EP0910697A1 - Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture - Google Patents
Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufactureInfo
- Publication number
- EP0910697A1 EP0910697A1 EP97915390A EP97915390A EP0910697A1 EP 0910697 A1 EP0910697 A1 EP 0910697A1 EP 97915390 A EP97915390 A EP 97915390A EP 97915390 A EP97915390 A EP 97915390A EP 0910697 A1 EP0910697 A1 EP 0910697A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fresh
- pigment
- weight
- filler
- fillers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 116
- 239000000945 filler Substances 0.000 title claims abstract description 93
- 239000000123 paper Substances 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000011111 cardboard Substances 0.000 title claims abstract description 18
- 239000011087 paperboard Substances 0.000 title abstract 3
- 239000002002 slurry Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 41
- 239000010802 sludge Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000010216 calcium carbonate Nutrition 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 8
- 239000002761 deinking Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 7
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- -1 aluminum silicates Chemical class 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007646 gravure printing Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims 1
- 239000010440 gypsum Substances 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000000746 purification Methods 0.000 abstract 2
- 239000004927 clay Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 14
- 239000004816 latex Substances 0.000 description 13
- 229920000126 latex Polymers 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 229920001807 Urea-formaldehyde Polymers 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 239000004848 polyfunctional curative Substances 0.000 description 10
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 239000010801 sewage sludge Substances 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 4
- 239000010893 paper waste Substances 0.000 description 4
- 229920001592 potato starch Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000009459 flexible packaging Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000009838 combustion analysis Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/01—Waste products, e.g. sludge
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/66—Pulp catching, de-watering, or recovering; Re-use of pulp-water
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S162/00—Paper making and fiber liberation
- Y10S162/09—Uses for paper making sludge
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/928—Paper mill waste, e.g. white water, black liquor treated
Definitions
- the invention relates to a process for recycling fillers and coating pigments from the manufacture of paper, cardboard and cardboard from the residual water sludge from the coating waste water, deinking plants, internal sewage treatment plants or separating devices, and the use of pigment slurries thus obtained as a filler for the production of paper or as Pigment slurry for the production of a coating slip for the paper industry.
- the raw material i.e. H. Pulp, wood, straw pulp or hard pulp also added waste pulp, fillers and pigments with which a closed surface is to be achieved in order to improve the properties of the paper, in particular the whiteness, the opacity and the printability of the paper.
- fillers which give printing and writing papers in particular an even formation, better softness, whiteness and grip.
- These fillers which are usually called “ashes”, since they remain as ashes during combustion analysis, are either added to the fiber suspension or applied during brushing.
- Natural printing papers contain up to 35% by weight fillers, coated papers 25% to 50% by weight.
- the amount of filler depends very much on the intended use of the paper. Heavily weighted papers have lower strengths and poorer sizing properties.
- the proportion of filler in the paper pulp is usually between 5 and 35% by weight and consists of primary pigment or of recirculated coating pigments which are from Remaining coating colors or deleted scrap can come.
- the grain size plays an important role, since it strongly influences the filler yield and influences the physical properties of the paper, especially the porosity.
- the amount of filler remaining in the paper is between 20 and 80% of the amount added to the fiber suspension. The yield depends on the type of filler as well as on the composition, the degree of grinding, the fixation of the filler particles by resin and aluminum sulfate, the paper weight, the paper machine speed, the type of Dehydration and the fineness of the sieve.
- kaolin calcium carbonate
- artificial aluminum silicates and oxide hydrates titanium dioxide
- satin white talc
- calcium silicate a product that is now more important as fillers and coating pigments: kaolin, calcium carbonate, artificial aluminum silicates and oxide hydrates, titanium dioxide, satin white, talc and calcium silicate.
- the fillers and pigments are a waste product, especially in deinking plants.
- This waste product consists, for example, of 50% by weight of cellulose, 25% by weight of kaolin and 20% by weight of calcium carbonate, although other small proportions of calcium sulfate, titanium dioxide, talc or other solids may also be present, these mixtures more or less can contain large amounts of fibers.
- EP 0 492 121 B1 describes the previous processing of waste paper in such a way that these waste materials are separated out of the process as a waste water / solid mixture, a pure waste product being produced which contains about 50% solids and is stored in landfills. It is proposed here to mix the sludge-like water-solid mixture intensively and then to comminute this mixture of water and solid roughly, finely or very finely and only then to carry out the further use with the addition of an appropriate additive. It will use this Materials from raw material for dyes, adhesives, fillers and hydraulic binders are proposed.
- DE 40 34 054 C1 proposes a process for the recovery of raw materials from the mechanical residual sewage sludge of the paper industry.
- the residual water sludge is first freed of the black particle content by centrifugation and then divided into fibers, fillers, pigments and agglomerates by means of fractional sieving.
- the agglomerates are treated with shear and discarded, while the fibers, fillers and pigments are reused if necessary after further treatment.
- EP 0 576 177 A1 discloses a process for recycling and reusing raw materials from the residual water sludges of the paper industry, which is characterized in that the sludge suspension is subjected to a first sieving / cleaning process with a relatively low consistency in a first process step, then thickened and heated and passed through a disperser before reusing this slurry in papermaking.
- the process is characterized by the setting of a defined solid content, the separation of the coarse dirt, the separation of the Black particle fractions, the fractionated fine sieving of the good fraction and the return of the fiber fraction and the filler and pigment fraction to the raw material processing of the paper mill.
- the fillers and coating pigments are often in agglomerated form and have a low whiteness, which limits direct reuse in raw material processing, especially in the coating.
- the object of the invention is to provide a method for recycling paper raw materials, in particular the fillers and the coating pigments, while saving energy costs and raw material costs as well as transportation costs.
- the above-mentioned object is achieved according to the invention by a process for recycling fillers and coating pigments from paper, cardboard and cardboard production from residual water sludge from the coating waste water, deinking plants, internal sewage treatment plants or separating devices, which is characterized in that the filler and coating pigments are included Residual water sludge of the mixing and then the grinding to a pigment slurry with fresh pigment or fresh filler as a powder, fresh pigment-containing and / or fresh filler-containing slurry.
- the fillers and coating pigments In papermaking, it is common for both the fillers and coating pigments as a powder or in the form of a concentrated slurry, which has 50 to 80 wt .-% solids. These fillers and pigments are usually provided by the manufacturers with the desired whiteness and grain size distribution.
- the essence of the present invention now consists in the delivery of the pigment in a type of "base grain", preferably as a solid or also as a highly concentrated slurry, for example with a solids content of 70% by weight to 85% by weight or more, for example with a average grain diameter of 50% ⁇ 2 ⁇ m to 10 ⁇ m, in particular 2 ⁇ m to 5 ⁇ m and grinding in the aqueous phase on site in a satellite grinding system to the desired whiteness and grain size.
- base grain preferably as a solid or also as a highly concentrated slurry, for example with a solids content of 70% by weight to 85% by weight or more, for example with a average grain diameter of 50% ⁇ 2 ⁇
- the above-mentioned residual water sludges are not added to the raw materials that have been delivered or prepared, but are first milled to the desired whiteness and fineness by mixing and then grinding fresh pigment or fresh filler as a powder, fresh pigment-containing and / or fresh filler-containing slurry and then as a filler or coating pigment used.
- the mineral fillers and pigments mentioned are usually ground to the desired particle size in wet or dry processes. A large proportion of water is naturally required for wet grinding. According to the invention, it has now been found that part or all of the water required for mixing and then grinding the fresh pigments or fillers as a powder, slurry containing fresh pigment and / or filler can be replaced by the residual water sludge, which may contain fibers.
- the sieve pass obtained in this way consists of fibers, fillers, pigments, fine sand, black particles and agglomerates of fillers and pigments or pigments, fibers and fillers.
- Filler is usually understood to mean the fine particles used in the pulp; pigment means the fine particles used in the coating color.
- the normally unusable black particles have a large grain size variation. They mainly consist of gray to black colored sand, soil abrasion, machine abrasion, coked lubricants, acid-attacked organic particles, rust and agglomerated dust or a mixture thereof.
- the pigment and filler particles of the residual water sludge which are intended for use as filler or pigment, act here as grinding aids and dispersing aids for the destruction of the agglomerates in the grinding process.
- the residual water sludge acts as a dispersing aid and grinding aid for the fillers and pigments in the grinding process, so that the conventional amounts of dispersing aids and grinding aids can be reduced according to the invention.
- the invention it is particularly preferred according to the invention to mix the residual water sludge with a solids concentration of 0.02% by weight to 50% by weight, in particular 1% by weight to 30% by weight, and then to grind it with fresh pigment or Fresh filler as powder, fresh pigment-containing and / or fresh filler-containing slurry. If the concentration is too low, the recycling process becomes uneconomical.
- the ratio of fillers and / or pigments to fibers in the residual water sludges can vary within a wide range.
- it is particularly preferred to use residual water sludges with an optionally enriched concentration of fillers and / or pigments which are in the range from 2% by weight to 80% by weight, in particular 20% by weight to 60% by weight.
- % is based on the solids content.
- the fiber content on the one hand or the filler and / or pigment content on the other hand can vary, for example, from 2 to 98% by weight or 98 to 2% by weight. Fiber-free residual water sludges can of course also be used according to the invention.
- the preferred compositions of various sewage sludges are exemplified here.
- the waste water from production preferably comprises 0.5 to 5% by weight, in particular 2.5% by weight, of material loss with a special fresh water requirement of 10 to 100 l / kg, in particular 20 l / kg.
- the consistency is preferably 0.02 to 0.5, in particular 0.125% by weight.
- a ratio of fiber to filler and / or pigment to 20 to 80 wt .-% or 80 to 20 wt .-%, in particular fibers to pigment in a ratio of 40 to 60 wt .-% of a waste water is particularly preferred for the purposes of the invention from production.
- the pH value of the residual water sludge which accumulates as waste water from production, can vary within wide limits.
- the pH is particularly preferably set in the range from 4.5 to 8.5, in particular in the neutral range around pH 7.
- Waste water from the coating plant which can be used according to the invention can, for example, have a solids content of 0.1 to 20% by weight, in particular 1% by weight before precipitation and 1 to 30% by weight, in particular 5% by weight after precipitation. exhibit.
- the pH can be, for example, in the range from 6.5 to 10, preferably 7.5 before the precipitation and 6.0 to 10.0, preferably 7.0, after the precipitation be.
- the ash content should in particular be in the range from 60 to 95% by weight, in particular 90% by weight.
- a typical composition contains 1 to 90% by weight, in particular 20% by weight of kaolin, 1 to 90% by weight, in particular 60% by weight of calcium carbonate, 0.5 to 50% by weight, in particular 15% by weight .-% talc and 0.1 to 40 wt .-%, in particular 5 wt .-% other.
- kaolin, natural or precipitated calcium carbonates, artificial or natural aluminum silicates and oxide hydrates, titanium dioxide, satin white, dolomite, mica, metal, in particular aluminum flakes, bentonite, rutile, magnesium hydroxide are preferably used as fresh pigment and / or filler.
- Plaster, layered silicate, talc, calcium silicate and other stones and earth are used.
- Fresh pigment or fresh filler is preferably mixed as a powder, slurries containing fresh pigment and / or fresh filler in the presence of the residual water sludge and optionally conventional grinding aids and / or dispersing aids to form a slurry with a solids content of 30 to 85% by weight, in particular 40 to 75% by weight and ground.
- the fresh pigments or fresh fillers as powder, fresh pigment-containing and / or fresh filler-containing slurries preferably have a particle size distribution of
- Grain size distributions for coating pigments are known from EP 0 625 611 A1, which are also preferably adjusted using the present invention. So it is particularly preferred in the sense of the present invention that the Pigments have the following particle size distribution: a) 95 to 100% by weight of particles ⁇ 10 ⁇ m b) 50 to 100% by weight of particles ⁇ 2 ⁇ m, in particular 50 to 95% by weight of particles ⁇ 2 ⁇ m c) 27 up to 95% by weight of particles ⁇ 1 ⁇ m, in particular 27 to 75% by weight of particles ⁇ 1 ⁇ m and d) 0.1 to 55% by weight of particles ⁇ 0.2 ⁇ m, in particular 0.1 to 35% by weight of particles ⁇ 0.2 ⁇ m, in each case based on the equivalent diameter of the particles.
- a large variation in the whiteness and grain size distributions is also possible, which can be controlled in particular by the type and duration of the grinding. It is thus possible to mix relatively coarse fresh filler with a large amount of residual water sludge on site in order to introduce this slurry into the paper pulp after grinding. In the same way, it is possible to use a smaller amount of residual water sludge on site for finer grinding with fresh pigment, which then serves as a coating pigment and / or filler. The paper manufacturer is therefore no longer tied to predetermined particle sizes of the fresh pigments and / or fresh fillers and pigment slurries from suppliers of the raw materials.
- Pigment slurries from raw material suppliers are usually characterized by the number of percentages by weight of particles smaller than 2 ⁇ m, for example as types: 95, 90, 75, 60, 50 etc.
- the paper manufacturer is therefore able to produce pigments as slurry itself on site in a satellite system according to the respective needs. This allows a flexible and quick reaction to quality and production requirements, for example the different paper raw materials for the paper pulp, the pigments or slurries for the primer, top coat and single coat or the pigmentation alone, as well as the mixing with other pigments. Above all, however, this is a considerable one Reduction in transport costs evident, since ready-made slurries with a high water content do not necessarily have to be transported over long distances.
- the method according to the invention is particularly suitable for the processing of waste water sludges or fiber slurry partial streams from the waste paper processing paper industry and the reuse of paper scrap, in particular in the treatment of waste paper from the ash removal stage, where particularly great importance is attached to a pure type and korn conductingnspez 'rfische separation of the fillers and pigments is applied in order to exploit this here by re-use, and thereby to utilize the energy introduced and value.
- the coating pigment slurries obtainable with the aid of the present invention can be used particularly advantageously in the paper industry, in particular for producing a coating color for the paper coating or in the paper pulp.
- the use for the production of a coating pigment slurry for offset paper is particularly preferred.
- the slurries according to the invention are also suitable for the production of a coating slip for lightweight, coated papers, in particular also at high application speed, and for the production of roll offset papers, in particular for the production of lightweight, coated roll offset papers, the coating of cardboard and special paper, such as labels, wallpaper, silicon base paper, carbonless, and the addition to gravure paper.
- the coating pigment slurries obtainable according to the invention are particularly useful in sheetfed offset, in particular for sheetfed offset single coat, sheetfed offset double coat: sheetfed offset pre-coat and sheetfed offset top coat; - in web offset, especially for the LWC web offset single line, web offset double line: web offset primer and web offset topcoat; - In rotogravure, especially for the LWC-Tiefd ⁇ ck single line, rotogravure double line: rotogravure pre-coat and rotogravure top coat; - In the carton, especially for the double-line carton: carton pre-coat and carton top coat and for special papers, especially for labels and flexible packaging.
- the process offers the possibility of using the pigment slurries produced according to the invention without any loss of quality in the base papers, coatings and, in particular, the final qualities produced therewith.
- Solids content 64% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
- Solids content 62% Brookfield viscosity (100 / min): 1,400 mPas pH: 8.5
- Formaldehyde, epoxy resin 0.5 part by weight of commercially available brightener (opt.)
- Solids content 66% Brookfield viscosity (100 / min): 1,200 mPas pH: 9.0
- Solids content 58% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
- Formaldehyde, epoxy resin 0.6 parts by weight of commercially available Ca stearate
- Solids content 60% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
- Solids content 58% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
- Silos of any size are used to hold and store dry fillers and pigments with a uniform or possibly different basic grain size, for example calcium carbonate.
- Dosing devices discharge the filler and / or pigment powder with subsequent transport, if necessary to day silo container (s), if necessary with cleaning devices.
- Dosing devices for the powder (s) possibly controlled by programmable logic controllers (PLC) with the electronically integrated recipes, determine gravimetrically and / or volumetrically the quantities of the components to be mixed, which are required for mixing with water, fresh water or circulating water from the paper mill.
- PLC programmable logic controllers
- a residual water sludge with a solids content of in particular 0.02 to 50% by weight is partially or completely, optionally with the addition of water at a higher concentration of
- Residual water sludge used Residual water sludge used. Accordingly, containers for storing the residual water sludge, dosing devices for the residual water sludge, which determine the amount to be used gravimetrically or volumetrically, are also required. In addition, containers are required to hold the mixture of fresh pigment or filler as a powder, slurry containing fresh pigment and / or filler and residual water sludge / water, optionally grinding aids and dispersing aids or other aids. Dispersing devices (dissolvers) or other agitators are required for dispersion and stability adjustment.
- the grinding of the fresh pigments and / or fresh fillers as powder, fresh-pigment-containing and / or fresh-filler-containing slurry with the residual water slurries can be carried out continuously according to the invention in conventional stirred ball mills, for example with a content of 700 to 5000 l or greater. Grinding media, preferably grinding balls, in particular with a diameter of 1 to 4 mm, are used.
- sieves are usually used, preferably curved sieves for separating contaminants (broken balls, separating Fabrics, rust, etc.). Laser measuring instruments are used to determine and control the fineness of grinding during the grinding process and the computer-aided control of the agitator ball mill system. If necessary, further dosing injection devices are required for the subsequent dosing of dispersing and grinding aids on the agitator ball mill. After the pigment slurry has been discharged, sieves may be required for the further separation of pollutants with a size of more than 20 ⁇ m.
- the fresh pigment and / or filler material used in particular calcium carbonate powder used in dry form, has a whiteness according to DIN 53163 of more than 90%, in particular a whiteness of more than 95% in a fineness of d 97 ⁇ 25 ⁇ m, a fineness not greater d 97 100 ⁇ m, a purity of the carbonate ⁇ 98%, a proportion of SiO 2 ⁇ 1.0, in particular ⁇ 0.2%.
- Varying proportions of carbonate, for example, mixed with residual water slurry are ground to a slurry which has a solids content which can be adjusted, for example, to a usable coating color. If necessary, the solids content can also be set higher if the pigment slurry is to be stored for a longer period.
- the fineness of the slurry is determined in particular by the dwell time and / or the energy consumption during production in the agitator ball mill.
- the whiteness of the pigment slurry results, among other things, from the mixing ratio of fresh pigment to residual water sludge and, in particular, the type of fresh pigment used.
- Table 1 An embodiment of the composition of the residual water sludge, as can be used according to the invention, is shown in Table 1 below: Table 1
- the water content of the sewage sludge was 19.5%.
- the pH was measured in a 10% solution and was 6.8.
- a portion of the dried sewage sludge was heated at 450 ° C for 2 hours.
- the loss on ignition (organic proportions) was 13.4%.
- the degree of whiteness (brightness R y , C / 2 ° DIN 53163) after grinding was:
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Abstract
The invention concerns a method of reusing fillers and coating pigments used in the manufacture of paper, paperboard and cardboard and obtained from the residual water slurries of waste water from paintworks, de-inking plants, intra-plant purification plants or separation devices. The invention further concerns the use of pigment slurry occurring in this way to produce a coating compound for the paper industry and for the use of compound in paper manufacture. The method according to the invention for reusing fillers and coating pigments used in the manufacture of paper, paperboard and cardboard and obtained from the residual water slurries of waste water from paintworks, de-inking plants, intra-plant purification plants or separation devices is characterized in that the residual water slurries containing fillers and coating pigments are delivered as a powder or slurry containing fresh pigment and/or fresh fillers to a mixing stage and subsequently to a comminution stage in order to form a pigment slurry containing fresh pigment or fresh fillers.
Description
VERFAHREN ZUR WIEDERVERWERTUNG VON FÜLLSTOFFEN METHOD FOR RECYCLING FILLERS
UND STREICH PIGMENTEN DER PAPIER-, PAPPE- UNDAND PRINT PIGMENTS OF PAPER, CARDBOARD AND
KARTONHERSTELLUNGCARDBOARD PRODUCTION
Gegenstand der Erfindung ist ein Verfahren zur Wiederverwertung von Füllstoffen und Streichpigmenten der Papier-, Pappe- und Kartonherstellung aus den Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen Kläranlagen oder Abscheidevorrichtungen sowie die Verwendung so an- fallender Pigment-Slurries als Füllstoff zur Herstellung von Papier oder als Pigment- Slurry zur Herstellung einer Streichmasse für die Papierindustrie.The invention relates to a process for recycling fillers and coating pigments from the manufacture of paper, cardboard and cardboard from the residual water sludge from the coating waste water, deinking plants, internal sewage treatment plants or separating devices, and the use of pigment slurries thus obtained as a filler for the production of paper or as Pigment slurry for the production of a coating slip for the paper industry.
Bei der Herstellung von Papier werden dem Rohstoff, d. h. Zellstoff, Holz, Strohzellstoff oder Hardemhalbstoff auch Altpapierhalbstoff, Füllstoffe und Pigmente zugesetzt, mit denen eine geschlossene Oberfläche erzielt werden soll, um die Eigenschaften des Papiers, insbesondere den Weißgrad, die Opazität und die Bedruckbarkeit des Papiers zu verbessern.In the manufacture of paper, the raw material, i.e. H. Pulp, wood, straw pulp or hard pulp also added waste pulp, fillers and pigments with which a closed surface is to be achieved in order to improve the properties of the paper, in particular the whiteness, the opacity and the printability of the paper.
Fast alle Papiere werden mit Füllstoffen versetzt, die besonders Druck- und Schreibpapieren eine gleichmäßige Formation, bessere Weiche, Weiße und Griff geben. Diese meist "Asche" genannten Füllstoffe, da sie bei der Verbrennung- anaiyse als Asche zurückbleiben, werden entweder der Fasersuspension zugegeben oder beim Streichen aufgetragen.Almost all papers are filled with fillers, which give printing and writing papers in particular an even formation, better softness, whiteness and grip. These fillers, which are usually called "ashes", since they remain as ashes during combustion analysis, are either added to the fiber suspension or applied during brushing.
Naturdruckpapiere (ungestrichene Papiere) enthalten bis zu 35 Gew. -% Füllstoffe, gestrichene Papiere 25 Gew-% bis 50 Gew.-%. Die Füllstoffmenge hängt sehr vom Verwendungszweck des Papiers ab. Stark beschwerte Papiere besitzen geringere Festigkeiten und schlechteres Leimungsvermögen.Natural printing papers (uncoated papers) contain up to 35% by weight fillers, coated papers 25% to 50% by weight. The amount of filler depends very much on the intended use of the paper. Heavily weighted papers have lower strengths and poorer sizing properties.
Der Füllstoffanteil in der Papiermasse liegt üblicherweise zwischen 5 bis 35 Gew.-% und besteht aus Primärpigment oder aus rezirkulierten Streichpigmenten, die von
Reststreichfarben oder gestrichenem Ausschuß stammen können. Neben der Weiße des Füllstoffs, der für weiß-getonte Papiere wichtig ist, spielt die Korngröße eine wesentliche Rolle, da sie die Fullstoffausbeute stark und die physikalischen Eigenschaften des Papiers, insbesondere die Porosität beiemflußt. Der im Papier verbleibende Füllstoffanteil betragt zwischen 20 und 80 % der der Fasersuspension zugesetzten Menge Die Ausbeute hangt sowohl von der Füllstoffart als auch von der Stoffzusammensetzung, dem Mahlgrad, der Fixierung der Füllstoffteilchen durch Harz und Aluminiumsulfat, dem Papiergewicht, der Papiermaschinengeschwindigkeit, der Art des Wasserentzuges und der Feinheit des Siebes ab.The proportion of filler in the paper pulp is usually between 5 and 35% by weight and consists of primary pigment or of recirculated coating pigments which are from Remaining coating colors or deleted scrap can come. In addition to the whiteness of the filler, which is important for white-toned papers, the grain size plays an important role, since it strongly influences the filler yield and influences the physical properties of the paper, especially the porosity. The amount of filler remaining in the paper is between 20 and 80% of the amount added to the fiber suspension.The yield depends on the type of filler as well as on the composition, the degree of grinding, the fixation of the filler particles by resin and aluminum sulfate, the paper weight, the paper machine speed, the type of Dehydration and the fineness of the sieve.
Entsprechend dem Verbrauch haben folgende Produkte als Füllstoff und Streichpigment heute größere Bedeutung Kaolin, Calciumcarbonat, künstliche Aluminiumsili- kate und -oxidhydrate, Titandioxid, Satin-Weiß, Talkum und Calciumsilicat.Depending on consumption, the following products are now more important as fillers and coating pigments: kaolin, calcium carbonate, artificial aluminum silicates and oxide hydrates, titanium dioxide, satin white, talc and calcium silicate.
Bei der Verwertung von Altpapier fallen die Füllstoffe und Pigmente als Abfallprodukt insbesondere in Deinkinganlagen an. Dieses Abfallprodukt besteht beispielsweise aus 50 Gew -% Zellulose, 25 Gew.-% Kaolin und 20 Gew.-% Calciumcarbonat, wobei aber auch weitere geringe Anteile Calciumsulfat, Titan- dioxid, Talkum oder andere Feststoffe vorliegen können, wobei diese Gemische mehr oder weniger große Faseranteile enthalten können.When recycling waste paper, the fillers and pigments are a waste product, especially in deinking plants. This waste product consists, for example, of 50% by weight of cellulose, 25% by weight of kaolin and 20% by weight of calcium carbonate, although other small proportions of calcium sulfate, titanium dioxide, talc or other solids may also be present, these mixtures more or less can contain large amounts of fibers.
In EP 0 492 121 B1 wird die bisherige Aufbereitung von Altpapier derart beschrieben, daß diese Abfallstoffe als ein Abwasser- Feststoffgemisch aus dem Prozeß ausgesondert werden, wobei ein reines Abfallprodukt entsteht, daß etwa 50 % Feststoffanteile enthalt und auf Deponien gelagert wird. Hier wird vorgeschlagen, das schlammartige Wasser-Feststoffgemisch intensiv zu mischen und dann anschließend dieses Gemisch aus Wasser und Feststoff grob, fein beziehungsweise feinst zu zerkleinern und erst dann die Weiterverwendung unter Zugabe entsprechender Zuschlage durchzufuhren. Es wird der Einsatz dieses
Materials aus Ausgangsstoff für Farbstoffe, Kleber, Füllstoffe und hydraulische Bindemittel vorgeschlagen.EP 0 492 121 B1 describes the previous processing of waste paper in such a way that these waste materials are separated out of the process as a waste water / solid mixture, a pure waste product being produced which contains about 50% solids and is stored in landfills. It is proposed here to mix the sludge-like water-solid mixture intensively and then to comminute this mixture of water and solid roughly, finely or very finely and only then to carry out the further use with the addition of an appropriate additive. It will use this Materials from raw material for dyes, adhesives, fillers and hydraulic binders are proposed.
In DE 40 34 054 C1 wird ein Verfahren zur Rückgewinnung von Rohstoffen aus dem mechanischen Restabwasserschlamm der Papierindustrie vorgeschlagen. Bei diesem Verfahren wird der Restwasserschlamm nach Abscheidung des Grobschmutzes zunächst mittels Zentrifugieren vom Schwarzpartikelgehalt befreit und daran anschließend mittels fraktioniertem Sieben in Fasern, Füllstoffe, Pigmente und Agglomerate aufgeteilt. Die Agglomerate werden mittels Scherung behandelt und verworfen, während die Fasern, Füllstoffe und Pigmente gegebenenfalls nach weiterer Behandlung einem gezielten Wiedereinsatz zugeführt werden.DE 40 34 054 C1 proposes a process for the recovery of raw materials from the mechanical residual sewage sludge of the paper industry. In this process, after removing the coarse dirt, the residual water sludge is first freed of the black particle content by centrifugation and then divided into fibers, fillers, pigments and agglomerates by means of fractional sieving. The agglomerates are treated with shear and discarded, while the fibers, fillers and pigments are reused if necessary after further treatment.
Aus EP 0 576 177 A1 ist ein Verfahren zur Wiederverwertung und Wiederverwendung von Rohmaterialien aus den Restwasserschlämmen der Papierindustrie bekannt, das dadurch gekennzeichnet ist, daß die Schlammsuspension in einem ersten Verfahrensschritt einem ersten Sieb-/Reinigungsverfahren bei relativ niedriger Konsistenz unterworfen, anschließend eingedickt, erhitzt und durch einen Dispergierer gegeben wird, bevor dieser Schlamm in der Papierherstellung wieder eingesetzt wird.EP 0 576 177 A1 discloses a process for recycling and reusing raw materials from the residual water sludges of the paper industry, which is characterized in that the sludge suspension is subjected to a first sieving / cleaning process with a relatively low consistency in a first process step, then thickened and heated and passed through a disperser before reusing this slurry in papermaking.
In EP 0554285 B1 wird berichtet, daß alle Rückgewinnungsverfahren auf die Ent- stoffung an sich wenig verschmutzter Kreisläufe gerichtet sind, da der Wiedereinsatz des aus Faser- und Füllstoff bestehenden sogenannten Fang- oder Dickstoffes in den Papierherstellungsprozeß ein höherer Schmutzanteil verbietet. Demgemäß wird ein Verfahren beschrieben, die im Restabwasserschlamm der mechanischen Kläranlage enthaltenen brauchbaren Fasern und Füllstoffe zurückzugewinnen.In EP 0554285 B1 it is reported that all recovery processes are aimed at the removal of contaminated circuits, since the reuse of the so-called capture or thick matter consisting of fiber and filler in the paper manufacturing process prohibits a higher proportion of dirt. Accordingly, a method is described for recovering the useful fibers and fillers contained in the residual sewage sludge of the mechanical sewage treatment plant.
Das Verfahren ist gekennzeichnet durch die Einstellung eines definierten Feststoffgehalts, das Abscheiden der Grobschmutzanteile, das Abscheiden der
Schwarzpartikelanteile, das fraktionierte Feinsieben des Gutanteils und die Rückführung des Faseranteils und des Füllstoff- und Pigmentanteils in die Rohstoffaufbereitung der Papierfabrik.The process is characterized by the setting of a defined solid content, the separation of the coarse dirt, the separation of the Black particle fractions, the fractionated fine sieving of the good fraction and the return of the fiber fraction and the filler and pigment fraction to the raw material processing of the paper mill.
In den Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen Anlagen oder Abscheidevorrichtungen liegen die Füllstoffe und Streichpigmente häufig in agglomerierter Form und mit geringer Weiße vor, die eine direkte Wiederverwendung in der Rohstoffaufbereitung, insbesondere im Strich einschränkt.In the residual water sludge of the coating wastewater, deinking plants, in-house plants or separators, the fillers and coating pigments are often in agglomerated form and have a low whiteness, which limits direct reuse in raw material processing, especially in the coating.
Die Aufgabe der Erfindung besteht in der Bereitstellung eines Verfahrens zur Wiederverwertung von Papierrohstoffen, insbesondere der Füllstoffe und der Streichpigmente bei gleichzeitiger Einsparung von Energiekosten und Rohstoffkosten sowie Transportkosten.The object of the invention is to provide a method for recycling paper raw materials, in particular the fillers and the coating pigments, while saving energy costs and raw material costs as well as transportation costs.
Die vorstehend genannte Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zu Wiederverwertung von Füllstoffen und Streichpigmenten der Papier-, Pappe- und Kartonherstellung aus Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen Kläranlagen oder Abscheidevorrichtungen, das dadurch gekennzeichnet ist, daß man die Füllstoff- und Streichpigment-haltigen Restwasserschlämme der Vermischung und anschließend der Vermahlung zu einer Pigment-Slurry mit Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry zuführt.The above-mentioned object is achieved according to the invention by a process for recycling fillers and coating pigments from paper, cardboard and cardboard production from residual water sludge from the coating waste water, deinking plants, internal sewage treatment plants or separating devices, which is characterized in that the filler and coating pigments are included Residual water sludge of the mixing and then the grinding to a pigment slurry with fresh pigment or fresh filler as a powder, fresh pigment-containing and / or fresh filler-containing slurry.
Mit Hilfe der vorliegenden Erfindung des oben beschriebenen Verfahrens wird eine definierte, konzentrierte Pigment-Slurry oder Füllstoffslurry erhalten, die in der Papier-, Pappe- und Kartonherstellung eingesetzt werden kann.With the help of the present invention of the method described above, a defined, concentrated pigment slurry or filler slurry is obtained which can be used in the manufacture of paper, cardboard and cardboard.
In der Papierherstellung ist es üblich, die Füllstoffe und Streichpigmente sowohl
als Pulver oder in Form einer konzentrierten Slurry, die 50 bis 80 Gew.-% Feststoffanteile aufweist, einzusetzen. Diese Füllstoffe und Pigmente werden üblicherweise von den Herstellern mit der gewünschten Weiße und Korngrößenverteilung zur Verfügung gestellt. Der Kern der vorliegenden Erfindung besteht nunmehr in der Anlieferung des Pigments in einer Art "Grundkörnung", vorzugsweise als Feststoff oder auch als hochkonzentrierte Slurry, beispielsweise mit einem Feststoffgehalt von 70 Gew.-% bis 85 Gew.-% oder mehr, beispielsweise mit einem mittleren Korndurchmesser von 50% <2μm bis 10μm, insbesondere 2 μm bis 5 μm und Vermahlung in wäßriger Phase vor Ort in einer Satellitenmahlanlage auf die gewünschte Weiße und Korngröße. Somit werden die obengenannten Restwasserschlämme nicht den fertig angelieferten oder fertig zubereiteten Rohstoffen beigemischt, sondern diese zunächst durch Vermischung und anschließend der Vermahlung von Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry auf die gewünschte Weiße und Feinheit vermählen und dann als Füllstoff oder Streichpigment eingesetzt. Die genannten mineralischen Füllstoffe und Pigmente werden üblicherweise in Naßoder Trockenverfahren auf die gewünschte Korngröße vermählen. Bei der Naßvermahlung ist naturgemäß ein großer Anteil Wasser erforderlich. Erfmdungsgemäß wurde nun festgestellt, daß ein Teil oder die gesamte Menge des notwendigen Wassers zur Vermischung und anschließend der Vermahlung der Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry durch die Restwasserschlämme ersetzt werden kann, die gegebenenfalls Fasern enthalten. Üblicherweise in den Restwasserschlämmen vorliegende Agglomerate der Füllstoffe oder Pigmente stören hierbei wenig, da diese im Verlauf des Naßmahlprozesses auf die gewünschten Korngrößen zerkleinert werden. Weitere Vorteile der Erfindung bestehen in der gegenüber dem Stand der Technik erhöhten Flexibilität der erhältlichen gewünschten Korngrößen vor Ort, den geringeren Frachtkosten durch Wegfall des Transports von Wasser in marktüblicher Slurry, sowie die verbesserte Stabilität der selbst hergestellten
Pigment-Slurry.In papermaking, it is common for both the fillers and coating pigments as a powder or in the form of a concentrated slurry, which has 50 to 80 wt .-% solids. These fillers and pigments are usually provided by the manufacturers with the desired whiteness and grain size distribution. The essence of the present invention now consists in the delivery of the pigment in a type of "base grain", preferably as a solid or also as a highly concentrated slurry, for example with a solids content of 70% by weight to 85% by weight or more, for example with a average grain diameter of 50% <2 μm to 10 μm, in particular 2 μm to 5 μm and grinding in the aqueous phase on site in a satellite grinding system to the desired whiteness and grain size. Thus, the above-mentioned residual water sludges are not added to the raw materials that have been delivered or prepared, but are first milled to the desired whiteness and fineness by mixing and then grinding fresh pigment or fresh filler as a powder, fresh pigment-containing and / or fresh filler-containing slurry and then as a filler or coating pigment used. The mineral fillers and pigments mentioned are usually ground to the desired particle size in wet or dry processes. A large proportion of water is naturally required for wet grinding. According to the invention, it has now been found that part or all of the water required for mixing and then grinding the fresh pigments or fillers as a powder, slurry containing fresh pigment and / or filler can be replaced by the residual water sludge, which may contain fibers. Agglomerates of the fillers or pigments usually present in the residual water sludges do not cause much disruption here, since these are comminuted to the desired particle sizes in the course of the wet grinding process. Further advantages of the invention consist in the increased flexibility of the desired grain sizes available on site compared to the prior art, the lower freight costs by eliminating the transport of water in commercially available slurry, and the improved stability of the self-produced slurry Pigment slurry.
Bei der Aufbereitung von Restwasserschlämmen ist es naturgemäß erforderlich, den Grobschmutzanteil, der aus Splittern, Sandkörnern und sonstigen Unreinheiten besteht, abzutrennen und zu verwerfen. Der so erhaltene Siebdurchgang besteht aus Fasern, Füllstoffen, Pigmenten, Feinsand, Schwarzpartikeln und Agglomeraten aus Füllstoffen und Pigmenten oder Pigmenten, Fasern und Füllstoffen. Unter Füllstoff werden dabei üblicherweise die in der Papiermasse eingesetzten Feinteilchen verstanden; unter Pigment werden die in der Streichfarbe eingesetzten feinen Teilchen verstanden. Die normalerweise nicht brauchbaren Schwarzpartikel weisen eine große Korngrößenvariation auf. Sie bestehen in der Hauptsache aus grau- bis schwarz gefärbtem Sand, Bodenabrieb, Maschinenabrieb, verkokten Schmiermitteln, sauer attackierten organischen Teilchen, Rost und agglomeriertem Staub oder einer Mischung daraus. Üblicherweise ist eine Abscheidung dieser Schwarzpartikel mittels Zentrifugieren oder Flottieren erforderlich, wenn die Abwasserschlämme der Rohstoffaufbereitung zugeführt werden sollen. Erfindungsgemäß ist jedoch eine entsprechende Abtrennung der Schwarzpartikel nicht notwendigerweise erforderlich, da diese Partikel bei der Vermahlung der Frischfüllstoffe und Frischpigmente in der Regel derart zerkleinert werden, daß der Weißgrad durch die Schwarzpartikel weniger stark beeinflußt wird.When processing residual water sludge, it is naturally necessary to separate and discard the coarse dirt that consists of chips, grains of sand and other impurities. The sieve pass obtained in this way consists of fibers, fillers, pigments, fine sand, black particles and agglomerates of fillers and pigments or pigments, fibers and fillers. Filler is usually understood to mean the fine particles used in the pulp; pigment means the fine particles used in the coating color. The normally unusable black particles have a large grain size variation. They mainly consist of gray to black colored sand, soil abrasion, machine abrasion, coked lubricants, acid-attacked organic particles, rust and agglomerated dust or a mixture thereof. Separation of these black particles by means of centrifugation or floatation is usually necessary if the waste water sludge is to be fed to the raw material treatment. According to the invention, however, a corresponding separation of the black particles is not absolutely necessary, since these particles are generally comminuted in the grinding of the fresh fillers and fresh pigments in such a way that the degree of whiteness is less influenced by the black particles.
Dennoch ist selbstverständlich auch eine Abscheidung der Schwarzpartikel insbesondere mittels Zentrifugieren, wie beispielsweise in EP 0 554 285 B1 beschrieben, auch im Sinne der vorliegenden Erfindung möglich, um ganz besondere Qualitäten der Füllstoffe oder Pigmente im Sinne der Erfindung zu erhalten.Nevertheless, it is of course also possible to separate the black particles, in particular by means of centrifugation, as described, for example, in EP 0 554 285 B1, in the sense of the present invention, in order to obtain very special qualities of the fillers or pigments in the sense of the invention.
In gleicher Weise ist es gegebenenfalls sinnvoll, Faserabtrennungsverfahren insbesondere bei der Aufbereitung von Restwasserschlämmen aus Deinkinganlagen,
Kläranlagen und Abscheidevorrichtungen durchzuführen. Als bekannte Verfahren bieten sich hier die Flockung und Sedimentation, die Filtrierung, Siebung, Zentrifugierung sowie sonstige chemische Behandlungsverfahren, wie beispielsweise die Oxidation an. In diesem Falle liegt dann üblicherweise ein Gemisch unterschiedlicher Pigmente vor, das häufig Kaolin, Calciumcarbonat und Talkum enthält. Durch Flockung und Umladung bilden sich bei den Abtrennungsverfahren häufig Agglomerate. Die Restwasserschlämme mit niedrigem Feststoffgehalt sind an sich dementsprechend kaum als Rohstoff einsetzbar.In the same way, it may make sense to use fiber separation processes, especially when processing residual water sludge from deinking plants, Sewage treatment plants and separation devices. Flocculation and sedimentation, filtration, sieving, centrifugation and other chemical treatment processes, such as oxidation, are available as known processes. In this case there is usually a mixture of different pigments, which often contains kaolin, calcium carbonate and talc. Flocculation and reloading often form agglomerates in the separation processes. The residual water sludge with a low solids content can therefore hardly be used as a raw material.
Zur Herstellung von Streichfarben ist daher eine Anhebung des Feststoffgehalts des Pigmentgemisches sowie in der Regel eine Anhebung der Weiße nach an sich bekannten Verfahren erforderlich. Die Zerstörung von Agglomeraten, die das Laufverhalten einer Streichfarbe am Blade durch Rakelstreifen stören und die Eigenschaften des Strichs negativ beeinflussen, ist besonders bevorzugt. Die Pigment- und Füllstoffteilchen des Restwasserschlamms, die zum Einsatz als Füllstoff oder Pigment vorgesehen sind, wirken hierbei als Mahlhilfsmittel und Dispergierhilfsmittel für die Zerstörung der Agglomerate bei dem Mahlprozeß. Gleichzeitig wirkt der Restwasserschlamm inklusive der beladenen Partikel als Dispergierhilfsmittel und Mahlhilfsmittel für die Füllstoffe und Pigmente bei dem Mahlprozeß, so daß die an sich üblichen Mengen an Dispergierhilfsmitteln und Mahlhilfsmitteln erfindungsgemäß verringert werden können.To produce coating colors, it is therefore necessary to increase the solids content of the pigment mixture and, as a rule, to increase the whiteness by methods known per se. It is particularly preferred to destroy agglomerates that interfere with the running behavior of a coating color on the blade due to squeegee strips and adversely affect the properties of the coating. The pigment and filler particles of the residual water sludge, which are intended for use as filler or pigment, act here as grinding aids and dispersing aids for the destruction of the agglomerates in the grinding process. At the same time, the residual water sludge, including the loaded particles, acts as a dispersing aid and grinding aid for the fillers and pigments in the grinding process, so that the conventional amounts of dispersing aids and grinding aids can be reduced according to the invention.
Dementsprechend ist es erfindungsgemäß besonders bevorzugt, den Restwasser- schlämm mit einer Feststoffkonzentration von 0,02 Gew.-% bis 50 Gew.-%, insbesondere 1 Gew.-% bis 30 Gew.-% zur Vermischung und anschließend der Vermahlung mit Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry einzustellen. Bei einer zu geringen Konzentration wird das Wiederverwertungsverfahreπ unwirtschaftlich.
In den Restwasserschlämmen kann das Verhältnis von Füllstoffen und/oder Pigmenten zu Fasern in einer großen Bandbreite variieren. Besonders bevorzugt ist es im Sinne der vorliegenden Erfindung Restwasserschlämme mit einer gegebenenfalls angereicherten Konzentration an Füllstoffen und/oder Pigmenten einzusetzen, die im Bereich von 2 Gew.-% bis 80 Gew.-%, insbesondere 20 Gew.- % bis 60 Gew.-% bezogen auf den Feststoffgehalt liegt. So kann der Faseranteil einerseits oder der Füllstoff- und/oder Pigmentanteil andererseits beispielsweise von 2 bis 98 Gew.-% oder 98 bis 2 Gew.-% variieren. Auch sind selbstverständlich Faser-freie Restwasserschlämme erfindungsgemäß einsetzbar.Accordingly, it is particularly preferred according to the invention to mix the residual water sludge with a solids concentration of 0.02% by weight to 50% by weight, in particular 1% by weight to 30% by weight, and then to grind it with fresh pigment or Fresh filler as powder, fresh pigment-containing and / or fresh filler-containing slurry. If the concentration is too low, the recycling process becomes uneconomical. The ratio of fillers and / or pigments to fibers in the residual water sludges can vary within a wide range. For the purposes of the present invention, it is particularly preferred to use residual water sludges with an optionally enriched concentration of fillers and / or pigments which are in the range from 2% by weight to 80% by weight, in particular 20% by weight to 60% by weight. % is based on the solids content. The fiber content on the one hand or the filler and / or pigment content on the other hand can vary, for example, from 2 to 98% by weight or 98 to 2% by weight. Fiber-free residual water sludges can of course also be used according to the invention.
Beispielhaft seien hier die bevorzugten Zusammensetzungen verschiedener Abwasserschlämme erläutert. Vorzugsweise umfaßt das Abwasser aus der Produktion 0,5 bis 5 Gew.-%, insbesondere 2,5 Gew.-% Stoffveriust bei einem speziellen Frischwasserbedarf von 10 bis 100 l/kg, insbesondere 20 l/kg. Die Stoffdichte beträgt vorzugsweise 0,02 bis 0,5, insbesondere 0,125 Gew.-%. Besonders bevorzugt im Sinne der Erfindung ist hier ein Mengenverhältnis von Faseranteil zu Füllstoff und/oder Pigmentanteil von 20 zu 80 Gew.-% oder 80 zu 20 Gew.-%, insbesondere Fasern zu Pigment im Verhältnis 40 zu 60 Gew.-% eines Abwassers aus der Produktion.The preferred compositions of various sewage sludges are exemplified here. The waste water from production preferably comprises 0.5 to 5% by weight, in particular 2.5% by weight, of material loss with a special fresh water requirement of 10 to 100 l / kg, in particular 20 l / kg. The consistency is preferably 0.02 to 0.5, in particular 0.125% by weight. A ratio of fiber to filler and / or pigment to 20 to 80 wt .-% or 80 to 20 wt .-%, in particular fibers to pigment in a ratio of 40 to 60 wt .-% of a waste water is particularly preferred for the purposes of the invention from production.
Der pH-Wert der Restwasserschlämme, die als Abwasser aus der Produktion anfallen, kann in weiten Grenzen variieren. Besonders bevorzugt wird der pH-Wert im Bereich von 4,5 bis 8,5, insbesondere im neutralen Bereich um pH 7 eingestellt.The pH value of the residual water sludge, which accumulates as waste water from production, can vary within wide limits. The pH is particularly preferably set in the range from 4.5 to 8.5, in particular in the neutral range around pH 7.
Erfindungsgemäß einsetzbares Abwasser aus der Streicherei kann beispielsweise einen Feststoffgehalt von 0,1 bis 20 Gew.-%, insbesondere 1 Gew.-% vor der Fällung und nach der Fällung von 1 bis 30 Gew.-%, insbesondere bei 5 Gew.-% aufweisen. Der pH-Wert kann beispielsweise im Bereich von 6,5 bis 10, vorzugsweise 7,5 vor der Fällung und 6,0 bis 10,0, vorzugsweise 7,0, nach der Fällung
betragen. Der Aschegehalt sollte insbesondere im Bereich von 60 bis 95 Gew.-%, insbesondere bei 90 Gew.-% liegen. Eine typische Zusammensetzung enthält 1 bis 90 Gew.-%, insbesondere 20 Gew.-% Kaolin, 1 bis 90 Gew.-%, insbesondere 60 Gew.-% Calciumcarbonat., 0,5 bis 50 Gew.-%, insbesondere 15 Gew.-% Talkum und 0,1 bis 40 Gew.-%, insbesondere 5 Gew.-% Sonstiges.Waste water from the coating plant which can be used according to the invention can, for example, have a solids content of 0.1 to 20% by weight, in particular 1% by weight before precipitation and 1 to 30% by weight, in particular 5% by weight after precipitation. exhibit. The pH can be, for example, in the range from 6.5 to 10, preferably 7.5 before the precipitation and 6.0 to 10.0, preferably 7.0, after the precipitation be. The ash content should in particular be in the range from 60 to 95% by weight, in particular 90% by weight. A typical composition contains 1 to 90% by weight, in particular 20% by weight of kaolin, 1 to 90% by weight, in particular 60% by weight of calcium carbonate, 0.5 to 50% by weight, in particular 15% by weight .-% talc and 0.1 to 40 wt .-%, in particular 5 wt .-% other.
Im Rahmen der vorliegenden Erfindung werden vorzugsweise als Frischpigment und/oder Frischfüllstoff Kaolin, natürliche oder gefällte Calciumcarbonate, künstliche oder natürliche Aluminiumsiiikate und -oxidhydrate, Titandioxid, Satin-Weiß, Dolomit, Glimmer, Metall-, insbesondere Aluminiumflakes, Bentonit, Rutil, Magnesiumhydroxid, Gips, Schichtsilikate, Talkum, Calciumsilikat sowie sonstige Steine und Erden einsetzt.In the context of the present invention, kaolin, natural or precipitated calcium carbonates, artificial or natural aluminum silicates and oxide hydrates, titanium dioxide, satin white, dolomite, mica, metal, in particular aluminum flakes, bentonite, rutile, magnesium hydroxide are preferably used as fresh pigment and / or filler. Plaster, layered silicate, talc, calcium silicate and other stones and earth are used.
Bevorzugterweise wird Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries in Anwesenheit der Restwasserschlämme und gegebenenfalls üblichen Mahlhilfsmitteln und/oder Dispergierhilfsmitteln zu einer Slurry mit einem Feststoffgehalt von 30 bis 85 Gew.- %, insbesondere 40 bis 75 Gew.-% vermischt und vermahlt.Fresh pigment or fresh filler is preferably mixed as a powder, slurries containing fresh pigment and / or fresh filler in the presence of the residual water sludge and optionally conventional grinding aids and / or dispersing aids to form a slurry with a solids content of 30 to 85% by weight, in particular 40 to 75% by weight and ground.
Die Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries werden vorzugsweise zu einer Korngrößenverteilung vonThe fresh pigments or fresh fillers as powder, fresh pigment-containing and / or fresh filler-containing slurries preferably have a particle size distribution of
10 bis 99 Gew.-% an Teilchen <1 μm, insbesondere10 to 99% by weight of particles <1 μm, in particular
10 bis 95 Gew.-% an Teilchen <1 μm jeweils bezogen auf den Äquivalentdurchmesser vermahlt.10 to 95 wt .-% of particles <1 μm each ground based on the equivalent diameter.
Aus EP 0 625 611 A1 sind Korngrößenverteilungen für Streichpigmente bekannt, die auch mit Hilfe der vorliegenden Erfindung vorzugsweise eingestellt werden. So ist es besonders bevorzugt im Sinne der vorliegenden Erfindung, daß die
Pigmente folgende Korngrößenverteilung aufweisen: a) 95 bis 100 Gew.-% an Teilchen < 10 μm b) 50 bis 100 Gew.-% an Teilchen < 2 μm, insbesondere 50 bis 95 Gew.-% an Teilchen < 2 μm c) 27 bis 95 Gew.-% an Teilchen < 1 μm, insbesondere 27 bis 75 Gew.-% an Teilchen < 1 μm und d) 0,1 bis 55 Gew.-% an Teilchen < 0,2 μm, insbesondere 0,1 bis 35 Gew.-% an Teilchen < 0,2 μm, jeweils bezogen auf den Äquivalentdurchmesser der Teilchen.Grain size distributions for coating pigments are known from EP 0 625 611 A1, which are also preferably adjusted using the present invention. So it is particularly preferred in the sense of the present invention that the Pigments have the following particle size distribution: a) 95 to 100% by weight of particles <10 μm b) 50 to 100% by weight of particles <2 μm, in particular 50 to 95% by weight of particles <2 μm c) 27 up to 95% by weight of particles <1 μm, in particular 27 to 75% by weight of particles <1 μm and d) 0.1 to 55% by weight of particles <0.2 μm, in particular 0.1 to 35% by weight of particles <0.2 μm, in each case based on the equivalent diameter of the particles.
Erfindungsgemäß ist darüber hinaus eine große Variation der Weiße und Korngrößenverteilungen möglich, die insbesondere durch die Art und Dauer der Mahlung gesteuert werden kann. So ist es möglich, vor Ort relativ groben Frischfüllstoff mit einer großen Menge an Restwasserschlamm zu vermischen, um diese Slurry nach der Vermahlung in die Papiermasse einzubringen. In gleicher Weise ist es möglich, vor Ort durch Einsatz einer geringeren Menge an Restwasserschlamm diese zur feineren Vermahlung mit Frischpigment einzusetzen, was dann als Streichpigment und/oder Füllstoff dient. Der Papierhersteller ist somit nicht mehr an vorgegebene Teilchengrößen der Frischpigmente und/oder Frischfüllstoffe sowie Pigment-Slurries von Anbietern der Rohstoffe gebunden. DieAccording to the invention, a large variation in the whiteness and grain size distributions is also possible, which can be controlled in particular by the type and duration of the grinding. It is thus possible to mix relatively coarse fresh filler with a large amount of residual water sludge on site in order to introduce this slurry into the paper pulp after grinding. In the same way, it is possible to use a smaller amount of residual water sludge on site for finer grinding with fresh pigment, which then serves as a coating pigment and / or filler. The paper manufacturer is therefore no longer tied to predetermined particle sizes of the fresh pigments and / or fresh fillers and pigment slurries from suppliers of the raw materials. The
Pigment-Slurries der Rohstoffanbieter werden üblicherweise mit der Zahl der Gewichtsprozente an Teilchen kleiner als 2 μm charakterisiert, beispielsweise als Typ: 95, 90, 75, 60, 50 etc. . Der Papierhersteller ist somit in der Lage, Pigmente als Slurry den jeweiligen Bedürfnissen entsprechend selbst vor Ort in einer Satellitenanlage herzustellen. Dies erlaubt eine flexible und schnelle Reaktion auf Qualitäts- und Produktionsanforderungen, beispielsweise der verschiedenen Papierrohstoffe für die Papiermasse, die Pigmente oder Slurries für den Vorstrich, Deckstrich und Einfachstrich oder die Pigmentierung allein, sowie die Vermischung mit anderen Pigmenten. Vor allem aber ist hierdurch eine beträchtliche
Reduzierung der Transportkosten ersichtlich, da nicht notwendigerweise Fertigslurries mit hohem Wassergehalt über große Entfernungen transportiert werden müssen.Pigment slurries from raw material suppliers are usually characterized by the number of percentages by weight of particles smaller than 2 μm, for example as types: 95, 90, 75, 60, 50 etc. The paper manufacturer is therefore able to produce pigments as slurry itself on site in a satellite system according to the respective needs. This allows a flexible and quick reaction to quality and production requirements, for example the different paper raw materials for the paper pulp, the pigments or slurries for the primer, top coat and single coat or the pigmentation alone, as well as the mixing with other pigments. Above all, however, this is a considerable one Reduction in transport costs evident, since ready-made slurries with a high water content do not necessarily have to be transported over long distances.
Auch wenn im Sinne der vorliegenden Erfindung an sich bekannte Netzmittel, Stabilisierungsmittel, Mahlhilfsmittel und Dispergierhilfsmittel während der Vermischung und der Vermahlung der Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry mit Restwasserschlämmen eingesetzt werden können, wie sie beispielsweise aus EP 0 625 611 A1 bekannt sind, so ist doch erfindungsgemäß die erforderliche Menge gegenüber dem Stand der Technik deutlich verringert. Zum einen enthalten die Restabwasserschlämme bereits eine gewisse Menge der genannten Mittel. Zum anderen ist es aufgrund der Möglichkeit der direkten Vermahlung vor Ort nicht notwendig, die Netz-, Stabilisierungs-, Mahl- und Dispergierhilfsmittel in üblichen Größenordnungen einzusetzen, da die Zeitspanne zwischen Herstellung der Slurry und der Verwendung stark verkürzt werden kann. Ein weiterer Vorteil der geringeren Einsatzmengen an Hilfsmitteln ist die verbesserte Retention der Pigmente bei der Papierherstellung, da größere Mengen einen negativen Einfluß auf die Retention haben.Even if, for the purposes of the present invention, known wetting agents, stabilizers, grinding aids and dispersing aids can be used as powder, fresh pigment-containing and / or fresh-filler-containing slurry with residual water slurries during the mixing and grinding of the fresh pigments or fresh fillers, as described, for example, in EP 0 625 611 A1 are known, the amount required according to the invention is significantly reduced compared to the prior art. On the one hand, the residual sewage sludge already contains a certain amount of the agents mentioned. On the other hand, because of the possibility of direct grinding on site, it is not necessary to use the wetting, stabilizing, grinding and dispersing aids in the usual order of magnitude, since the time period between production of the slurry and use can be greatly shortened. Another advantage of the lower amounts of auxiliaries used is the improved retention of the pigments in paper production, since larger amounts have a negative influence on the retention.
Das erfindungsgemäße Verfahren eignet sich besonders für die Aufarbeitung aus Füll- und Faserstoff bestehenden Abwasserschlämmen oder Faserstoffsuspensions-Teilströmen der Altpapier-verarbeitenden Papierindustrie und der Wiederverwertung von Papierausschuß, insbesondere bei der Aufbereitung von Altpapier aus der Stufe der Entaschung, wo besonders großen Wert auf eine sortenreine und korngrößenspez'rfische Auftrennung der Füllstoffe und Pigmente gelegt wird, um diese hier durch Wiedereinsatz zu verwerten, und dadurch eingebrachte Energie und Wertigkeit zu nutzen.
Die mit Hilfe der vorliegenden Erfindung erhältlichen Streichpigment-Slurries können besonders vorteilhaft in der Papierindustrie, insbesondere zur Herstellung einer Streichfarbe für den Papierstrich oder in der Papiermasse eingesetzt werden. Besonders bevorzugt ist die Verwendung zur Herstellung einer Streichpigment- Slurry für Offsetpapier. Darüber hinaus eignen sich die erfindungsgemäßen Slurries auch zur Herstellung einer Streichmasse für leichtgewichtige, gestrichene Papiere, insbesondere auch bei hoher Auftragsgeschwindigkeit, sowie zur Herstellung von Rollen-Offsetpapieren, insbesondere zur Herstellung von leichtgewichtigen, gestrichenen Rollen-Offsetpapieren, das Streichen von Karton und Spezialpapier, wie Etiketten, Tapeten, Silikoπrohpapier, selbstdurchschreibend, sowie der Beimischung bei Tiefdruckpapieren. In diesem Sinne sind die erfindungsgemäß erhältlichen Streichpigment-Slurries, insbesondere einsetzbar im Bogenoffset, insbesondere für den Bogenoffset-Einfachstrich, Bogenoffset- Doppelstrich: Bogenoffset-Vorstrich und Bogenoffset-Deckstrich; - im Rollenoffset, insbesondere für den LWC-Rollenoffset-Einfachstrich, Rollenoffset-Doppelstrich: Rollenoffset-Vorstrich und Rollenoffset-Deckstrich; - im Tiefdruck, insbesondere für den LWC-Tiefdπ ck-Einfachstrich, Tiefdruck-Doppelstrich: Tiefdruck-Vorstrich und Tiefdruck-Deckstrich; - im Karton, insbesondere für den Karton-Doppelstrich: Karton-Vorstrich und Karton-Deckstrich und für Spezialpapiere, insbesondere für Etiketten und flexible Verpackungen.The method according to the invention is particularly suitable for the processing of waste water sludges or fiber slurry partial streams from the waste paper processing paper industry and the reuse of paper scrap, in particular in the treatment of waste paper from the ash removal stage, where particularly great importance is attached to a pure type and korngrößenspez 'rfische separation of the fillers and pigments is applied in order to exploit this here by re-use, and thereby to utilize the energy introduced and value. The coating pigment slurries obtainable with the aid of the present invention can be used particularly advantageously in the paper industry, in particular for producing a coating color for the paper coating or in the paper pulp. The use for the production of a coating pigment slurry for offset paper is particularly preferred. In addition, the slurries according to the invention are also suitable for the production of a coating slip for lightweight, coated papers, in particular also at high application speed, and for the production of roll offset papers, in particular for the production of lightweight, coated roll offset papers, the coating of cardboard and special paper, such as labels, wallpaper, silicon base paper, carbonless, and the addition to gravure paper. In this sense, the coating pigment slurries obtainable according to the invention are particularly useful in sheetfed offset, in particular for sheetfed offset single coat, sheetfed offset double coat: sheetfed offset pre-coat and sheetfed offset top coat; - in web offset, especially for the LWC web offset single line, web offset double line: web offset primer and web offset topcoat; - In rotogravure, especially for the LWC-Tiefdπ ck single line, rotogravure double line: rotogravure pre-coat and rotogravure top coat; - In the carton, especially for the double-line carton: carton pre-coat and carton top coat and for special papers, especially for labels and flexible packaging.
Das Verfahren bietet die Möglichkeit, die erfindungsgemäß hergestellten Pigment- Slurries ohne Qualitätseinbuße bei den damit hergestellten Rohpapieren, Strichen und insbesondere den Endqualitäten einzusetzen.The process offers the possibility of using the pigment slurries produced according to the invention without any loss of quality in the base papers, coatings and, in particular, the final qualities produced therewith.
Nachfolgend werden beispielhaft einige Streichrezepturen angegeben, die mit Hilfe der vorliegenden Erfindung erhalten werden können (alle Angaben in Gewichtsteile fest gerechnet (atro Wirkstoff)):
1. BogenoffsetSome coating formulations are given below, which can be obtained with the aid of the present invention (all figures in parts by weight (atro active ingredient)): 1. Sheetfed offset
1.1 Boαenoffset-Einfachstrich1.1 Boαenoffset single line
70 Gew.-Teile handelsübliches CaCO3 (Typ 90)70 parts by weight of commercially available CaCO 3 (type 90)
30 Gew.-Teile handelsüblicher Clay (fein, z. B. US No. 1 ) 11 Gew.-Teile handelsüblicher Latex (Acrylat) 0,6 Gew.-Teile handelsübliche Carboxymethylcellulose (CMC) 0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin- Formaldehyd-, Epoxidharz)30 parts by weight of commercially available clay (fine, e.g. US No. 1) 11 parts by weight of commercial latex (acrylate) 0.6 parts by weight of commercial carboxymethyl cellulose (CMC) 0.8 parts by weight of commercial hardener (Urea-formaldehyde, melamine-formaldehyde, epoxy resin)
0,5 Gew.-Teile handelsüblicher Aufheller (Opt.) 0,5 Gew.-Teile handelsübliches Ca-Stearat0.5 part by weight of commercially available brightener (opt.) 0.5 part by weight of commercially available Ca stearate
Feststoffgehalt: 64 % Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Solids content: 64% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
1.2 Boαenoffset-Doppelstrich1.2 Boαenoffset double line
1.2.1 Boαenoffset-Vorstrich1.2.1 Boαenoffset-Vorstrich
100 Gew.-Teile handelsübliches CaCO3 (Typ 60 oder 75) 10 Gew.-Teile handelsüblicher Latex100 parts by weight of commercial CaCO 3 (type 60 or 75) 10 parts by weight of commercial latex
4 Gew.-Teile handelsübliche Stärke (native, oxidierte-, Mais- oder Kartoffelstärke) 0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin- Formaldehyd-, Epoxidharz) 0,5 Gew.-Teile handelsüblicher Aufheller (Opt.)
Feststoffgehalt: 66 %4 parts by weight of commercially available starch (native, oxidized, corn or potato starch) 0.8 parts by weight of commercially available hardener (urea-formaldehyde, melamine, formaldehyde, epoxy resin) 0.5 parts by weight of commercially available brightener ( Opt.) Solids content: 66%
Brookfield-Viskosität (100/min): 1.100 mPas pH-Wert: 9,0Brookfield viscosity (100 / min): 1,100 mPas pH: 9.0
1.2.2 Bogenoffset-Deckstrich1.2.2 Sheet offset top coat
70 Gew.-Teile handelsübliches CaCO3 (Typ 90) 30 Gew.-Teile handelsüblicher Clay (fein, z. B. US No. 1) 10 Gew.-Teile handelsüblicher Latex (Acrylat) 0,6 Gew.-Teile handelsübliche CMC70 parts by weight of commercial CaCO 3 (type 90) 30 parts by weight of commercial clay (fine, e.g. US No. 1) 10 parts by weight of commercial latex (acrylate) 0.6 parts by weight of commercial CMC
0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin-0.8 part by weight of commercially available hardener (urea-formaldehyde, melamine
Formaldehyd-, Epoxidharz)Formaldehyde, epoxy resin)
0,5 Gew.-Teile handelsüblicher Aufheller (Opt.)0.5 part by weight of commercially available brightener (opt.)
0,7 Gew.-Teile handelsübliches Ca-Stearat0.7 parts by weight of commercially available Ca stearate
Feststoffgehalt: 64 %Solids content: 64%
Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
2. Rollenoffset2. Web offset
2.1 LWC-Rollenoffset-Einfachstrich2.1 LWC web offset single line
50 Gew.-Teile handelsübliches CaCO3 (Typ 90) 50 Gew.-Teile handelsüblicher Clay (fein/ engl. Clay)50 parts by weight of commercially available CaCO 3 (type 90) 50 parts by weight of commercially available clay (fine / English clay)
2 Gew.-Teile handelsübliche Stärke (native, oxidierte-, Mais- oder Kartoffelstärke) 12 Gew.-Teile handelsüblicher Latex (XSB)2 parts by weight of commercial starch (native, oxidized, corn or potato starch) 12 parts by weight of commercial latex (XSB)
0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin- Formaldehyd-, Epoxidharz)
0,7 Gew.-Teile handelsüblicher Aufheller (Opt.) 0,5 Gew.-Teile handelsübliches Ca-Stearat0.8 part by weight of commercially available hardener (urea-formaldehyde, melamine-formaldehyde, epoxy resin) 0.7 part by weight of commercially available brightener (opt.) 0.5 part by weight of commercially available Ca stearate
Feststoffgehalt: 62 % Brookfield-Viskosität (100/min): 1.400 mPas pH-Wert: 8,5Solids content: 62% Brookfield viscosity (100 / min): 1,400 mPas pH: 8.5
2.2 Rollenoffset-Doppelstrich2.2 Web offset double line
2.2.1 Rollenoffset-Vorstrich2.2.1 Web offset primer
100 Gew.-Teile handelsübliches CaC03 (Typ 60 oder 75) 4 Gew.-Teile handelsübliche Stärke (native, oxidierte-, Mais- oder Kartoffelstärke) 12 Gew.-Teile handelsüblicher Latex (XSB) 0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin-100 parts by weight of commercial CaC0 3 (type 60 or 75) 4 parts by weight of commercial starch (native, oxidized, corn or potato starch) 12 parts by weight of commercial latex (XSB) 0.8 parts by weight of commercial Hardener (urea-formaldehyde, melamine
Formaldehyd-, Epoxidharz) 0,5 Gew.-Teile handelsüblicher Aufheller (Opt.)Formaldehyde, epoxy resin) 0.5 part by weight of commercially available brightener (opt.)
Feststoffgehalt: 66 % Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 9,0Solids content: 66% Brookfield viscosity (100 / min): 1,200 mPas pH: 9.0
2.2.2 Rollenoffset-Deckstrich2.2.2 Web offset top coat
60 Gew.-Teile handelsübliches CaCO3 (Typ 95)60 parts by weight of commercially available CaCO 3 (type 95)
40 Gew.-Teile handelsüblicher Clay (fein/ engl. Clay)40 parts by weight of commercially available clay (fine / English clay)
10 Gew.-Teile handelsüblicher Latex (XSB)10 parts by weight of commercially available latex (XSB)
0,6 Gew.-Teile handelsübliche CMC0.6 parts by weight of commercially available CMC
0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin-
Formaldehyd-, Epoxidharz)0.8 part by weight of commercially available hardener (urea-formaldehyde, melamine Formaldehyde, epoxy resin)
0,5 Gew.-Teile handelsüblicher Aufheller (Opt.)0.5 part by weight of commercially available brightener (opt.)
0,5 Gew.-Teile handelsübliches Ca-Stearat0.5 part by weight of commercially available Ca stearate
Feststoffgehalt: 64 %Solids content: 64%
Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
3. Tiefdruck3. Gravure printing
3.1 LWC-Tiefdruck-Einfachstrich3.1 LWC gravure single line
70 Gew.-Teile handelsüblicher Clay (normal/engl. Clay) 30 Gew.-Teile handelsübliches Talkum 5,0 Gew.-Teile handelsüblicher Latex (Acrylat-Alleinbinder) 0,2 Gew.-Teile handelsüblicher Verdicker (synth.) 1 ,0 Gew.-Teile handelsübliches Ca-Stearat70 parts by weight of commercial clay (normal / English clay) 30 parts by weight of commercial talc 5.0 parts by weight of commercial latex (acrylate sole binder) 0.2 parts by weight of commercial thickener (synth.) 1, 0 parts by weight of commercially available Ca stearate
Feststoffgehalt: 58 % Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Solids content: 58% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
3.2 Tiefdruck-Doppelstrich3.2 Intaglio double line
3.2.1 Tiefdruck-Vorstrich3.2.1 Gravure primer
100 Gew.-Teile handelsüblicher CaCO3 (Typ 75)100 parts by weight of commercially available CaCO 3 (type 75)
6,0 Gew.-Teile handelsüblicher Latex (Acrylat-Alleinbinder)6.0 parts by weight of commercially available latex (acrylate sole binder)
0,3 Gew.-Teile handelsüblicher Verdicker (synth.)
0,5 Gew.-Teile handelsübliches Ca-Stearat0.3 part by weight of commercially available thickener (synth.) 0.5 part by weight of commercially available Ca stearate
Feststoffgehalt: 66 %Solids content: 66%
Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 9,0Brookfield viscosity (100 / min): 1,200 mPas pH: 9.0
3.2.2 Tiefdruck-Deckstrich3.2.2 Rotogravure top coat
85 Gew.-Teile handelsüblicher Clay (engl. Clay) 15 Gew.-Teile handelsüblicher Clay (calcinierter Clay)85 parts by weight of commercially available clay 15 parts by weight of commercially available clay (calcined clay)
5,0 Gew.-Teile handelsüblicher Latex (Acrylat-Alleinbinder) 0,2 Gew.-Teile handelsüblicher Verdicker (synth.) 0,8 Gew.-Teile handelsübliches Ca-Stearat5.0 parts by weight of commercially available latex (acrylate sole binder) 0.2 parts by weight of commercially available thickener (synth.) 0.8 parts by weight of commercially available Ca stearate
Feststoffgehalt: 57 %Solids content: 57%
Brookfield-Viskosität (100/min): 1.300 mPas pH-Wert: 8,5Brookfield viscosity (100 / min): 1,300 mPas pH: 8.5
4. Karton4. Carton
4.1 Karton-Doppelstrich4.1 Cardboard double line
4.1.1 Karton-Vorstrich4.1.1 Cardboard primer
100 Gew.-Teile handelsübliches CaCO3 (Typ 75)100 parts by weight of commercially available CaCO 3 (type 75)
3 Gew.-Teile handelsübliche Stärke (native, oxidierte-, Mais- oder Kartoffelstärke) 14 Gew.-Teile handelsüblicher Latex (XSB)3 parts by weight of commercial starch (native, oxidized, corn or potato starch) 14 parts by weight of commercial latex (XSB)
0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin- Formaidehyd-, Epoxidharz)
0,5 Gew.-Teile handelsüblicher Aufheller (Opt.)0.8 part by weight of commercially available hardener (urea-formaldehyde, melamine, formaldehyde, epoxy resin) 0.5 part by weight of commercially available brightener (opt.)
Feststoffgehalt: 66 %Solids content: 66%
Brookfield-Viskosität (100/min): 1.000 mPas pH-Wert: 9,0Brookfield viscosity (100 / min): 1,000 mPas pH: 9.0
4.1.2 Karton-Deckstrich4.1.2 Cardboard top coat
50 Gew.-Teile handelsübliches CaCO3 (Typ 90) 50 Gew.-Teile handelsüblicher Clay (fein/ engl. Clay)50 parts by weight of commercially available CaCO 3 (type 90) 50 parts by weight of commercially available clay (fine / English clay)
13 Gew.-Teile handelsüblicher Latex (Acrylat) 2 Gew.-Teile handelsüblicher Cobinder (Acrylat)13 parts by weight of commercially available latex (acrylate) 2 parts by weight of commercial cobinder (acrylate)
0,8 Gew.-Teile handelsüblicher Härter (Harnstoff-Formaldehyd-, Melamin-0.8 part by weight of commercially available hardener (urea-formaldehyde, melamine
Formaldehyd-, Epoxidharz) 0,6 Gew.-Teile handelsübliches Ca-StearatFormaldehyde, epoxy resin) 0.6 parts by weight of commercially available Ca stearate
Feststoffgehalt: 60 %Solids content: 60%
Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
5. Spezialpapier5. Special paper
5.1 Etiketten5.1 labels
70 Gew.-Teile handelsüblicher Clay (normal/engl. Clay) 10 Gew.-Teile handelsübliches TiO2 (Rutil) 20 Gew.-Teile handelsübliches CaCO3 (Typ 90) 16 Gew.-Teile handelsüblicher Latex (XSB) 0,5 Gew.-Teile handelsüblicher Härter (EH) (Hamstoff-Formaldehyd-, Melamin-
Formaldehyd-, Epoxidharz)70 parts by weight of commercial clay (normal / English clay) 10 parts by weight of commercial TiO 2 (rutile) 20 parts by weight of commercial CaCO 3 (type 90) 16 parts by weight of commercial latex (XSB) 0.5 Parts by weight of commercially available hardener (urea-formaldehyde, melamine Formaldehyde, epoxy resin)
0,6 Gew.-Teile handelsübliches Ca-Stearat0.6 parts by weight of commercially available Ca stearate
Feststoffgehalt: 60 % Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Solids content: 60% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
5.2 Flexible Verpackung5.2 Flexible packaging
80 Gew.-Teile handelsüblicher Clay (normal/engl. Clay)80 parts by weight of commercially available clay (normal / English clay)
20 Gew.-Teile handelsübliches CaC03 (Typ 90)20 parts by weight of commercially available CaC0 3 (type 90)
14 Gew.-Teile handelsüblicher Latex (Acrylat)14 parts by weight of commercially available latex (acrylate)
0,8 Gew.-Teile handelsübliche CMC0.8 parts by weight of commercially available CMC
0,5 Gew.-Teile handelsüblicher Härter (Hamstoff-Formaldehyd-, Metamin- Formaldehyd-, Epoxidharz)0.5 part by weight of commercially available hardener (urea-formaldehyde, metamine-formaldehyde, epoxy resin)
0,6 Gew.-Teile handelsüblicher Aufheller (Opt.)0.6 parts by weight of commercially available brighteners (opt.)
1 ,0 Gew.-Teile handelsübliches Ca-Stearat1.0 part by weight of commercially available Ca stearate
Feststoffgehalt: 58 % Brookfield-Viskosität (100/min): 1.200 mPas pH-Wert: 8,5Solids content: 58% Brookfield viscosity (100 / min): 1,200 mPas pH: 8.5
Die erfindungsgemäße Prozeßdurchführung in einer üblichen Papierfabrik kann wie folgt beschrieben werden:The process implementation according to the invention in a conventional paper mill can be described as follows:
Silos in einer beliebigen Größe, beispielsweise von 50 bis 1000 m3 dienen zur Aufnahme und Lagerung von trockenen Füllstoffen und Pigmenten einer einheitlichen oder gegebenenfalls unterschiedlichen Grundkörnung, beispielsweise Calciumcarbonat. Durch Dosiervorrichtungen wird ein Austrag des Füllstoff-
und/oder Pigmentpulvers mit anschließendem Transport gewährleistet, gegebenenfalls zu Tagessilobehälter(n), gegebenenfalls mit Reinigungsvorrichtungen. Dosierungsvorrichtungen für das/die Pulver, gegebenenfalls gesteuert durch speicherprogrammierbare Steuerungen (SPS) mit den elektronisch integrierten Rezepten bestimmen gravimetrisch und/oder volumetrisch die zur Vermischung mit Wasser, Frischwasser oder Kreislaufwasser der Papierfabrik erforderlichen Mengen der zu mischenden Bestandteile. Erfindungsgemäß wird anstelle des Frischwassers oder des Kreislaufwassers teilweise oder vollständig ein Restwasserschlamm mit einem Feststoffgehalt von insbesondere 0,02 bis 50 Gew.- %, gegebenenfalls unter Zugabe von Wasser bei höherer Konzentration desSilos of any size, for example from 50 to 1000 m 3, are used to hold and store dry fillers and pigments with a uniform or possibly different basic grain size, for example calcium carbonate. Dosing devices discharge the filler and / or pigment powder with subsequent transport, if necessary to day silo container (s), if necessary with cleaning devices. Dosing devices for the powder (s), possibly controlled by programmable logic controllers (PLC) with the electronically integrated recipes, determine gravimetrically and / or volumetrically the quantities of the components to be mixed, which are required for mixing with water, fresh water or circulating water from the paper mill. According to the invention, instead of the fresh water or the circulating water, a residual water sludge with a solids content of in particular 0.02 to 50% by weight is partially or completely, optionally with the addition of water at a higher concentration of
Restwasserschlamms eingesetzt. Dementsprechend sind weiterhin erforderlich, Behälter zur Lagerung des Restwasserrschlamms, Dosiervorrichtungen für den Restwasserschlamm, die die einzusetzende Menge gravimetrisch oder volumetrisch bestimmen. Daneben sind erforderlich Behälter zur Aufnahme des Gemisches aus Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry und Restwasserschlamm/Wasser, gegebenenfalls Mahlhilfsmittel und Dispergierhilfsmittel oder sonstige Hilfsmittel. Zur Dispergierung und Stabilitätseinstellung sind Dispergiereinrichtungen (Dissolver) oder sonstige Rührwerke erforderlich.Residual water sludge used. Accordingly, containers for storing the residual water sludge, dosing devices for the residual water sludge, which determine the amount to be used gravimetrically or volumetrically, are also required. In addition, containers are required to hold the mixture of fresh pigment or filler as a powder, slurry containing fresh pigment and / or filler and residual water sludge / water, optionally grinding aids and dispersing aids or other aids. Dispersing devices (dissolvers) or other agitators are required for dispersion and stability adjustment.
Das Vermählen der Frischpigmente und/oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry mit den Restwasserschlämmen, kann erfindungsgemäß kontinuierlich in üblichen Rührwerkskugelmühlen, beispielsweise mit einem Inhalt von 700 bis 5000 I oder größer durchgeführt werden. Zum Einsatz kommen Mahlmedien, vorzugsweise Mahlkugeln, insbesondere mit einem Durchmesser von 1 bis 4 mm.The grinding of the fresh pigments and / or fresh fillers as powder, fresh-pigment-containing and / or fresh-filler-containing slurry with the residual water slurries can be carried out continuously according to the invention in conventional stirred ball mills, for example with a content of 700 to 5000 l or greater. Grinding media, preferably grinding balls, in particular with a diameter of 1 to 4 mm, are used.
Zur Aufbereitung der Restwasserschlämme werden üblicherweise Siebe, vorzugsweise Bogensiebe zum Abscheiden von Verunreinigungen (Kugelbruch, Trenn-
Stoffe, Rost etc.) eingesetzt. Lasermeßinstrumente dienen der Bestimmung und Steuerung der Mahlfeinheit während des Mahlvorgangs und der Rechner-gestütz- ten Steuerung der Rührwerkskugelmühlenanlage. Gegebenenfalls sind weitere Dosierinjektionseinrichtungen zum Nachdosieren von Dispergier- und Mahlhilfs- mittein an der Rührwerkskugelmühle erforderlich. Nach dem Austrag der Pigment- Slurry sind gegebenenfalls Siebe zur nochmaligen Trennung von Schadstoffen mit einer Größe von mehr als 20 μm erforderlich. Typischerweise weist das eingesetzte Frischpigment- und/oder Füllstoffmaterial, insbesondere eingesetzes Calciumcarbonatpulver in trockener Form einen Weißgrad nach DIN 53163 von mehr als 90 %, insbesondere einen Weißgrad von mehr als 95 % in einer Feinheit von d97 < 25 μm, eine Feinheit nicht größer d97 100 μm, eine Reinheit des Carbonats ≥ 98 %, einen Anteil SiO2 < 1 ,0, insbesondere < 0,2% auf.To process the residual water sludge, sieves are usually used, preferably curved sieves for separating contaminants (broken balls, separating Fabrics, rust, etc.). Laser measuring instruments are used to determine and control the fineness of grinding during the grinding process and the computer-aided control of the agitator ball mill system. If necessary, further dosing injection devices are required for the subsequent dosing of dispersing and grinding aids on the agitator ball mill. After the pigment slurry has been discharged, sieves may be required for the further separation of pollutants with a size of more than 20 μm. Typically, the fresh pigment and / or filler material used, in particular calcium carbonate powder used in dry form, has a whiteness according to DIN 53163 of more than 90%, in particular a whiteness of more than 95% in a fineness of d 97 <25 μm, a fineness not greater d 97 100 μm, a purity of the carbonate ≥ 98%, a proportion of SiO 2 <1.0, in particular <0.2%.
Wechselnde Anteile von beispielsweise Carbonat, vermischt mit Restwasser- schlämm werden zu einer Slurry vermählen, die einen Feststoffgehalt aufweist, der beispielsweise auf eine gebrauchsfähige Streichfarbe eingestellt werden kann. Gegebenenfalls ist der Feststoffgehalt auch höher einstellbar, wenn die Pigment- Slurry länger zwischengelagert werden soll. Die Feinheit der Slurry wird insbesondere durch die Verweiizeit und/oder die Energieaufnahme während der Produktion in der Rührwerkskugelmühle bestimmt.Varying proportions of carbonate, for example, mixed with residual water slurry are ground to a slurry which has a solids content which can be adjusted, for example, to a usable coating color. If necessary, the solids content can also be set higher if the pigment slurry is to be stored for a longer period. The fineness of the slurry is determined in particular by the dwell time and / or the energy consumption during production in the agitator ball mill.
Der Weißgrad der Pigment-Slurry ergibt sich unter anderem aus dem Mischungsverhältnis Frischpigment zu Restwasserschlamm und insbesondere dem eingesetzten Frischpigmenttyp.The whiteness of the pigment slurry results, among other things, from the mixing ratio of fresh pigment to residual water sludge and, in particular, the type of fresh pigment used.
Eine Ausführungsform der Zusammensetzung der Restwasserschlämme, wie sie erfindungsgemäß eingesetzt werden können, ist nachfolgend in der Tabelle 1 wiedergegeben:
Tabelle 1An embodiment of the composition of the residual water sludge, as can be used according to the invention, is shown in Table 1 below: Table 1
MgO % 2,15MgO% 2.15
Al203 % 24,38Al 2 0 3 % 24.38
Si02 % 29,84Si0 2 % 29.84
P205 % 0,81P 2 0 5 % 0.81
CaO % 27,26CaO% 27.26
Ti02 % 0,20Ti0 2 % 0.20
V205 % <0,01V 2 0 5 % <0.01
Cr2O3 % 0,01Cr 2 O 3 % 0.01
MnO % 0,01MnO% 0.01
Na2O % 0,29 κ2o % 0,82Na 2 O% 0.29 κ 2 o% 0.82
Fe2O3 % 0,54Fe 2 O 3 % 0.54
SO4 % 0,14SO 4 % 0.14
Cl % 0,01Cl% 0.01
NiO % <0,01NiO% <0.01
CuO % 0,02CuO% 0.02
ZnO % 0,01ZnO% 0.01
Ga2O3 % <0,01Ga 2 O 3 % <0.01
SrO % 0,02SrO% 0.02
ZrO2 % 0,01ZrO 2 % 0.01
PbO % 0,02PbO% 0.02
BaO % 0,06BaO% 0.06
Glühverlust % 13,40Loss on ignition% 13.40
Summe % 100,00
Ein Abwasserschlamm mit der in Tabelle 1 dargestellten Zusammensetzung wurde getrocknet; die Feinheit und der Farbwert gemessen.Total% 100.00 A sewage sludge having the composition shown in Table 1 was dried; the fineness and the color value measured.
Die gefundenen Werte lauten:The values found are:
Feinheit: (Cilas 850)Fineness: (Cilas 850)
D50-Wert = 15,0 μmD 50 value = 15.0 μm
D32-Wert = 1 ,0 μmD 32 value = 1.0 μm
Weißgrad:Whiteness:
(Helligkeit Ryι C/2° DIN 53163)(Brightness R yι C / 2 ° DIN 53163)
Ry-Wert = 84,1 Gelbwert: (C/2°) = -5,6R y value = 84.1 yellow value: (C / 2 °) = -5.6
Der Wassergehalt des Abwasserschlamms betrug 19,5 %. Der pH-Wert wurde in einer 10 %igen Lösung gemessen und betrug 6,8. Ein Teil des getrockneten Abwasserschlamms wurde 2 Stunden bei 450°C erhitzt. Der Glühverlust (organische Anteile) betrug 13,4%.The water content of the sewage sludge was 19.5%. The pH was measured in a 10% solution and was 6.8. A portion of the dried sewage sludge was heated at 450 ° C for 2 hours. The loss on ignition (organic proportions) was 13.4%.
Im Labormaßstab wurde anschließend der Abwasserschlamm zu 40 Gew.-% mit 60 Gew.-% Frischpigment Calcicell®, einem natürlichen, kristallinen Calciumcarbonat (Korngrößenbereich 0 - 20 μm, Dgo-Wert = 5,5 μm, Weißgrad C/2° DIN 53163 = 95 ±1 ) aufgeschlämmt und in der Mühle kurz vermählen.On a laboratory scale, then the waste water sludge to 40 wt .-% with 60 wt .-% of fresh pigment Calcicell ®, a natural, crystalline by weight calcium carbonate (particle size range 0 - .mu.m 20 Dgo value = 5.5 .mu.m, whiteness C / 2 ° to DIN 53163 = 95 ± 1) slurried and grind briefly in the mill.
Danach wurde am vermahlenen und getrockneten Produkt die Feinheit und der
Farbwert gemessen.Then the fineness and the Color value measured.
Die gefundenen Werte lauten:The values found are:
Feinheit: (Cilas 850) D50-Wert = 9,2 μm D9-Wert = 1 ,0 μmFineness: (Cilas 850) D 50 value = 9.2 μm D 9 value = 1.0 μm
Der Weißgrad (Helligkeit Ry, C/2° DIN 53163) nach der Vermahlung betrug:The degree of whiteness (brightness R y , C / 2 ° DIN 53163) after grinding was:
Ry-Wert = 92,0 Gelbwert: (C/2°) = -2,6R y value = 92.0 yellow value: (C / 2 °) = -2.6
(Alle genannten Feinheitsmerkmale wurden durch Lagersedimentationsanalyse mit dem Gerät Cilas 850 der Firma Cilas, Frankreich, bestimmt. Die Dispergierung der Proben in Alkohol wurde mittels Schnellrührer und Ultraschall vorgenommen.)
(All the fineness characteristics mentioned were determined by storage sedimentation analysis using the Cilas 850 from Cilas, France. The samples were dispersed in alcohol using a high-speed stirrer and ultrasound.)
Claims
1. Verfahren zur Wiederverwertung von Füllstoffen und Streichpigmenten der 5 Papier-, Pappe- und Kartonherstellung aus den Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen Kläranlagen oder Abscheidevorrichtungen, dadurch gekennzeichnet, daß man die Füllstoff- und Streichpigment-haltigen Restwasserschlämme der Vermischung und anschließend der Vermahlung zu einer Pigment-Slurry mit o Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry zuführt.1. Process for recycling fillers and coating pigments of the 5 paper, cardboard and cardboard production from the residual water sludges from the coating waste water, deinking plants, internal sewage treatment plants or separators, characterized in that the filler and coating pigment-containing residual water sludges of the mixing and then the grinding to a pigment slurry with o fresh pigment or fresh filler as a powder, fresh pigment-containing and / or fresh filler-containing slurry.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man Restwasserschlämme einsetzt, die ein Verhältnis von Faseranteil zu Füllstoff- 5 und/oder Pigmentanteil von 2 bis 98 Gew.-% zu 98 bis 2 Gew.-% aufweisen.2. The method according to claim 1, characterized in that residual water sludges are used which have a ratio of fiber content to filler 5 and / or pigment content of 2 to 98 wt .-% to 98 to 2 wt .-%.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man die Restwasserschlämme von Deinkinganlagen, innerbetrieblichen Kläranlagen 0 und Abscheidevorrichtungen einer Faserabtrennung unterwirft.3. The method according to claim 1, characterized in that the residual water sludge from deinking plants, internal sewage treatment plants 0 and separating devices is subjected to a fiber separation.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man die Faserabtrennung durch Flockung und Sedimentation, Filtrierung, Siebung, Zentrifugierung und/oder chemisches Behandeln, insbesondere Oxidation 5 durchführt.4. The method according to claim 3, characterized in that one carries out the fiber separation by flocculation and sedimentation, filtration, sieving, centrifugation and / or chemical treatment, in particular oxidation 5.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Restwasserschlämme mit einer Feststoffkonzentration von 0,02 Gew.-% bis 50 Gew.-%, insbesondere 1 Gew.-% bis 30 Gew.-% einsetzt.5. The method according to one or more of claims 1 to 4, characterized in that the residual water sludge with a solids concentration of 0.02 wt .-% to 50 wt .-%, in particular 1 wt .-% to 30 wt .-% uses.
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Restwasserschlämme mit einer Konzen- tration an Füllstoffen und/oder Streichpigmenten in einer Menge von 2 bis6. The method according to one or more of claims 1 to 5, characterized in that the residual water sludge with a concentration of fillers and / or coating pigments in an amount of 2 to
80 Gew.-%, insbesondere 20 bis 60 Gew.-%, bezogen auf den Feststoffgehalt einsetzt.80 wt .-%, in particular 20 to 60 wt .-%, based on the solids content.
7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man als Frischpigment und/oder Frischfüllstoff Kaolin, natürliche oder gefällte Calciumcarbonate, künstliche oder natürliche Aluminiumsilikate und -oxidhydrate, Titandioxid, Satin-Weiß, Dolomit, Glimmer, Metall-, insbesondere Aluminiumflakes, Bentonit, Rutil, Magnesiumhydroxid, Gips, Schichtsilikate, Talkum, Calciumsilikat sowie sonstige Steine und Erden einsetzt.7. The method according to one or more of claims 1 to 6, characterized in that as fresh pigment and / or fresh filler kaolin, natural or precipitated calcium carbonates, artificial or natural aluminum silicates and oxide hydrates, titanium dioxide, satin white, dolomite, mica, metal -, in particular aluminum flakes, bentonite, rutile, magnesium hydroxide, gypsum, layered silicates, talc, calcium silicate and other stones and soils.
8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries in Anwesenheit der Restwasserschlämme und gegebenenfalls üblichen Mahlhilfsmitteln und/oder Dispergierhilfsmitteln zu einer Slurry mit einem Feststoffgehalt von 30 bis 85 Gew.-%, insbesondere 40 bis 75 Gew.-% vermischt und vermahlt.8. The method according to one or more of claims 1 to 7, characterized in that fresh pigment or filler as a powder, fresh pigment-containing and / or fresh filler-containing slurries in the presence of the residual water sludge and, if appropriate, conventional grinding aids and / or dispersing aids to form a slurry with a solids content of 30 up to 85 wt .-%, in particular 40 to 75 wt .-% mixed and ground.
9. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries zu einer Korngrößenverteilung von 10 bis 99 Gew.-% an Teilchen <1 μm, insbesondere9. The method according to one or more of claims 1 to 8, characterized in that fresh pigments or fresh fillers as powder, fresh pigment-containing and / or fresh filler-containing slurries to a particle size distribution of 10 to 99% by weight of particles <1 μm, in particular
10 bis 95 Gew.-% an Teilchen <1 μm, jeweils bezogen auf den Äquivalentdurchmesser vermahlt.10 to 95% by weight of particles <1 μm, each based on the equivalent diameter, ground.
10. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries zu einer Korngrößenverteilung von a) 95 bis 100 Gew.-% an Teilchen <10 μm b) 50 bis 100 Gew.-% an Teilchen < 2 μm, insbesondere 50 bis 95 Gew.-% an Teilchen < 2 μm c) 27 bis 95 Gew.-% an Teilchen < 1 μm, insbesondere 27 bis 75 Gew.-% an Teilchen < 1 μm und d) 0,1 bis 55 Gew.-% an Teilchen < 0,2 μm, insbesondere 0,1 bis 35 Gew.- % an Teilchen < 0,2 μm, jeweils bezogen auf den Äquivalentdurchmesser der Teilchen.10. The method according to one or more of claims 1 to 8, characterized in that fresh pigments or fresh fillers as powder, fresh pigment-containing and / or fresh filler-containing slurries to a particle size distribution of a) 95 to 100 wt .-% of particles <10 microns b) 50 to 100% by weight of particles <2 μm, in particular 50 to 95% by weight of particles <2 μm c) 27 to 95% by weight of particles <1 μm, in particular 27 to 75% by weight Particles <1 μm and d) 0.1 to 55% by weight of particles <0.2 μm, in particular 0.1 to 35% by weight of particles <0.2 μm, in each case based on the equivalent diameter of the particles.
11. Verfahren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß man den Weißgrad der Pigment-Slurries durch das Mengenverhältnis von gemahlenem oder ungemahlenem Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige oder frischfüllstoffhaltige Slurries zu Restwasserschlamm einstellt.11. The method according to one or more of claims 1 to 10, characterized in that the whiteness of the pigment slurries is adjusted by the ratio of ground or unground fresh pigment or fresh filler as a powder, fresh pigment-containing or fresh filler-containing slurries to residual water sludge.
12. Verfahren einem oder mehreren der Ansprüche 1 bis 11 , dadurch gekenn- zeichnet, daß man den Weißgrad der Pigment-Slurries durch Auswahl der chemischen Reinheit, insbesondere des Weißgrades und/oder des Gelbwertes der Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries einstellt. 12. The method one or more of claims 1 to 11, characterized in that the degree of whiteness of the pigment slurries by selecting the chemical purity, in particular the degree of whiteness and / or the yellowness of the fresh pigments or fillers as a powder, fresh pigment-containing and / or slurries containing fresh filler.
13. Verwendung einer Pigment-Slurry nach einem oder mehreren der vorhergehenden Ansprüche zur Herstellung einer Streichmasse für die Papierindustrie, insbesondere von Streichmassen für verschiedene Segmente, wie Bogenoffset, Rollenoffset, Tiefdruck, Karton und Spezialpapiere.13. Use of a pigment slurry according to one or more of the preceding claims for producing a coating slip for the paper industry, in particular coating slips for different segments, such as sheetfed offset, web offset, gravure printing, cardboard and special papers.
14. Verwendung nach Anspruch 13, zur Herstellung von üblichen Streichmassen in teilweisem oder vollständigem Austausch der Streichpigmente.14. Use according to claim 13, for the production of conventional coating slips in partial or complete exchange of the coating pigments.
15. Verwendung einer Pigment-Slurry nach einem oder mehreren der An- sprüche 1 bis 11 für den Masseeinsatz bei der Papierherstellung. 15. Use of a pigment slurry according to one or more of claims 1 to 11 for mass use in papermaking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI9730180T SI0910697T1 (en) | 1996-07-09 | 1997-03-19 | Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19627523 | 1996-07-09 | ||
| DE19627523A DE19627523C1 (en) | 1996-07-09 | 1996-07-09 | Preparation of filler or pigment coating material for paper, pulp or board from waste sludge |
| PCT/EP1997/001375 WO1998001621A1 (en) | 1996-07-09 | 1997-03-19 | Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0910697A1 true EP0910697A1 (en) | 1999-04-28 |
| EP0910697B1 EP0910697B1 (en) | 2001-07-04 |
Family
ID=7799271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97915390A Expired - Lifetime EP0910697B1 (en) | 1996-07-09 | 1997-03-19 | Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture |
Country Status (19)
| Country | Link |
|---|---|
| US (3) | US6214166B1 (en) |
| EP (1) | EP0910697B1 (en) |
| JP (1) | JP4046764B2 (en) |
| CN (1) | CN1120262C (en) |
| AT (1) | ATE202810T1 (en) |
| AU (1) | AU2288997A (en) |
| BR (1) | BR9710866A (en) |
| CA (1) | CA2250475C (en) |
| CZ (1) | CZ298816B6 (en) |
| DE (2) | DE19627523C1 (en) |
| DK (1) | DK0910697T3 (en) |
| ES (1) | ES2160936T3 (en) |
| GR (1) | GR3036174T3 (en) |
| HU (1) | HU221442B (en) |
| NO (1) | NO324375B1 (en) |
| PL (1) | PL187463B1 (en) |
| PT (1) | PT910697E (en) |
| TR (1) | TR199900012T2 (en) |
| WO (1) | WO1998001621A1 (en) |
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| AT501868B1 (en) | 2005-06-13 | 2007-04-15 | Andritz Ag Maschf | METHOD FOR THE RECYCLING OF FILLERS AND PIGMENTS OF PAPER, PAPER OR CARTON MANUFACTURING |
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| JP5468281B2 (en) * | 2009-03-24 | 2014-04-09 | 大王製紙株式会社 | Method for producing regenerated particles |
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-
1996
- 1996-07-09 DE DE19627523A patent/DE19627523C1/en not_active Expired - Lifetime
-
1997
- 1997-03-19 TR TR1999/00012T patent/TR199900012T2/en unknown
- 1997-03-19 JP JP50468698A patent/JP4046764B2/en not_active Expired - Fee Related
- 1997-03-19 HU HU9903637A patent/HU221442B/en not_active IP Right Cessation
- 1997-03-19 CZ CZ0002299A patent/CZ298816B6/en not_active IP Right Cessation
- 1997-03-19 PL PL97331011A patent/PL187463B1/en unknown
- 1997-03-19 WO PCT/EP1997/001375 patent/WO1998001621A1/en active IP Right Grant
- 1997-03-19 BR BR9710866-9A patent/BR9710866A/en not_active IP Right Cessation
- 1997-03-19 AU AU22889/97A patent/AU2288997A/en not_active Abandoned
- 1997-03-19 CA CA002250475A patent/CA2250475C/en not_active Expired - Lifetime
- 1997-03-19 PT PT97915390T patent/PT910697E/en unknown
- 1997-03-19 EP EP97915390A patent/EP0910697B1/en not_active Expired - Lifetime
- 1997-03-19 AT AT97915390T patent/ATE202810T1/en active
- 1997-03-19 ES ES97915390T patent/ES2160936T3/en not_active Expired - Lifetime
- 1997-03-19 DE DE59703962T patent/DE59703962D1/en not_active Expired - Lifetime
- 1997-03-19 DK DK97915390T patent/DK0910697T3/en active
- 1997-03-19 CN CN97196175A patent/CN1120262C/en not_active Expired - Lifetime
-
1999
- 1999-01-08 NO NO19990074A patent/NO324375B1/en not_active IP Right Cessation
- 1999-01-08 US US09/227,533 patent/US6214166B1/en not_active Expired - Lifetime
-
2000
- 2000-12-21 US US09/741,023 patent/US6444092B1/en not_active Expired - Lifetime
-
2001
- 2001-07-05 GR GR20010401005T patent/GR3036174T3/en not_active IP Right Cessation
-
2002
- 2002-07-15 US US10/193,902 patent/US7887629B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
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| See references of WO9801621A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9710866A (en) | 2000-01-11 |
| ES2160936T3 (en) | 2001-11-16 |
| JP4046764B2 (en) | 2008-02-13 |
| CZ298816B6 (en) | 2008-02-13 |
| CN1120262C (en) | 2003-09-03 |
| US6444092B1 (en) | 2002-09-03 |
| NO990074L (en) | 1999-01-08 |
| US20020088587A1 (en) | 2002-07-11 |
| US7887629B2 (en) | 2011-02-15 |
| HU221442B (en) | 2002-10-28 |
| PL187463B1 (en) | 2004-07-30 |
| GR3036174T3 (en) | 2001-10-31 |
| JP2000514510A (en) | 2000-10-31 |
| PT910697E (en) | 2001-10-30 |
| US20030041990A1 (en) | 2003-03-06 |
| CN1225144A (en) | 1999-08-04 |
| HUP9903637A2 (en) | 2000-03-28 |
| US6214166B1 (en) | 2001-04-10 |
| HUP9903637A3 (en) | 2001-04-28 |
| WO1998001621A1 (en) | 1998-01-15 |
| NO324375B1 (en) | 2007-10-01 |
| DK0910697T3 (en) | 2001-09-24 |
| TR199900012T2 (en) | 1999-04-21 |
| PL331011A1 (en) | 1999-06-21 |
| AU2288997A (en) | 1998-02-02 |
| ATE202810T1 (en) | 2001-07-15 |
| DE19627523C1 (en) | 1997-10-23 |
| NO990074D0 (en) | 1999-01-08 |
| CA2250475A1 (en) | 1998-01-15 |
| DE59703962D1 (en) | 2001-08-09 |
| EP0910697B1 (en) | 2001-07-04 |
| CA2250475C (en) | 2005-12-27 |
| CZ2299A3 (en) | 1999-06-16 |
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