EP1825056B1 - Bentonite for binding impurities during paper production - Google Patents
Bentonite for binding impurities during paper production Download PDFInfo
- Publication number
- EP1825056B1 EP1825056B1 EP05826382.3A EP05826382A EP1825056B1 EP 1825056 B1 EP1825056 B1 EP 1825056B1 EP 05826382 A EP05826382 A EP 05826382A EP 1825056 B1 EP1825056 B1 EP 1825056B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bentonite
- pulp
- cec
- fiber suspension
- weight
- 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.)
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Links
- 229910000278 bentonite Inorganic materials 0.000 title claims description 79
- 239000000440 bentonite Substances 0.000 title claims description 79
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims description 79
- 239000012535 impurity Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims description 50
- 150000001768 cations Chemical class 0.000 claims description 35
- 239000000725 suspension Substances 0.000 claims description 30
- 229920001131 Pulp (paper) Polymers 0.000 claims description 27
- 239000000454 talc Substances 0.000 claims description 20
- 229910052623 talc Inorganic materials 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 13
- 238000005341 cation exchange Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000012216 bentonite Nutrition 0.000 description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000000356 contaminant Substances 0.000 description 16
- 235000012222 talc Nutrition 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 11
- 239000004927 clay Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 229910000281 calcium bentonite Inorganic materials 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 238000000684 flow cytometry Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 150000003626 triacylglycerols Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229930182558 Sterol Natural products 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003432 sterols Chemical class 0.000 description 3
- 235000003702 sterols Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 241000005308 Orsa Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- FCSQOYVFTFXVDZ-UHFFFAOYSA-N [Ca].[Mg].[K].[Na].[Li] Chemical compound [Ca].[Mg].[K].[Na].[Li] FCSQOYVFTFXVDZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 238000009300 dissolved air flotation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010875 treated wood Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
-
- 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
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Definitions
- the present invention relates to the use of specific bentonites having a high cation exchange capacity in the binding or removal of impurities in papermaking.
- Disturbance removal or binding in papermaking is becoming increasingly important.
- the problem is also based on the fact that the paper obtained in the production of water is recycled, with impurities gradually accumulate in it.
- These contaminants can thus lead to a wide variety of product failures, such as the formation of deposits on the rolls of the paper machine, the gluing of the screens, etc. These effects lead to interruptions in the paper production.
- Most of the relevant contaminants are negatively charged. These are, for example Humic acids, tree resin colloids, lingin derivatives, lignosulfonates, which are introduced from the fibers into the paper cycle.
- anionic impurities which are introduced into the paper machine by recycling paper broke. This paper break is typically redispersed and introduced into the paper machine. As a result, the ingredients and aids contained in it are completely recycled. In addition, eg carboxymethylcelluloses, polyacrylates, polyphosphonates and silicates are registered. Other anionic charged impurities are the latices used in the paper coating which, while typically hydrophobic, also carry anionic charges. These strongly tend to agglomerate, whereby the agglomerates are deposited as sticky, white residues on the paper machine (so-called white pitch).
- a method for reducing the impurities in papermaking is described.
- a particulate composition containing (a) a water-soluble cationic polymer coated on (b) a substantially water-insoluble particulate substrate is used.
- the polymer should be sufficiently electropositive so that the particulate composition has a zeta potential of at least about +30 mV.
- the polymer is preferably a poly (dialkyldialylammonium halide).
- the substrate is, for example, a phyllosilicate mineral.
- the EP 0 760 406 A2 a combination of a poly (dadmac / acrylamide) and a bentonite in impurity binding.
- a smectite clay for impurity control wherein the smectite clay is modified as follows: monovalent exchangeable cations are present in an equivalent ion content in the range of 0.20 to 0.60; a first type of bivalent exchangeable cations is present in an equivalent ion content in the range of 0.40 to 0.80; and a second type of bivalent exchangeable cations is present in an equivalent ion content in the range of 0.00 to 0.20, the first type of bivalent exchangeable cations comprising calcium and the second type of bivalent exchangeable cations comprising magnesium.
- An object of the present invention was therefore to provide an improved process for impurity binding in papermaking, in which a simple and inexpensive to produce means can be used and which enables a high degree of impurity binding, even of hydrophobic moieties.
- this object is achieved by the method according to claim 1.
- impurities are understood here as meaning both sticky substances, which are also referred to in the literature as “adhesives” or “stickies”, and the so-called “pitch”, ie primarily tree resin components.
- adheresives or “stickies”
- Pitch ie primarily tree resin components.
- a detailed list of "Pitch” and “Stickies” components can be found, for example, in the WO01 / 71092 on pages 1 and 2, and the disclosure thereon is hereby incorporated by reference into the present specification.
- the impurities are therefore primarily anionic (negatively charged) or hydrophobic.
- the highly activated bentonites used according to the invention with high CEC can bind both anionic and hydrophobic contaminant fractions very well and neutralize their harmful effect.
- the inventively used Bentonites themselves have a relatively high negative layer charge and then provide this high (negative) surface charge in the delaminated form of the pulp. This would not expect a good impurity binding for anionic or hydrophobic impurities.
- a calcium bentonite better binds such impurities, because a large part of the charges of the bentonites is saturated by the calcium ions and these could immobilize impurities eg in the form of soaps and fatty acids in tree resin.
- the stickies such as tree resin particles contain many rather nonpolar (hydrophobic) components, such as triglycerides. These should bond particularly well to non-polar surfaces such as talc. Talc has no surface charges and is therefore described in the prior art as optimal for the binding of (hydrophobic) impurities.
- paper pulp and pulp suspension should generally include all pulp-containing compositions or streams used in papermaking. Otherwise, the terms "pulp” and “pulp suspension”, the skilled worker and need not be explained in detail here.
- the pulp or pulp suspension is a wood (fine) slurry-containing suspension.
- wood pulp is concerned in general, finely digested (finely ground wood, usually without further chemical or thermal treatment).
- the wood pulp suspension is either used directly after crushing or subjected to peroxide bleaching, in which case so-called peroxide-bleached wood pulp is produced.
- the bentonite used in accordance with the invention shows particularly good results in wood pulp or peroxide-treated pulp-containing paper grades.
- the inventive method can also be used advantageously in other types of paper.
- the pulp or pulp suspension in addition to the groundwood
- the invention further provides very good results in so-called "deinked pulp” (DIP substance). It is a pulp made from waste paper. In particular, there are hydrophobic stickies, from the glue of magazines and newspapers. These, too, can easily be incorporated into the end product using the bentonite used according to the invention.
- paper materials in which the bentonite according to the invention can be advantageously used comprise TMP material (Thermo Mechanical Pulp), sulphate pulp, sulphite pulp and mixtures of different pulps. Depending on the paper type and location of the paper mill, such pulps are mixed in different proportions and adapted to the material requirements of the final product.
- the preferred wood pulp content in the paper pulp or pulp suspension is according to an advantageous embodiment of the invention at least 10 wt .-%; in particular at least 30% by weight, in each case based on the dry weight of the entire pulp or suspension.
- the bentonite in the process of the present invention is likely to act without the invention being limited to the accuracy of this assumption by binding or interacting with the contaminants and thus preventing aggregation and deposition on the parts of the paper machine, such as e.g. the rollers, counteracts.
- the bentonite used has a cation exchange capacity (CEC) of at least 85 meq / 100 g, preferably at least 90 meq / 100 g, in particular at least 95 meq / 100 g.
- CEC cation exchange capacity
- CEC cation exchange capacity
- the cation exchange capacity thus includes, for example, the sum of all exchangeable divalent and monovalent cations, such as calcium, magnesium, sodium, lithium and potassium ions.
- the bentonite is treated with an ammonium chloride solution. Due to the high affinity of the ammonium ions for bentonite, virtually all exchangeable cations are exchanged for ammonium ions. After separation and washing, the nitrogen content of the bentonite is determined and from this the content of ammonium ions is calculated.
- bringing into contact can take place in any manner known to those skilled in the art, for example by preparing a solid mixture, a suspension with the layered silicate and the sodium carbonate or by spraying the layered silicate with a solution of the sodium carbonate.
- a calcium-containing crude bentonite having a water content of about 25 to 40% by weight is kneaded with solid sodium carbonate, dried and ground.
- the crude bentonite is pre-crushed to pieces less than 3 cm in diameter. If the crude bentonite does not have the specified water content, this is adjusted by spraying with water.
- the activation can, for example, also be carried out as follows: 350 g of crude bentonite having a water content of about 30 to 35% by weight are introduced into a mixing device (eg a Werner & Pfleiderer mixer (kneader)) and kneaded for 1 minute. Then, while continuing to run the mixer, the amount of sodium carbonate (soda) corresponding to the difference between CEC and sodium content of the bentonite is further kneaded for 10 minutes. The amounts added are based on the anhydrous bentonite. If necessary, some distilled water is added, so that the plasticine "sheared" well.
- a mixing device eg a Werner & Pfleiderer mixer (kneader)
- kneader Werner & Pfleidererer mixer
- the putty is then crushed into small pieces and dried in a convection oven at about 75 ° C for 2 to 4 hours to a water content of 10 ⁇ 2%.
- the dry material is then ground in a rotary rotor mill (eg in a Retsch mill) over a 0.12 mm sieve.
- the CEC and the proportion of sodium ions thereto were determined as described below.
- An overactivation of the bentonite eg with soda is also possible, wherein More soda can be used than stoichiometrically required for complete activation of the bentonite.
- the specified proportion of monovalent cations refers to the proportion of sodium, potassium and lithium ions, in particular the sodium ions.
- the bentonite used has a swelling capacity of at least 25 ml / 2 g, in particular of at least 30 ml / 2 g, more preferably at least 35 ml / 2 g.
- the swelling volume is determined as follows: A calibrated 100 ml graduated cylinder is distilled with 100 ml. Filled with water. 2.0 g of the substance to be measured are slowly added in portions of 0.1 to 0.2 g on the water surface. After lowering the material, the next quantum is abandoned. After completion of the addition, wait for 1 hour and then read the volume of the swollen substance in ml / 2g.
- the proportion of iron ions at the CEC should preferably be below about 0.005 (0.5%). It has been found that such bentonites provide better results in terms of the degree of whiteness of the pulp.
- the proportion of monovalent cations in the CEC of the bentonite is more than 0.7, in particular more than 0.8, preferably more than 0.81, more preferably more than 0.85. It is furthermore preferred that the proportion of calcium and / or magnesium ions in the CEC of the bentonite is less than 0.2, in particular less than 0.18, preferably less than 0.15.
- the BET surface area (determined according to DIN 66131) of the bentonites used is less than 100 m 2 / g, in particular less than 90 m 2 / g. It is surprising that bentonites with a relatively low specific BET surface area show a particularly advantageous contaminant binding in comparison to bentonites, which can provide a higher specific surface area for contaminant adsorption.
- the concentration of impurities in papermaking is typically determined in the white water by the three common methods cation (s) required (cationic charge demand), turbidity measurement and chemical oxygen demand.
- cation demand it is assumed that the contaminants are all negatively charged and the white water is filtered in short-chain cationic polyelectrolytes. Consumption is converted into the so-called cation requirement.
- turbidity measurement it is assumed that the contaminants are partly colloidal and their concentration can be determined by the extinction caused by the turbidity.
- chemical oxygen demand the amount of organic compounds present is tested via an oxidizing agent.
- the addition of the bentonite used according to the invention to the pulp or pulp suspension can take place at any point in the papermaking industry suitable for the person skilled in the art. Especially recommended is the addition directly in the pulper, because there is the possibility of a long contact time to the pulp, and the likelihood of a high level of impurity binding is given. Further additions are in the entire so-called thick matter area. Also conceivable is an addition for the "dissolved air flotation" for water purification. In many cases, an already existing addition point for additives, for example in the form of a metering device or metering pump, will also be present in the respectively used papermaking apparatus which can be used for the addition of the bentonite used according to the invention.
- the bentonite can be used both in powder form, as well as in the form of a suspension or slurry. The suspension or slurry will in many cases allow for better meterability and is easier to automate in large-scale, continuous processes.
- the particle size of the bentonite is selected such that the wet sieve residue is less than 2% by weight, preferably less than 1% by weight, in particular less than 0.5% by weight, to 45 ⁇ m .
- the determination of Nasssiebrückstands is explained in more detail before the examples.
- the preferred particle size can also be determined by the light scattering method (Malvern).
- the mean particle size (D50) (based on the sample volume) is between 0.5 and 10 ⁇ m , in particular between 2 and 6 ⁇ m , particularly preferably between 3 and 5 ⁇ m .
- bentonite used in the process according to the invention can be routinely determined by the person skilled in the art on the basis of empirical experiments. In most cases amounts are between 0.5 and 12 kg / t paper pulp or pulp suspension, preferably between 1 and 8 kg / t, in particular between 1.5 and 7 kg / t, in each case based on the anhydrous pulp / suspension (dry weight ), be beneficial.
- the process according to the invention not only enables a very good binding of anionic impurity fractions, such as fatty acids, but also outstanding binding or elimination of hydrophobic impurity fractions, such as sterols, steryl esters and triglycerides.
- anionic impurity fractions such as fatty acids
- hydrophobic impurity fractions such as sterols, steryl esters and triglycerides.
- Another aspect of the present invention relates to the use of a bentonite as described herein for impurity binding in papermaking.
- the bentonite is preferably used in a paper pulp or pulp suspension containing wood pulp.
- all types of paper or pulp are included in the use according to the invention.
- Particularly preferred are the above-mentioned types of paper such as groundwood or peroxide-treated wood pulp containing paper types, those (in addition to the groundwood) also contain highly purified fiber fractions, as is the case for example in so-called news print paper, so-called “deinked pulp” (DIP). Substance), TMP (Thermo Mechanical Pulp), sulphate pulp, sulphite pulp and mixtures of different pulps.
- Nessler's reagent (Merck, item No. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0.1 N hydrochloric acid; NaCl solution, 0.1%; KCl solution, 0.1%
- Detection of the ionic freedom of the wash water is performed on NH 4 + ions with the sensitive Nessler's reagent.
- the washing rate can vary between 30 minutes and 3 days depending on the key.
- the washed out NH 4 + bentonite is removed from the filter, dried at 110 ° C. for 2 hours, ground, sieved (63 ⁇ m sieve) and dried again at 110 ° C. for 2 hours. Thereafter, the NH 4 + content of the bentonite is determined according to Kjeldahl.
- the CEC of the clay is the Kjeldahl NH 4 + content of the NH 4 + bentonite (CEC of some clay minerals, see Appendix). The data are given in mval / 100 g clay (meq / 100g).
- the cations released by the exchange are in the wash water (filtrate).
- the proportion and the type of monovalent cations ("exchangeable cations") was determined spectroscopically in the filtrate according to DIN 38406, part 22.
- the washing water (filtrate) is concentrated for AAS determination, transferred to a 250 ml volumetric flask and filled up with deionised water to the measuring mark. Suitable measuring conditions for FAAS can be found in the following tables.
- Ionisationspuffer 0.1% KCl 0.1% NaCl 0.1% NaCl 0.1% KCl 0.1% KCl torch position 15-20 ° - - - - Calibration level (mg / l): 1-5 mg / l 1-5 mg / l 2-10 mg / l 0.5-3 mg / l (5-40 mg / l) 1-5 mg / l element aluminum iron Wavelength (nm): 309.3 248.3 Gap width (nm): 0.5 0.2 Integral time (sec): 3 3 3 Flame gases: N 2 O / C 2 H 2 Air / C 2 H 2 Untergrundkomp .: Yes No Measurement type: conc. conc. Ionisationspuffer: 0.1% KCl - torch position - - Calibration mode. (Mg / l): 10-50 mg / l 1-5 mg / l
- overactivated bentonites ie those which have been activated with a greater than stoichiometric amount of, for example, soda
- the sum of the determined amounts of monovalent cations can exceed the CEC determined as indicated above.
- the total monovalent cation content Li, K, Na is considered to be 100% of the CEC.
- Instruments Analytical balance, plastic cup, Pendraulik LD 50; Sieve: 200 mm diameter, mesh size 0.025 (25 ⁇ m ), 0.045 mm (45 ⁇ m ), 0.053 mm (53 ⁇ m ) or 0.063 mm (63 ⁇ m ); Ultrasonic bath.
- the selected stock (eg 45% pulp and 55% peroxide bleached wood pulp) can either be obtained directly from the mill or stored in the refrigerator before use.
- the stock was then shaken well at 20g dry to 2% with warm deionized water in a 2000ml beaker. While stirring at 400 rpm, the pulp batch was heated to 40 ° C. using a hot plate. When the temperature is reached, the amount of adsorbent to be tested is added to the stock batch using a Pasteur pipette. Subsequently, the adsorption time in the batch is fixed at 40 ° C. for 30 minutes and the mixture is stirred at 400 rpm for as long as possible. Thereafter, the paper stock approach with the adsorbent diluted to 1% solids content using deionized water (40 ° C).
- the analytical data of the calcium bentonite used are summarized in Table 1.
- the shares in the CEC can be found in Table 2.
- Table 1 Analytical data of the calcium bentonite (bentonite 1) water content 12.2% by weight pH (5% by weight suspension in water) 9.0 Montmorillonite content (methylene blue method) 100% by weight quartz 0.5% by weight calcite ⁇ 1% by weight specific surface area (BET) 86 m 2 / g
- Bentonite 2 was obtained from bentonite 1 by kneading bentonite 1 with 5% by weight soda based on the anhydrous bentonite according to the above method, dried to a water content of 10% by weight and then to a corresponding particle size such as bentonite 1 (comparison Table 2) was ground. These processing steps do not alter the mineralogical data of the bentonite, so that the montmorillonite content and the content of accompanying minerals remain unchanged.
- the BET surface area was 85 ⁇ 2 m 2 / g.
- the sample treated with the bentonite 2 according to the invention shows with respect to both cationized talc treated as well as the non-inventive calcium bentonite (bentonite 1) treated sample significantly better binding / removal of fatty acids, lignins, styrenes, styryl esters and triglycerides.
- the bentonite of the present invention was compared to conventional bentonites which had at least 0.7 (70%) monovalent cation content at the CEC but a CEC of less than 85 meq / 100g.
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Description
Die vorliegende Erfindung betrifft die Verwendung von speziellen Bentoniten mit einer hohen Kationenaustauschkapazität bei der Bindung oder Entfernung von Störstoffen in der Papierherstellung.The present invention relates to the use of specific bentonites having a high cation exchange capacity in the binding or removal of impurities in papermaking.
Die Störstoffentfernung bzw. -bindung bei der Papierherstellung gewinnt immer mehr an Bedeutung. Die Problematik beruht auch darauf, dass das bei der Papierherstellung anfallende Wasser im Kreislauf gefahren wird, wobei sich Störstoffe nach und nach darin anreichern. Diese Störstoffe können so zu den unterschiedlichsten Produktstörungen führen, wie z.B. zur Bildung von Ablagerungen auf den Walzen der Papiermaschine, zur Verklebung der Siebe, etc.. Diese Effekte führen zu Unterbrechungen bei der Papierproduktion. Um die Anzahl der Produktionsstopps zu minimieren, ist es wünschenswert, die im Kreislaufwasser anfallenden Störstoffe zu binden, indem man Polymere oder Adsorbentien bereits im Stoffauflauf einsetzt. Die meisten relevanten Störstoffe sind dabei negativ geladen. Dabei handelt es sich beispielsweise um Huminsäuren, Baumharzkolloide, Linginderivate, Ligninsulfonate, die aus den Fasern in den Papierkreislauf eingetragen werden. Hinzu kommen anionische Störstoffe, die in die Papiermaschine durch ein Recycling von Papierbruch eingetragen werden. Dieser Papierbruch wird typischerweise wieder dispergiert und in die Papiermaschine eingebracht. Dadurch werden die darin enthaltenen Inhaltsstoffe und Hilfsmittel komplett in den Kreislauf zurückgeführt. Eingetragen werden dadurch zusätzlich z.B. Carboxymethylcellulosen, Polyacrylate, Polyphosphonate und Silicate. Weitere anionische geladene Störstoffe sind die Latices, die im Papierstrich verwendet werden, welche typischerweise zwar hydrophob sind, jedoch auch anionische Ladungen tragen. Diese neigen stark zur Agglomeration, wobei die Agglomerate als klebrige, weiße Rückstände auf der Papiermaschine abgelagert werden (sog. White Pitch).Disturbance removal or binding in papermaking is becoming increasingly important. The problem is also based on the fact that the paper obtained in the production of water is recycled, with impurities gradually accumulate in it. These contaminants can thus lead to a wide variety of product failures, such as the formation of deposits on the rolls of the paper machine, the gluing of the screens, etc. These effects lead to interruptions in the paper production. In order to minimize the number of production stops, it is desirable to bind the resulting in the circulating water impurities by using polymers or adsorbents already in the headbox. Most of the relevant contaminants are negatively charged. These are, for example Humic acids, tree resin colloids, lingin derivatives, lignosulfonates, which are introduced from the fibers into the paper cycle. There are also anionic impurities which are introduced into the paper machine by recycling paper broke. This paper break is typically redispersed and introduced into the paper machine. As a result, the ingredients and aids contained in it are completely recycled. In addition, eg carboxymethylcelluloses, polyacrylates, polyphosphonates and silicates are registered. Other anionic charged impurities are the latices used in the paper coating which, while typically hydrophobic, also carry anionic charges. These strongly tend to agglomerate, whereby the agglomerates are deposited as sticky, white residues on the paper machine (so-called white pitch).
Im Stand der Technik ist umfangreich bereits der Austrag von klebrigen Stoffen (sog. "Stickys") durch den Einsatz von Talkum (Talk) beschrieben. So ist gemäß
Weiterhin ist beispielsweise in der
In der
In ähnlicher Weise betrifft die
In der
Verfahren zur Verringerung von Störstoffen werden auch in
Viele der im Stand der Technik eingesetzten Mittel zur Störstoffbindung sind recht kostspielig und für bestimmte Störstoffzusammensetzungen nicht optimal geeignet. Es besteht somit ein ständiger Bedarf an Mitteln zur Bindung von Störstoffen in der Papierherstellung.Many of the impurity binding agents used in the prior art are quite expensive and not optimally suited for certain contaminant compositions. Thus, there is a continuing need for agents for binding contaminants in papermaking.
Eine Aufgabe der vorliegenden Erfindung war es daher, ein verbessertes Verfahren zur Störstoffbindung in der Papierherstellung bereitzustellen, bei dem ein einfach und kostengünstig herzustellendes Mittel eingesetzt werden kann und das ein hohes Maß an Störstoffbindung, auch von hydrophoben Anteilen, ermöglicht.An object of the present invention was therefore to provide an improved process for impurity binding in papermaking, in which a simple and inexpensive to produce means can be used and which enables a high degree of impurity binding, even of hydrophobic moieties.
Nach einem Aspekt der Erfindung wird diese Aufgabe durch das Verfahren gemäß Anspruch 1 gelöst.According to one aspect of the invention, this object is achieved by the method according to
So wurde im Rahmen der vorliegenden Erfindung überraschend gefunden, dass durch die Verwendung eines Bentonits, der einen Anteil der einwertigen Kationen an der Kationenaustauschkapazität (hierin als CEC (aus dem Englischen) bzw. KAK bezeichnet) von mindestens etwa 0,7 (d.h. 70%) und eine CEC (gesamt) von mindestens 85 meq/100g aufweist, eine überraschend gute Störstoffbindung in einem Verfahren zur Störstoffbindung in der Papierherstellung bereitgestellt werden kann.Thus, it has surprisingly been found within the scope of the present invention that by using a bentonite which has a proportion of the monovalent cations in the cation exchange capacity (referred to herein as CEC) of at least about 0.7 (ie 70%). ) and having a CEC (total) of at least 85 meq / 100g, a surprisingly good impurity binding can be provided in a process for impurity binding in papermaking.
Unter Störstoffen werden dabei in Rahmen der vorliegenden Erfindung sowohl klebrige Substanzen, in der Literatur auch als "Kleber" bzw. "Stickies" bezeichnet, als auch das sogenannte "Pitch" d.h. in erster Linie Baumharzkomponenten, verstanden. Hier kann auf die in der Beschreibungseinleitung gemachten Ausführungen zu den Störstoffen verwiesen werden. Eine detaillierte Auflistung der "Pitch" und "Stickies"-Bestandteile findet sich beispielsweise in der
Wie vorstehend ausgeführt, sind die Störstoffe somit in erster Linie anionisch (negativ geladen) oder hydrophob. Somit war es umso überraschender, dass die erfindungsgemäß eingesetzten hochaktivierten Bentonite mit hoher CEC sowohl anionische als auch hydrophobe Störstoffanteile sehr gut binden und in ihrer schädlichen Wirkung neutralisieren können. Die erfindungsgemäß eingesetzten Bentonite weisen selbst eine relativ hohe negative Schichtladung auf und stellen diese hohe (negative) Oberflächenladung dann in der delaminierten Form der Papiermasse zur Verfügung. Damit würde man keine gute Störstoffbindung für anionische oder hydrophobe Störstoffe erwarten. Auch wäre zu erwarten, dass ein Calciumbentonit besser solche Störstoffe bindet, weil ein Großteil der Ladungen der Bentonite durch die Calciumionen abgesättigt ist und diese z.B. über Seifenbildung und Fettsäuren in Baumharz Störstoffe immobilisieren könnten. Insbesondere die Stickies wie Baumharzpartikel enthalten viele eher unpolare (hydrophobe) Komponenten, z.B. Triglyceride. Diese sollten besonders gut an unpolare Oberflächen, wie z.B. die von Talk binden. Talk hat keine Oberflächenladungen und wird deshalb auch im Stand der Technik als optimal für die Bindung von (hydrophoben) Störstoffen beschrieben.As stated above, the impurities are therefore primarily anionic (negatively charged) or hydrophobic. Thus, it was all the more surprising that the highly activated bentonites used according to the invention with high CEC can bind both anionic and hydrophobic contaminant fractions very well and neutralize their harmful effect. The inventively used Bentonites themselves have a relatively high negative layer charge and then provide this high (negative) surface charge in the delaminated form of the pulp. This would not expect a good impurity binding for anionic or hydrophobic impurities. It would also be expected that a calcium bentonite better binds such impurities, because a large part of the charges of the bentonites is saturated by the calcium ions and these could immobilize impurities eg in the form of soaps and fatty acids in tree resin. In particular, the stickies such as tree resin particles contain many rather nonpolar (hydrophobic) components, such as triglycerides. These should bond particularly well to non-polar surfaces such as talc. Talc has no surface charges and is therefore described in the prior art as optimal for the binding of (hydrophobic) impurities.
Die Ergebnisse im Rahmen der vorliegenden Erfindung, wonach im erfindungsgemäßen Verfahren mit Bentoniten, die eine große Oberfläche mit zahlreichen negativen Ladungen zur Verfügung stellt, sowohl unpolare als auch anionische Störstoffe effizient gebunden werden können, waren daher unerwartet.The results in the context of the present invention, according to which in the process according to the invention with bentonites which provides a large surface area with numerous negative charges, both non-polar and anionic impurities can be bound efficiently, were therefore unexpected.
Das erfindungsgemäße Verfahren unter Verwendung des hierin beschriebenen speziellen Bentonits kann allgemein in allen Verfahren zur Papier- oder Kartonherstellung eingesetzt werden. Entsprechend sollen die Ausdrücke Papierpulpe und Faserstoffsuspension allgemein alle störstoffhaltigen Zusammensetzungen bzw. Ströme umfassen, die bei der Papierherstellung verwendet werden. Ansonsten sind die Ausdrücke "Pulpe" und "Faserstoffsuspension", dem Fachmann geläufig und müssen hier nicht näher erläutert werden.The process of the invention using the specific bentonite described herein can be used generally in all paper or board making processes. Accordingly, the terms paper pulp and pulp suspension should generally include all pulp-containing compositions or streams used in papermaking. Otherwise, the terms "pulp" and "pulp suspension", the skilled worker and need not be explained in detail here.
Nach einer bevorzugten erfindungsgemäßen Ausführungsform handelt es sich bei der Pulpe bzw. der Faserstoffsuspension um eine holz (fein) schliffhaltige Suspension. Bei Holzschliff handelt es sich allgemein um fein aufgeschlossenes (fein gemahlenes Holz, zumeist ohne weitere chemische oder thermische Behandlung). Die Holzschliffsuspension wird dabei entweder direkt nach dem Zerkleinern eingesetzt oder einer Peroxidbleiche unterzogen, wobei dann sogenannter Peroxid-gebleichter Holzschliff entsteht. Es hat sich überraschend gezeigt, dass der erfindungsgemäß verwendete Bentonit bei Holzschliff oder Peroxid-behandelten Holzschliff enthaltenden Papiersorten besonders gute Ergebnisse zeigt. Das erfindungsgemäße Verfahren kann aber auch vorteilhaft bei anderen Papierarten eingesetzt werden. So kann z.B. die Pulpe bzw. Faserstoffsuspension (neben dem Holzschliff) auch noch hochgereinigte Faseranteile enthalten, wie dies z.B. bei sogenannten News Print Papier der Fall ist. Die Erfindung liefert weiterhin sehr gute Ergebnisse bei sogenannter "Deinked Pulp" (DIP-Stoff). Dabei handelt es sich um einen Papierstoff, der aus Altpapier hergestellt wird. Dort fallen insbesondere hydrophobe Stickies an, aus dem Kleber von Magazinen und Zeitung. Auch diese lassen sich mit dem erfindungsgemäß verwendeten Bentonit in das Endprodukt gut einbinden. Weitere sogenannte Papierstoffe, bei denen der erfindungsgemäße Bentonit vorteilhaft eingesetzt werden kann umfassen TMP Stoff (Thermo Mechanical Pulp), Sulfatzellstoff, Sulfitzellstoff sowie Mischungen aus unterschiedlichen Zellstoffen. Je nach Papiertyp und Lokalisation der Papierfabrik werden solche Zellstoffe in unterschiedlichen Verhältnissen gemischt und auf die Materialanforderungen des Endproduktes hin angepasst.According to a preferred embodiment of the invention, the pulp or pulp suspension is a wood (fine) slurry-containing suspension. When wood pulp is concerned in general, finely digested (finely ground wood, usually without further chemical or thermal treatment). The wood pulp suspension is either used directly after crushing or subjected to peroxide bleaching, in which case so-called peroxide-bleached wood pulp is produced. It has surprisingly been found that the bentonite used in accordance with the invention shows particularly good results in wood pulp or peroxide-treated pulp-containing paper grades. The inventive method can also be used advantageously in other types of paper. Thus, for example, the pulp or pulp suspension (in addition to the groundwood) may also contain highly purified fiber fractions, as is the case with so-called news print paper, for example. The invention further provides very good results in so-called "deinked pulp" (DIP substance). It is a pulp made from waste paper. In particular, there are hydrophobic stickies, from the glue of magazines and newspapers. These, too, can easily be incorporated into the end product using the bentonite used according to the invention. Further so-called paper materials in which the bentonite according to the invention can be advantageously used comprise TMP material (Thermo Mechanical Pulp), sulphate pulp, sulphite pulp and mixtures of different pulps. Depending on the paper type and location of the paper mill, such pulps are mixed in different proportions and adapted to the material requirements of the final product.
Der bevorzugte Holzschliffanteil in der Papierpulpe bzw. Faserstoffsuspension liegt nach einer vorteilhaften erfindungsgemäßen Ausführungsform bei mindestens 10 Gew.-%; insbesondere mindestens 30 Gew.-%, jeweils bezogen auf das Trockengewicht der gesamten Pulpe bzw. Suspension.The preferred wood pulp content in the paper pulp or pulp suspension is according to an advantageous embodiment of the invention at least 10 wt .-%; in particular at least 30% by weight, in each case based on the dry weight of the entire pulp or suspension.
Der Bentonit im erfindungsgemäßen Verfahren wirkt wahrscheinlich, ohne das die Erfindung auf die Richtigkeit dieser Annahme beschränkt wäre, indem er die Störstoffe bindet bzw. mit diesen in Wechselwirkung tritt und somit der Aggregation und Ablagerung auf den Teilen der Papiermaschine, wie z.B. den Walzen, entgegenwirkt.The bentonite in the process of the present invention is likely to act without the invention being limited to the accuracy of this assumption by binding or interacting with the contaminants and thus preventing aggregation and deposition on the parts of the paper machine, such as e.g. the rollers, counteracts.
Erfindungsgemäß ist es wesentlich, dass der eingesetzte Bentonit ein Kationenaustauschkapazität (CEC) von mindestens 85 meq/100g, vorzugsweise mindestens 90 meq/100g, insbesondere mindestens 95 meq/100g aufweist.According to the invention, it is essential that the bentonite used has a cation exchange capacity (CEC) of at least 85 meq / 100 g, preferably at least 90 meq / 100 g, in particular at least 95 meq / 100 g.
Unter "Kationenaustauschkapazität" (CEC) wird dabei die Summe aller austauschbaren Kationen verstanden, angegeben in mVal (meq)/100 g und bestimmt nach der CEC-Analysenmethode wie nachstehend vor dem Beispielteil (Bestimmung der Kationenaustauschkapazität) erläutert. Die Kationenaustauschkapazität umfasst also beispielsweise die Summe aller austauschbaren zwei- und einwertigen Kationen wie Calcium-, Magnesium-, Natrium- Lithium- und Kaliumionen. Zur Bestimmung des Kationenaustauschkapazität wird der Bentonit mit einer Ammoniumchloridlösung behandelt. Dabei werden wegen der hohen Affinität der Ammoniumionen zum Bentonit praktisch alle austauschbaren Kationen durch Ammoniumionen ausgetauscht. Nach Abtrennen und Waschen wird der Stickstoffgehalt des Bentonits bestimmt und daraus der Gehalt an Ammoniumionen errechnet.The term "cation exchange capacity" (CEC) is understood to mean the sum of all exchangeable cations, expressed in mVal (meq) / 100 g and determined by the CEC analysis method as follows before the example part (determination of cation exchange capacity). The cation exchange capacity thus includes, for example, the sum of all exchangeable divalent and monovalent cations, such as calcium, magnesium, sodium, lithium and potassium ions. To determine the cation exchange capacity, the bentonite is treated with an ammonium chloride solution. Due to the high affinity of the ammonium ions for bentonite, virtually all exchangeable cations are exchanged for ammonium ions. After separation and washing, the nitrogen content of the bentonite is determined and from this the content of ammonium ions is calculated.
Es können sowohl natürliche Bentonite als auch durch Aktivierung z.B. von Calciumbentoniten gewonnene Bentonite verwendet werden, sofern die vorstehenden Bedingungen für den Anteil der einwertigen Kationen an der CEC und die Mindestwerte für die CEC eingehalten sind. Verfahren zur Erzeugung bzw. Aktivierung von Bentoniten sind dem Fachmann als solche bekannt und müssen hier nicht näher erläutert werden. Beispielsweise kann von einem Calciumbentonit mit geeigneter CEC ausgegangen und dieser mit einem Alkalicarbonat, z.B. Natriumcarbonat behandelt werden. Bei der Behandlung bzw. Aktivierung des Schichtsilicats kann das In-Kontakt-bringen auf beliebige dem Fachmann geläufige Weise erfolgen, z.B. durch Herstellung eines Feststoffgemisches, einer Suspension mit dem Schichtsilicat und dem Natriumcarbonat oder Beaufschlagung bzw. Besprühen des Schichtsilicates mit einer Lösung des Natriumcarbonates.It is possible to use both natural bentonites and bentonites obtained by activation, for example of calcium bentonites, provided that the above conditions for the proportion of monovalent cations on the CEC and the minimum values for the CEC are observed. Methods for generating or activating bentonites are known to the person skilled in the art and need not be explained in more detail here. For example, it can be assumed that a calcium bentonite with suitable CEC and this with a Alkali carbonate, eg sodium carbonate are treated. In the treatment or activation of the layered silicate, bringing into contact can take place in any manner known to those skilled in the art, for example by preparing a solid mixture, a suspension with the layered silicate and the sodium carbonate or by spraying the layered silicate with a solution of the sodium carbonate.
Beispielsweise wird nach der ersten Verfahrensvariante ein calciumhaltiger Rohbentonit mit einem Wassergehalt von etwa 25 bis 40 Gew.-% mit festem Natriumcarbonat verknetet, getrocknet und gemahlen. Der Rohbentonit wird auf Stücke von weniger als 3 cm Durchmesser vorgebrochen. Falls der Rohbentonit nicht den angegebenen Wassergehalt aufweist, wird dieser durch Besprühen mit Wasser eingestellt.For example, according to the first process variant, a calcium-containing crude bentonite having a water content of about 25 to 40% by weight is kneaded with solid sodium carbonate, dried and ground. The crude bentonite is pre-crushed to pieces less than 3 cm in diameter. If the crude bentonite does not have the specified water content, this is adjusted by spraying with water.
Die Aktivierung kann beispielsweise auch wie folgt erfolgen: 350 g Rohbentonit mit einem Wassergehalt von etwa 30 bis 35 Gew.-%, werden in eine Mischvorrichtung (z.B. einen Werner & Pfleiderer-Mischer (Kneter)) gegeben und für 1 Minute geknetet. Dann wird unter Weiterlaufen der Mischvorrichtung die Menge an Natriumcarbonat (Soda) zugefügt, die der Differenz zwischen CEC und Natriumgehalt des Bentonits entspricht, und 10 min weitergeknetet. Dabei sind die zugesetzten Mengen auf den wasserfreien Bentonit bezogen. Bei Bedarf wird noch etwas destilliertes Wasser zugegeben, so dass die Knetmasse gut "schert". Die Knetmasse wird danach in kleine Stücke zerkleinert und in einem Umlufttrockenschrank bei etwa 75°C 2 bis 4 Std. auf einem Wassergehalt von 10 ± 2 % getrocknet. Das Trockengut wird dann in einer Schlagrotormühle (z.B. in einer Retsch-Mühle) über einem 0,12 mm-Sieb vermahlen. Die CEC und der Anteil der Natriumionen hieran wurde wie weiter unten beschrieben bestimmt. Eine Überaktivierung des Bentonits z.B. mit Soda ist ebenfalls möglich, wobei mehr Soda eingesetzt werden kann als zur vollständigen Aktivierung des Bentonits stöchiometrisch erforderlich wäre.The activation can, for example, also be carried out as follows: 350 g of crude bentonite having a water content of about 30 to 35% by weight are introduced into a mixing device (eg a Werner & Pfleiderer mixer (kneader)) and kneaded for 1 minute. Then, while continuing to run the mixer, the amount of sodium carbonate (soda) corresponding to the difference between CEC and sodium content of the bentonite is further kneaded for 10 minutes. The amounts added are based on the anhydrous bentonite. If necessary, some distilled water is added, so that the plasticine "sheared" well. The putty is then crushed into small pieces and dried in a convection oven at about 75 ° C for 2 to 4 hours to a water content of 10 ± 2%. The dry material is then ground in a rotary rotor mill (eg in a Retsch mill) over a 0.12 mm sieve. The CEC and the proportion of sodium ions thereto were determined as described below. An overactivation of the bentonite eg with soda is also possible, wherein More soda can be used than stoichiometrically required for complete activation of the bentonite.
Nach einer besonders bevorzugten erfindungsgemäßen Ausführungsform bezieht sich der angegebene Anteil der einwertigen Kationen auf den Anteil der Natrium-, Kalium- und Lithiumionen, insbesondere der Natriumionen.According to a particularly preferred embodiment of the invention, the specified proportion of monovalent cations refers to the proportion of sodium, potassium and lithium ions, in particular the sodium ions.
Nach einer bevorzugten erfindungsgemäßen Ausführungsform weist der verwendete Bentonit ein Quellvermögen von mindestens 25 ml/2g, insbesondere von mindestens 30 ml/2g, weiter bevorzugt mindestens 35 ml/2g auf. So hat sich überraschend gezeigt, dass Bentonite mit solchen hohen Quellvermögen eine besonders vorteilhafte Störstoffbindung ermöglichen. Das Quellvolumen wird dabei wie folgt bestimmt: Ein kalibrierter 100 ml-Meßzylinder wird mit 100 ml dest. Wasser gefüllt. 2,0 g der zu messenden Substanz werden in Portionen von 0,1 bis 0,2 g langsam auf der Wasseroberfläche gegeben. Nach dem Absinken das Materials wird das nächste Quantum aufgegeben. Nach Beendigung der Zugabe wartet man 1 Stunde und liest dann das Volumen der aufgequollenen Substanz in ml/2g ab.According to a preferred embodiment of the invention, the bentonite used has a swelling capacity of at least 25 ml / 2 g, in particular of at least 30 ml / 2 g, more preferably at least 35 ml / 2 g. Thus, it has surprisingly been found that bentonites with such high swelling capacity enable a particularly advantageous impurity binding. The swelling volume is determined as follows: A calibrated 100 ml graduated cylinder is distilled with 100 ml. Filled with water. 2.0 g of the substance to be measured are slowly added in portions of 0.1 to 0.2 g on the water surface. After lowering the material, the next quantum is abandoned. After completion of the addition, wait for 1 hour and then read the volume of the swollen substance in ml / 2g.
Weiterhin hat sich gezeigt, dass der Anteil an Eisenionen an der CEC vorzugsweise unter etwa 0,005 (0,5%) liegen sollte. Es hat sich gezeigt, dass solche Bentonite bessere Ergebnisse im Hinblick auf den Weissgrad der Papiermasse liefern.Furthermore, it has been found that the proportion of iron ions at the CEC should preferably be below about 0.005 (0.5%). It has been found that such bentonites provide better results in terms of the degree of whiteness of the pulp.
Nach einem weiteren bevorzugten Aspekt liegt der Anteil der einwertigen Kationen an der CEC des Bentonits bei mehr als 0,7, insbesondere bei mehr als 0,8, vorzugsweise bei mehr als 0,81, weiter bevorzugt bei mehr als 0,85. Bevorzugt wird weiterhin, dass der Anteil von Calcium- und/oder Magnesiumionen an der CEC des Bentonits bei weniger als 0,2, insbesondere weniger als 0,18, vorzugsweise weniger als 0,15 liegt.According to a further preferred aspect, the proportion of monovalent cations in the CEC of the bentonite is more than 0.7, in particular more than 0.8, preferably more than 0.81, more preferably more than 0.85. It is furthermore preferred that the proportion of calcium and / or magnesium ions in the CEC of the bentonite is less than 0.2, in particular less than 0.18, preferably less than 0.15.
Nach einer weiteren bevorzugten erfindungsgemäßen Ausführungsform liegt die BET-Oberfläche (bestimmt nach DIN 66131) der verwendeten Bentonite bei weniger als 100 m2/g, insbesondere bei weniger als 90 m2/g. Dabei ist es überraschend, dass Bentonite mit relativ niedriger spezifischer BET-Oberfläche eine besonders vorteilhafte Störstoffbindung zeigen im Vergleich zu Bentoniten, die eine höhere spezifische Oberfläche zur Störstoffadsorption zur Verfügung stellen können.According to a further preferred embodiment of the invention, the BET surface area (determined according to DIN 66131) of the bentonites used is less than 100 m 2 / g, in particular less than 90 m 2 / g. It is surprising that bentonites with a relatively low specific BET surface area show a particularly advantageous contaminant binding in comparison to bentonites, which can provide a higher specific surface area for contaminant adsorption.
Typischerweise verringert sich bei der Durchführung des erfindungsgemäßen Verfahrens der Bedarf an kationischen Ladungen im Papierstoffauflauf. Dies belegt die Bindung der negativ geladenen Störstoffe durch Ladungswechselwirkungen.Typically, when carrying out the process according to the invention, the need for cationic charges in the paper headbox decreases. This demonstrates the binding of the negatively charged impurities by charge interactions.
Die Konzentration der Störstoffe bei der Papierherstellung wird typischerweise im Siebwasser durch die drei gängigen Verfahren Kation(en)bedarf (kationischer Ladungsbedarf), Trübungsmessung sowie chemischer Sauerstoffbedarf bestimmt. Beim Kationenbedarf geht man davon aus, dass die Störstoffe alle negativ geladen sind und filtriert das Siebwasser in kurzkettigen kationischen Polyelektrolyten. Der Verbrauch wird umgerechnet in den sogenannten Kationenbedarf. Bei der Trübungsmessung geht man davon aus, dass die Störstoffe zum Teil kolloidal vorliegen und ihre Konzentration über die durch die Trübung verursachte Extinktion bestimmt werden kann. Beim chemischen Sauerstoffbedarf wird über ein Oxidationsmittel der vorhandene Anteil an organischen Verbindungen getestet. Obwohl diese Methoden in der Papierwelt sehr verbreitet sind, haben neuere Untersuchungen gezeigt, dass diese über die ganzen Inhaltsstoffe in Siebwasser mitteln und besonders kritische Störstoffe nur zum Teil erfassen. Dies ergibt sich beispielsweise daraus, dass die sogenannten Baumharzkolloide, die zum Teil aus hydrophoben Verbindungen zusammengesetzt sind, nur geringe Oberflächenladungen tragen können und somit wenig zum Kationbedarf beitragen. Andererseits haben Lignine einen hohen Kationenbedarf; wenn sie im Siebwasser vorliegen, stören sie nur sehr wenig bei der Papierherstellung. Neuere Untersuchungen zeigen weiterhin, dass die Korrelation zwischen der Trübungsmessung und der Konzentration an kolloidalen Störstoffen nicht immer gegeben ist. Aufgrund dieser neueren Erfahrung mit den gängigen Störstoffbestimmungsmethoden wurden die erfindungsgemäßen Additive darüber hinaus in ihrer Wirkung mit neueren Verfahren charakterisiert. Dabei handelt es sich beispielsweise um eine gaschromatographische Analyse des Siebwassers nach der Methode von
Die Zugabe des erfindungsgemäß verwendeten Bentonits zu der Pulpe bzw. Faserstoffsuspension kann an jeder beliebigen, dem Fachmann geeigneten Stelle in der Papierherstellung erfolgen. Empfehlenswert ist dabei auch insbesondere die Zugabe direkt im Pulper, weil dort die Möglichkeit einer langen Kontaktzeit zum Papierstoff besteht, und die Wahrscheinlichkeit für eine hohe Störstoffbindung gegeben ist. Weitere Zugabestellen liegen im gesamten sogenannten Dickstoffbereich. Denkbar ist auch eine Zugabe für die "dissolved air-flotation" zur Wasserreinigung. In vielen Fällen wird auch bei den jeweils verwendeten Vorrichtungen zur Papierherstellung eine bereits vorhandene Zugabestelle für Additive, z.B. in Form in einer Dosiervorrichtung oder Dosierpumpe, vorhanden sein, die für die Zugabe des erfindungsgemäß verwendeten Bentonits verwendet werden kann. Der Bentonit kann dabei sowohl in Pulverform, als auch in Form einer Suspension bzw. Slurry eingesetzt werden. Die Suspension bzw. Slurry wird in vielen Fällen eine bessere Dosierbarkeit ermöglichen und ist in großindustriellen, kontinuierlich geführten Prozessen leichter automatisierbar.The addition of the bentonite used according to the invention to the pulp or pulp suspension can take place at any point in the papermaking industry suitable for the person skilled in the art. Especially recommended is the addition directly in the pulper, because there is the possibility of a long contact time to the pulp, and the likelihood of a high level of impurity binding is given. Further additions are in the entire so-called thick matter area. Also conceivable is an addition for the "dissolved air flotation" for water purification. In many cases, an already existing addition point for additives, for example in the form of a metering device or metering pump, will also be present in the respectively used papermaking apparatus which can be used for the addition of the bentonite used according to the invention. The bentonite can be used both in powder form, as well as in the form of a suspension or slurry. The suspension or slurry will in many cases allow for better meterability and is easier to automate in large-scale, continuous processes.
Es hat sich weiterhin gezeigt, dass die Wirkung des erfindungsgemäß eingesetzten Bentonits besonders positiv ist, wenn eine bestimmte Teichengröße eingehalten wird. So wird nach einer besonders bevorzugten Ausführungsform der Erfindung die Teilchengröße des Bentonits so gewählt, dass der Nasssiebrückstand auf 45 µm kleiner 2 Gew.-%, vorzugsweise kleiner 1 Gew.-%, insbesondere kleiner 0,5 Gew.-% liegt. Die Bestimmung des Nasssiebrückstands ist vor den Beispielen noch näher erläutert. Die bevorzugte Teilchengröße kann auch nach der Lichtstreuungsmethode (Malvern) bestimmt werden. Nach einer besonders bevorzugten erfindungsgemäßen Ausführungsform liegt dabei die mittlere Teilchengröße (D50) (auf das Probenvolumen bezogen) zwischen 0,5 und 10 µm, insbesondere zwischen 2 bis 6 µm, besonders bevorzugt zwischen 3 und 5 µm.It has also been shown that the effect of the bentonite used according to the invention is particularly positive if a certain pond size is maintained. Thus, according to a particularly preferred embodiment of the invention, the particle size of the bentonite is selected such that the wet sieve residue is less than 2% by weight, preferably less than 1% by weight, in particular less than 0.5% by weight, to 45 μm . The determination of Nasssiebrückstands is explained in more detail before the examples. The preferred particle size can also be determined by the light scattering method (Malvern). According to a particularly preferred embodiment of the invention, the mean particle size (D50) (based on the sample volume) is between 0.5 and 10 μm , in particular between 2 and 6 μm , particularly preferably between 3 and 5 μm .
Im Rahmen der vorliegenden Erfindung wurde auch überraschend gefunden, dass die Verwendung des erfindungsgemäß eingesetzten Bentonits zu einer besonders guten Störstoffbindung führt, wenn in dem Verfahren der Einsatz von Talk unterbleibt. Auch der Einsatz kationischer Polymere, wie z.B. Poly(dadmac) oder Polyacrylamid gemäß dem Stand der Technik kann mit Hilfe des erfindungsgemäß eingesetzten Bentonits reduziert werden oder sogar ganz unterbleiben.In the context of the present invention, it has also surprisingly been found that the use of the bentonite used according to the invention leads to a particularly good impurity binding when the use of talcum is omitted in the process. The use of cationic polymers, such as, for example, poly (dadmac) or polyacrylamide according to the prior art can also be achieved with the aid of the invention used bentonites are reduced or even completely omitted.
Die Einsatzmengen des Bentonits in dem erfindungsgemäßen Verfahren können vom Fachmann anhand empirischer Versuche routinemäßig bestimmt werden. In den meisten Fällen werden Einsatzmengen zwischen 0,5 und 12 kg/t Papierpulpe bzw. Faserstoffsuspension, vorzugsweise zwischen 1 und 8 kg/t, insbesondere zwischen 1,5 und 7 kg/t, jeweils bezogen auf die wasserfreie Pulpe/Suspension (Trockengewicht), vorteilhaft sein.The amounts of bentonite used in the process according to the invention can be routinely determined by the person skilled in the art on the basis of empirical experiments. In most cases amounts are between 0.5 and 12 kg / t paper pulp or pulp suspension, preferably between 1 and 8 kg / t, in particular between 1.5 and 7 kg / t, in each case based on the anhydrous pulp / suspension (dry weight ), be beneficial.
Überraschenderweise wurde im Rahmen der vorliegenden Erfindung auch gefunden, dass das erfindungsgemäße Verfahren nicht nur eine sehr gute Bindung von anionischen Störstoffanteilen, wie Fettsäuren, ermöglicht, sondern auch eine herausragende Bindung bzw. Beseitigung von hydrophoben Störstoffanteilen, wie Sterole, Sterylestern und Triglyceriden. Die hierbei erzielten Ergebnisse übertreffen überraschenderweise sowohl diejenigen, die mit herkömmlichen Bentoniten erhalten wurden, als auch diejenigen von Talkum.Surprisingly, it has also been found within the scope of the present invention that the process according to the invention not only enables a very good binding of anionic impurity fractions, such as fatty acids, but also outstanding binding or elimination of hydrophobic impurity fractions, such as sterols, steryl esters and triglycerides. The results obtained surprisingly surpass both those obtained with conventional bentonites and those of talc.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft die Verwendung eines Bentonits wie hierin beschrieben zur Störstoffbindung in der Papierherstellung. Wie vorstehend erwähnt, wird dabei der Bentonit vorzugsweise in einer Papierpulpe bzw. Faserstoffsuspension eingesetzt, die Holzschliffanteile enthält. Es sind jedoch alle Papiersorten bzw. Pulpen von der erfindungsgemäßen Verwendung umfasst. Besonders bevorzugt sind die weiter oben genannten Papierarten wie Holzschliff oder Peroxid-behandelten Holzschliff enthaltende Papiersorten, solche die (neben dem Holzschliff) auch hochgereinigte Faseranteile enthalten, wie dies z.B. bei sogenannten News Print Papier der Fall ist, sogenannter "Deinked Pulp" (DIP-Stoff), TMP-Stoff (Thermo Mechanical Pulp), Sulfatzellstoff, Sulfitzellstoff sowie Mischungen aus unterschiedlichen Zellstoffen.Another aspect of the present invention relates to the use of a bentonite as described herein for impurity binding in papermaking. As mentioned above, the bentonite is preferably used in a paper pulp or pulp suspension containing wood pulp. However, all types of paper or pulp are included in the use according to the invention. Particularly preferred are the above-mentioned types of paper such as groundwood or peroxide-treated wood pulp containing paper types, those (in addition to the groundwood) also contain highly purified fiber fractions, as is the case for example in so-called news print paper, so-called "deinked pulp" (DIP). Substance), TMP (Thermo Mechanical Pulp), sulphate pulp, sulphite pulp and mixtures of different pulps.
Methodenteil: Soweit nicht anders angegeben, wurden die im folgenden angegebenen Analyseverfahren verwendet: Methodology: Unless otherwise indicated, the following analytical methods were used:
Prinzip: Der Ton wird mit einem großen Überschuss an wässriger NH4-Cl-Lösung behandelt, ausgewaschen und die auf dem Ton verbliebene NH4 +-Menge nach Kjeldahl bestimmt.
Me+ (Ton)-+ NH4 +- NH4 +(Ton)-+Me+
(Me+ = H+, K+, Na+, 1/2 Ca2+, 1/2 Mg2+....)
Principle: The clay is treated with a large excess of aqueous NH 4 -Cl solution, washed out and the amount of NH 4 + remaining on the clay determined according to Kjeldahl.
Me + (clay) - + NH 4 + - NH 4 + (clay) - + Me +
(Me + = H + , K + , Na + , 1/2 Ca 2+ , 1/2 Mg 2+ ....)
Geräte: Sieb, 63 µm; Erlenmeyer-Schliffkolben, 300 ml; Analysenwaage; Membranfilternutsche, 400 ml; Zellulose-Nitrat-Filter, 0,15 µm (Fa. Sartorius); Trockenschrank; Rückflusskühler; Heizplatte; Destillationseinheit, VAPODEST-5 (Fa. Gerhardt, No. 6550); Messkolben, 250 ml; Flammen-AASEquipment: sieve, 63 μ m; Erlenmeyer grinding flasks, 300 ml; Analytical balance; Membrane filter chute, 400 ml; Cellulose nitrate filter, 0.15 μm (Sartorius); Drying oven; Reflux condenser; hot plate; Distillation unit, VAPODEST-5 (Gerhardt, No. 6550); Volumetric flask, 250 ml; Flame AAS
Chemikalien: 2N NH4Cl-Lösung Neßlers-Reagens (Fa. Merck, Art.Nr. 9028); Borsäure-Lösung, 2 %-ig; Natronlauge, 32 %-ig; 0,1 N Salzsäure; NaCl-Lösung, 0,1 %-ig; KCl-Lösung, 0,1 %-igChemicals: 2N NH 4 Cl solution Nessler's reagent (Merck, item No. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0.1 N hydrochloric acid; NaCl solution, 0.1%; KCl solution, 0.1%
Durchführung: 5 g Ton werden durch ein 63µm-Sieb gesiebt und bei 110°C getrocknet. Danach werden genau 2 g auf der Analysenwaage in Differenzwägung in den Erlenmeyer-Schliffkolben eingewogen und mit 100 ml 2N NH4Cl-Lösung versetzt. Die Suspension wird unter Rückfluss eine Stunde lang gekocht. Bei stark CaCo3-haltigen Bentoniten kann es zu einer Ammoniak-Entwicklung kommen. In diesen Fällen muss solange NH4Cl-Lösung zugegeben werden, bis kein Ammoniak-Geruch mehr wahrzunehmen ist. Eine zusätzliche Kontrolle kann mit einem feuchten Indikator-Papier durchgeführt werden. Nach einer Standzeit von ca. 16 h wird der NH4 +-Bentonit über eine Membranfilternutsche abfiltriert und bis zur weitgehenden Ionenfreiheit mit VE-Wasser (ca. 800 ml) gewaschen. Der Nachweis der Ionenfreiheit des Waschwassers wird auf NH4 +-Ionen mit dem dafür empfindlichen Neßlers-Reagens durchgeführt. Die Waschzahl kann je nach Tonart zwischen 30 Minuten und 3 Tagen variieren. Der ausgewaschene NH4 +-Bentonit wird vom Filter abgenommen, bei 110°C 2h lang getrocknet, gemahlen, gesiebt (63 µm-Sieb) und nochmals bei 110 °C 2 h lang getrocknet. Danach wird der NH4 +-Gehalt des Bentonits nach Kjeldahl bestimmt.Procedure: 5 g of clay are sieved through a 63 μm sieve and dried at 110 ° C. Then weigh exactly 2 g on the analytical balance in differential weighing into the Erlenmeyer grinding flask and add 100 ml of 2N NH 4 Cl solution. The suspension is boiled under reflux for one hour. In the case of strongly CaCo 3 -containing bentonites, ammonia development can occur. In these cases, as long as NH 4 Cl solution must be added until no ammonia smell is perceived. Additional control can be done with a wet indicator paper. After a service life of about 16 hours, the NH 4 + bentonite is filtered off through a membrane filter and until extensive Ion freedom washed with deionised water (about 800 ml). Detection of the ionic freedom of the wash water is performed on NH 4 + ions with the sensitive Nessler's reagent. The washing rate can vary between 30 minutes and 3 days depending on the key. The washed out NH 4 + bentonite is removed from the filter, dried at 110 ° C. for 2 hours, ground, sieved (63 μm sieve) and dried again at 110 ° C. for 2 hours. Thereafter, the NH 4 + content of the bentonite is determined according to Kjeldahl.
Berechnung der CEC: Die CEC des Tons ist der mittels Kjeldahl ermittelte NH4 +-Gehalt des NH4 +-Bentonits (CEC einiger Tonmineralien s. Anlage). Die Angaben erfolgen in mval/100 g Ton (meq/100g).Calculation of the CEC: The CEC of the clay is the Kjeldahl NH 4 + content of the NH 4 + bentonite (CEC of some clay minerals, see Appendix). The data are given in mval / 100 g clay (meq / 100g).
-
Molekulargewicht: N = 14,0067 g/mol
- CEC = 66,4 meq/100 g NH4 +-BentonitCEC = 66.4 meq / 100 g NH 4 + bentonite
- Ausgetauschte Kationen und deren Anteile:Exchanged cations and their proportions:
Die durch den Umtausch freigesetzten Kationen befinden sich im Waschwasser (Filtrat). Der Anteil und die Art der einwertigen Kationen ("austauschbare Kationen") wurde im Filtrat gemäß DIN 38406, Teil 22, spektroskopisch bestimmt. Beispielsweise wird zur AAS-Bestimmung das Waschwasser (Filtrat) eingeengt, in einen 250 ml Messkolben überführt und mit VE-Wasser bis zur Messmarke aufgefüllt. Geeignete Messbedingungen für FAAS sind aus den nachfolgenden Tabellen zu entnehmen.
Molmassen (g/mol): Ca=20,040; K=39,096; Li=6,94; Mg=12,156; Na=22,990; Al=8,994; Fe=18,616
Molar masses (g / mol): Ca = 20.040; K = 39.096; Li = 6.94; Mg = 12.156; Na = 22.990; Al = 8.994; Fe = 18.616
Bei sogenannten überaktivierten Bentoniten, d.h. solchen, die mit einer größeren als der stöchiometrischen Menge an z.B. Soda aktiviert wurden, kann die Summe der ermittelten Mengen an einwertigen Kationen die wie vorstehend angegeben bestimmte CEC übertreffen. In solchen Fällen wird der Gesamtgehalt an einwertigen Kationen (Li, K, Na) als 100% der CEC angesehen.In the case of so-called overactivated bentonites, ie those which have been activated with a greater than stoichiometric amount of, for example, soda, the sum of the determined amounts of monovalent cations can exceed the CEC determined as indicated above. In such cases, the total monovalent cation content (Li, K, Na) is considered to be 100% of the CEC.
Die Erfindung wird nun anhand der nachstehenden, nichtbeschränkenden Beispiele näher veranschaulicht.The invention will now be further illustrated by the following non-limiting examples.
Die Bestimmung erfolgte gemäß DIN 66131 (Mehrpunktbestimmung).The determination was made according to DIN 66131 (multipoint determination).
Bei dem Einsatz von Pigmenten und Füllstoffen interessiert es, ob und wie viel grobe Anteile das zu untersuchende Material enthält, die sich durch ihre Korngröße von den normalen Teilchen unterscheiden. Diese Anteile werden durch Siebung einer wässrigen Suspension mit Wasser als Spülflüssigkeit ermittelt. Als Nasssiebrückstand gilt der unter festgelegten Bedingungen ermittelte Rückstand.In the use of pigments and fillers, it is of interest whether and how much coarse fraction contains the material to be examined, which differ in their grain size from the normal particles. These proportions are determined by screening an aqueous suspension with water as the rinsing liquid. Wet residue is the residue determined under specified conditions.
Geräte: Analysenwaage, Plastikbecher, Pendraulik LD 50; Sieb: 200 mm Durchmesser, Maschenweite 0,025 (25 µm), 0,045 mm (45 µm), 0,053 mm (53 µm) oder 0,063 mm (63 µm); Ultraschallbad.Instruments: Analytical balance, plastic cup, Pendraulik LD 50; Sieve: 200 mm diameter, mesh size 0.025 (25 μm ), 0.045 mm (45 μm ), 0.053 mm (53 μm ) or 0.063 mm (63 μm ); Ultrasonic bath.
Es wurde zunächst eine 5 %ige Suspension des Bentonits (otro, d.h. nach Trocknung bei 110°C) in 2000 g Wasser hergestellt. Hierzu wird der Bentonit bei 930 UpM in ca. 5 min eingerührt. Nach einer Rührzeit von weiteren 15 min bei 1865 UpM wird die Suspension in das gesäuberte und getrocknete Sieb (Maschenweite 45 µm) gegossen und mit fließendem Leitungswasser unter Klopfen so lange gewaschen, bis das Waschwasser klar abläuft. Nach dem Waschen des Siebrückstandes mit Leitungswasser setzt man das Sieb für 5 min in ein Ultraschallbad, um die restlichen Feinanteile abzusieben. Es ist darauf zu achten, dass beim Einsetzen des Siebes im Ultraschallbad zwischen Wasseroberfläche und Siebboden keine Luft verbleibt. Nach der Ultraschallbehandlung nochmals mit Leitungswasser kurz nachspülen. Danach wird das Sieb entnommen und das Wasser im Ultraschallbad erneuert. Der Arbeitsvorgang im Ultraschallbad wird wiederholt, bis keine Verunreinigung des Wassers mehr zu erkennen ist. Das Sieb mit dem verbliebenen Rückstand wird bis zur Gewichtskonstanz (otro) im Umlufttrockenschrank getrocknet. Nach dem Abkühlen wird der Rückstand mit dem Pinsel in eine Schale überführt. Auswertung: Nasssiebrückstand (NSR) in (%) anhand der Auswaage.It was first prepared a 5% suspension of bentonite (otro, ie after drying at 110 ° C) in 2000 g of water. For this purpose, the bentonite is stirred in at 930 rpm in about 5 minutes. After a stirring time of a further 15 minutes at 1865 rpm, the suspension is poured into the cleaned and dried sieve (mesh size 45 μm ) and washed with running tap water under tapping until the wash water runs clear. After washing the sieve residue with tap water, place the sieve in an ultrasonic bath for 5 minutes to sift off the remaining fines. It is important to ensure that when inserting the sieve in the ultrasonic bath between the water surface and sieve bottom no air remains. Rinse briefly with tap water after sonication. Thereafter, the screen is removed and the water renewed in an ultrasonic bath. The work process in the ultrasonic bath is repeated until no more contamination of the water is detected. The sieve with the remaining residue is dried to constant weight (otro) in a circulating air drying cabinet. After cooling, the residue is transferred with the brush into a bowl. Evaluation: wet sieve residue (NSR) in (%) based on the weight.
Dabei handelt es sich um eine gängiges Verfahren. Es wurde ein Mastersizer der Firma Malvern Instruments Ltd, UK, entsprechend der Angaben des Herstellers eingesetzt. Die Messungen wurden mit der vorgesehenen Probenkammer ("dry powder feeder") in Luft durchgeführt und die auf das Probenvolumen bezogenen Werte ermittelt.This is a common procedure. A Mastersizer from Malvern Instruments Ltd, UK was used according to the manufacturer's instructions. The measurements were carried out with the provided dry powder feeder in air and the values related to the sample volume were determined.
Der gewählte Papierstoff (z.B. 45 % Zellstoff und 55% peroxid-gebleichter Holzschliff) kann entweder direkt aus der Papierfabrik erhalten werden, oder vor dem Einsatz im Kühlschrank aufbewahrt werden. Der Papierstoff wurde dann gut geschüttelt bei 20 g atro auf 2% mit warmem entionisiertem Wasser in einem 2000ml Becherglas verdünnt. Während mit 400 UpM gerührt wurde, erwärmte sich der Papierstoffansatz mit Hilfe einer Heizplatte auf 40°C. Wird die Temperatur erreicht, wird die zu testende Menge an Adsorbens mit Hilfe einer Pasteurpipette zu dem Papierstoffansatz zugegeben. Anschließend ist die Adsorptionszeit im Stoffansatz auf 30 min bei 40°C festgelegt und die Mischung wird solange mit 400 UpM gerührt. Danach wird der Papierstoffansatz mit dem Adsorbens auf 1% Feststoffgehalt mit Hilfe von entionisiertem Wasser (40°C) verdünnt.The selected stock (eg 45% pulp and 55% peroxide bleached wood pulp) can either be obtained directly from the mill or stored in the refrigerator before use. The stock was then shaken well at 20g dry to 2% with warm deionized water in a 2000ml beaker. While stirring at 400 rpm, the pulp batch was heated to 40 ° C. using a hot plate. When the temperature is reached, the amount of adsorbent to be tested is added to the stock batch using a Pasteur pipette. Subsequently, the adsorption time in the batch is fixed at 40 ° C. for 30 minutes and the mixture is stirred at 400 rpm for as long as possible. Thereafter, the paper stock approach with the adsorbent diluted to 1% solids content using deionized water (40 ° C).
Für die Siebwasserherstellung werden 1000g dieses verdünnten Stoffansatzes (1 Gew-% Feststoffanteil) im Entwässerungs- und Retentionsgerät (Mütek DF3 03 der Firma Mütek, DE) 420 Sekunden entwässert (Sieb 170 µm, Rührgeschwindigkeit 700 upM). Die Siebwasserproben werde analytisch untersucht.For the Siebwasserherstellung 1000g of this diluted material approach are (1 wt% solids) in the drainage and retention device (Mütek Mutek, DE DF3 03) dewatered 420 seconds (170 μ sieve m, stirring speed 700 rpm). The white water samples are analyzed analytically.
Hier wurde die sogenannte Durchflusszytometrie verwendet, wie in
Hier wurde die Methode von
Es zeigen:
-
zeigt eine Graphik zur Abhängigkeit der Konzentration der Störstoffteilchen im Siebwasser (Filtratwasser) von der Art und Menge des eingesetzten Adsorbens (Bentonit bzw. Talk).Figur 1
-
FIG. 1 shows a graph of the dependence of the concentration of impurity particles in the white water (filtrate water) on the type and amount of adsorbent used (bentonite or talc).
Die Erfindung wird nun anhand der nachstehenden nichtbeschränkenden Beispiele weiter veranschaulicht.The invention will now be further illustrated by the following non-limiting examples.
Es wurden die nachstehenden Materialien zur Störstoffbindung untersucht.The following materials for impurity binding were examined.
Die analytischen Daten des verwendeten Calciumbentonits sind in Tabelle 1 zusammengefasst. Die Anteile and der CEC finden sich in Tabelle 2.
Der Nasssiebrückstand (45µm) lag bei kleiner 0,5 Gew.-%.
Bentonit 2 wurde aus Bentonit 1 erhalten, indem gemäß dem vorstehenden Verfahren Bentonit 1 mit 5 Gew.-% Soda bezogen auf den wasserfreien Bentonit verknetet, auf einen Wassergehalt von 10 Gew.-% getrocknet und anschließend auf eine entsprechende Korngröße wie Bentonit 1 (Vergleich Tabelle 2) vermahlen wurde. Durch diese Verarbeitungsschritte werden die mineralogischen Daten des Bentonits nicht verändert, so dass der Montmorillonitgehalt sowie der Gehalt an Begleitmineralien unverändert bleibt. Die BET-Oberfläche lag bei 85 ± 2 m2/g.
Die analytischen Daten für Bentonit 2 sind in Tabelle 3 angegeben.
Mit den beiden Bentoniten 1 und 2 wurde die Störstoffbindung wie im Methodenteil beschrieben untersucht. Zur Durchführung der Filtrationsexperimente wurde ein Papierstoff eingesetzt, der einer Papiermaschine entnommen war und aus 45 % Langfaserzellstoff und 55% peroxid-gebleichtem Holzschliff bestand.With the two
Zum Vergleich wurde jeweils eine "Nullprobe" gefahren, d.h. es wurden keine Adsorbentien zur Störstoffbindung eingesetzt.For comparison, in each case a "zero sample" was driven, i. no adsorbents were used for impurity binding.
Zur Charakterisierung der Filtratwässer (Siebwässer) im Hinblick auf eine Reduktion von Störstoffen wurde die vorstehend angegebene Durchflusszytometrie verwendet. Die Ergebnisse sind in Figur 1 dargestellt. Dabei ist die Menge des eingesetzten Adsorbens (Bentonit bzw. Talk) gegen sie Konzentration der Störstoffteilchen im Siebwasser aufgetragen. Es zeigt sich deutlich, dass der erfindungsgemäße Bentonit 2 bereits bei einer geringen eingesetzten Menge von drei Kilogramm pro Tonne bezogen auf die Papierpulpe/Suspension in Trockenmasse eine wesentlich bessere Störstoffbindung zeigt als Bentonit 1 oder Talk.For the characterization of the filtrate waters (white water) with a view to a reduction of interfering substances, the above flow cytometry was used. The results are shown in FIG. The amount of adsorbent used (bentonite or talc) is plotted against it Concentration of Störstoffteilchen in white water. It can be clearly seen that
Über die gaschromatographische Analyse (siehe Methodenteil) wurde der Gehalt an Fettsäuren, Ligninen, Sterolen, Sterylestern sowie Triglyceriden für die vorstehenden Proben bestimmt. Die Bentonite 1 und 2 wurden dabei mit jeweils 6 kg/t Papier (Trockengewicht) eingesetzt; der kationisierte Talk wurde mit 11,25 kg/t Papier eingesetzt, da 6 kg/t schlechte Ergebnisse lieferten. Die erhaltenen Werte ergeben sich aus Tabelle 4.
Wie aus Tabelle 4 ersichtlich ist, zeigt die mit dem erfindungsgemäßen Bentonit 2 behandelte Probe sowohl gegenüber der mit kationisiertem Talk behandelten Probe als auch der mit dem nicht-erfindungsgemäßen Calciumbentonit (Bentonit 1) behandelten Probe eine deutlich bessere Bindung/Entfernung von Fettsäuren, Ligninen, Styrolen, Styrylestern sowie Triglyceriden.As can be seen from Table 4, the sample treated with the
In einem weiteren Beispiel wurde der erfindungsgemäße Bentonit mit herkömmlichen Bentoniten verglichen, die zwar einen Anteil der einwertigen Kationen an der CEC von mindestens 0,7 (70%) aufwiesen, jedoch eine CEC von weniger als 85 meq/100g.In another example, the bentonite of the present invention was compared to conventional bentonites which had at least 0.7 (70%) monovalent cation content at the CEC but a CEC of less than 85 meq / 100g.
Es zeigte sich wiederum eine wesentlich bessere Störstoffbindung des erfindungsgemäßen Bentonits im Vergleich zu den herkömmlichen Bentoniten bereits bei geringen Einsatzmengen.Again, it showed a much better impurity binding of the bentonite invention compared to the conventional bentonites even at low levels.
Claims (18)
- Method for binding impurities in paper production, comprising the following steps:a) provision of a bentonite, the proportion of the monovalent cations, based on the cation exchange capacity (CEC) of the bentonite, being at least 0.7 and the CEC being more than 85 meq/100 g, preferably more than 90 meq/100 g, in particular more than 95 meq/100 g;b) addition of the bentonite according to a) to a paper pulp or fiber suspension;c) binding of the impurities to the bentonite in the pulp or fiber suspension.
- Method according to Claim 1, characterized in that the proportion of the monovalent cations, based on the CEC of the bentonite, is more than 0.7, in particular more than 0.8, preferably more than 0.85.
- Method according to either of the preceding claims, characterized in that the proportion of calcium and/or magnesium ions, based on the CEC of the bentonite, is less than 0.2, in particular less than 0.18, preferably less than 0.15.
- Method according to any of the preceding claims, characterized in that the particle size of the bentonite is chosen so that in the wet sieve residue less than 2% by weight, preferably less than 1% by weight, in particular less than 0.5% by weight, is 45 µm.
- Method according to any of the preceding claims, characterized in that the monovalent cations are sodium, potassium and/or lithium, in particular sodium.
- Method according to any of the preceding claims, characterized in that the bentonite is present in particulate form having a median particle size (D50, based on volume) of from 0.5 to 10 µm, in particular from 2 to 6 µm, particularly preferably from 3 to 5 µm.
- Method according to any of the preceding claims, characterized in that the addition of the bentonite is effected in the absence of talc.
- Method according to any of the preceding claims, characterized in that the bentonite has a swellability of at least 25 ml/2 g, in particular of at least 30 ml/2 g, more preferably of at least 35 ml/2 g.
- Method according to any of the preceding claims, characterized in that the bentonite has a proportion of iron ions, based on the CEC, of preferably less than about 0.005.
- Method according to any of the preceding claims, characterized in that the bentonite has a BET surface area of less than 100 m2/g, in particular less than 90 m2/g.
- Method according to any of the preceding claims, characterized in that from about 0.5 to 10 kg of bentonite are added per tonne of paper pulp or fiber suspension (dry weight), in particular from 1 to 7 kg/t of pulp or fiber suspension.
- Methode according to any of the preceding claims, characterized in that the paper pulp or fiber suspension contains groundwood fractions.
- Methode according to any of the preceding claims, characterized in that the groundwood fraction in the paper pulp or the fiber suspension is at least 10% by weight, in particular at least 30% by weight, based on the total pulp or fiber suspension (dry weight).
- Method according to any of the preceding claims, characterized in that no additional talc is added to the paper pulp or fiber suspension.
- Use of a bentonite as defined in Claim 1. a) for binding impurities in paper production.
- Use according to the preceding claim, characterized in that the use is effected in a paper pulp or fiber suspension comprising groundwood fractions.
- Use according to either of Claims 15 and 16, characterized in that the use is effected without the additional use of talc.
- Use according to any of Claims 15 to 17 as a partial or complete replacement for other compositions for impurity elimination, such as polyelectrolytes or talc.
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PL05826382T PL1825056T3 (en) | 2004-12-16 | 2005-11-30 | Bentonite for binding impurities during paper production |
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DE102004060587A DE102004060587A1 (en) | 2004-12-16 | 2004-12-16 | Bentonites for impurity binding in papermaking |
PCT/EP2005/012775 WO2006063682A2 (en) | 2004-12-16 | 2005-11-30 | Bentonite for binding impurities during paper production |
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US (1) | US20090044921A1 (en) |
EP (1) | EP1825056B1 (en) |
JP (1) | JP2008524451A (en) |
KR (1) | KR20070089805A (en) |
BR (1) | BRPI0515785A (en) |
DE (1) | DE102004060587A1 (en) |
ES (1) | ES2531071T3 (en) |
MX (1) | MX2007006952A (en) |
PL (1) | PL1825056T3 (en) |
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JP4868282B2 (en) * | 2006-09-15 | 2012-02-01 | 星光Pmc株式会社 | Dirt prevention method |
US20100132251A1 (en) * | 2006-11-07 | 2010-06-03 | Ulrich Sohling | Method for purification of biodiesel |
EP1920829A1 (en) | 2006-11-07 | 2008-05-14 | Süd-Chemie Ag | Amorphous adsorbent, method of obtaining the same and its use in the bleaching of fats and/or oils |
EP1927397A1 (en) | 2006-11-13 | 2008-06-04 | Süd-Chemie Ag | Absorbent composition for surface treatment |
WO2010070682A1 (en) * | 2008-12-15 | 2010-06-24 | Imi Fabi S.P.A. | Talc- and/or chlorite-based compositions and use thereof in controlling pollutants in papermaking industry processes |
EP3128073A1 (en) | 2015-08-06 | 2017-02-08 | Clariant International Ltd | Composite material for combating impurities in the manufacture of paper |
SI3260597T1 (en) | 2016-06-22 | 2019-10-30 | Buchmann Ges Mit Beschraenkter Haftung | Multi-layer fibre product with an inhibited migration rate of aromatic or saturated hydrocarbons and method for producing the same |
CN115109451B (en) * | 2022-06-17 | 2023-08-18 | 阳原县仁恒精细粘土有限责任公司 | Water-based emulsion paint containing high-expansibility bentonite |
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DE3541163A1 (en) * | 1985-11-21 | 1987-05-27 | Basf Ag | METHOD FOR PRODUCING PAPER AND CARDBOARD |
GB8602121D0 (en) * | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
US4913775A (en) * | 1986-01-29 | 1990-04-03 | Allied Colloids Ltd. | Production of paper and paper board |
GB8628807D0 (en) * | 1986-12-02 | 1987-01-07 | Ecc Int Ltd | Clay composition |
US4964955A (en) * | 1988-12-21 | 1990-10-23 | Cyprus Mines Corporation | Method of reducing pitch in pulping and papermaking operations |
GB8828899D0 (en) * | 1988-12-10 | 1989-01-18 | Laporte Industries Ltd | Paper & paperboard |
US5032227A (en) * | 1990-07-03 | 1991-07-16 | Vinings Industries Inc. | Production of paper or paperboard |
GB9127173D0 (en) * | 1991-12-21 | 1992-02-19 | Vinings Ind Inc | Method for controlling pitch |
US5368692A (en) * | 1992-01-22 | 1994-11-29 | Vinings Industries Inc. | Method for controlling pitch |
DK0586755T3 (en) * | 1992-07-02 | 1997-12-01 | Ecc Int Ltd | Method of controlling pitch deposition in papermaking |
JPH0665892A (en) * | 1992-08-19 | 1994-03-08 | Mizusawa Ind Chem Ltd | Pitch adsorbent |
GB2297334A (en) * | 1995-01-25 | 1996-07-31 | Ecc Int Ltd | Agent for controlling the deposition of pitch in papermaking |
GB9604950D0 (en) * | 1996-03-08 | 1996-05-08 | Allied Colloids Ltd | Clay compositions and their use in paper making |
US5798023A (en) * | 1996-05-14 | 1998-08-25 | Nalco Chemical Company | Combination of talc-bentonite for deposition control in papermaking processes |
DE19627553A1 (en) * | 1996-07-09 | 1998-01-15 | Basf Ag | Process for the production of paper and cardboard |
JPH10194726A (en) * | 1997-01-09 | 1998-07-28 | Mizusawa Ind Chem Ltd | High-concentration bentonite aqueous slurry excellent in long-term storage, its application and use thereof |
JP2005522590A (en) * | 2002-04-08 | 2005-07-28 | チバ スペシャルティ ケミカルズ ウォーター トリートメント リミテッド | White pitch deposit treatment |
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PL1825056T3 (en) | 2015-07-31 |
DE102004060587A1 (en) | 2006-07-06 |
ES2531071T3 (en) | 2015-03-10 |
BRPI0515785A (en) | 2008-08-05 |
PT1825056E (en) | 2015-04-08 |
MX2007006952A (en) | 2007-06-25 |
WO2006063682A3 (en) | 2007-01-25 |
JP2008524451A (en) | 2008-07-10 |
KR20070089805A (en) | 2007-09-03 |
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US20090044921A1 (en) | 2009-02-19 |
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