
process substantially. measures or in dump construction could be possi-
ble, as far as the organic pollution does not bar it.
Secondary recycling: The rules of the KrW-/AbfG (§ 8) and the
In single cases it is possible to use mineral fibre BBodSchV (§ 12) have to be respected.
waste as additive in the brick industry after me-
chanical preparation of the material. Disposal: Usually a disposal is not necessary.
34 August 2004
ATV-DVWK-M 374E
There are simplified rules for smaller and minor ATV-DVWK-M 706: Kraftwerke und Entsorgungs-
amounts. betriebe:
Teil 1 – Abwasser, das bei der Wasseraufberei-
The application of the rules regarding dangerous tung entsteht. Juni 2000
goods has to be monitored by an appropriately Teil 2 – Abwasser, das beim Betrieb von Kühl-
trained representative with valid training certificate, systemen entsteht. April 1997
who has been appointed in writing. Exceptions are Teil 3 – Abwasser, das bei der Dampf- und
regulated by the "Gefahrgutbeauftragtenverord- Heißwassererzeugung entsteht. Juli 2003
nung (GbV)". AVV: Verordnung über das Europäische Abfallver-
zeichnis (Abfallverzeichnisverordnung) i. d. F.
vom 10. 12. 2001, BGBl. I S. 3379, gültig seit
01. 01. 2002; Stand: zuletzt geändert durch Ar-
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serverordnung) i. d. Neufassung durch Bek. v. 1999, S. 1554, gültig ab 17. 07. 1999
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gänge (Bundes-Immissionsschutzgesetz) in der
Anhang 39: Nichteisenmetallherstellung (BGBl. I Neufassung durch Bekanntmachung v.
2002, S. 4095-4097) 26. 09. 2002, BGBl. I S. 3830; Stand: zuletzt
Anhang 41: Herstellung und Verarbeitung von Glas geändert: zuletzt geändert durch Artikel 7 Ge-
und künstlichen Mineralfasern (BGBl. I 2002, setz v. 6. 1. 2004 BGBl. I S. 2
S. 4100-4102) BREF-Dokument: Referenzdokument über die bes-
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Beseitigung produktionsspezifischer Abfälle: sigkeiten – Teil 100: Anforderungen für die An-
Schlämme aus Zink- und Eisenphosphatieran- wendung von Abscheideranlagen nach DIN EN
lagen. Dezember 2003 858-1 und DIN EN 858-2. Oktober 2003
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ser, Böden und Gase; Grundlagen und Grenz-
werte. Juni 1991
August 2004 35
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vom 26. 03. 1998, BGBl. I S. 648, Stand: zuletzt Erzeugnisse mit einem Massenanteil an Rest-
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August 2004 37