EP1838463B2 - Verfahren zum klassieren eines teilchenförmigen wasserabsorbierenden harzes - Google Patents
Verfahren zum klassieren eines teilchenförmigen wasserabsorbierenden harzes Download PDFInfo
- Publication number
- EP1838463B2 EP1838463B2 EP05821876.9A EP05821876A EP1838463B2 EP 1838463 B2 EP1838463 B2 EP 1838463B2 EP 05821876 A EP05821876 A EP 05821876A EP 1838463 B2 EP1838463 B2 EP 1838463B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- sieving apparatus
- temperature
- range
- gas stream
- 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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- 239000011347 resin Substances 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 238000007873 sieving Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000012644 addition polymerization Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 238000012216 screening Methods 0.000 description 11
- 239000004971 Cross linker Substances 0.000 description 10
- 229920005601 base polymer Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
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- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229940087168 alpha tocopherol Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 150000007942 carboxylates Chemical group 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 239000004745 nonwoven fabric Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical class OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- NQQRXZOPZBKCNF-NSCUHMNNSA-N (e)-but-2-enamide Chemical compound C\C=C\C(N)=O NQQRXZOPZBKCNF-NSCUHMNNSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- QBGJZIGMETUVBL-UHFFFAOYSA-N 3-(2-hydroxyethyl)-1,3-oxazolidin-2-id-4-one Chemical compound OCCN1[CH-]OCC1=O QBGJZIGMETUVBL-UHFFFAOYSA-N 0.000 description 1
- CARNFEUGBMWTON-UHFFFAOYSA-N 3-(2-prop-2-enoxyethoxy)prop-1-ene Chemical compound C=CCOCCOCC=C CARNFEUGBMWTON-UHFFFAOYSA-N 0.000 description 1
- XUYDVDHTTIQNMB-UHFFFAOYSA-N 3-(diethylamino)propyl prop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C=C XUYDVDHTTIQNMB-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- 125000004080 3-carboxypropanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C(O[H])=O 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- QGXMPHBQJFXJCI-UHFFFAOYSA-N 4-(dimethylamino)butyl prop-2-enoate Chemical compound CN(C)CCCCOC(=O)C=C QGXMPHBQJFXJCI-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 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 description 1
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- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NEGKNLJVKTUFJV-UHFFFAOYSA-N [1-(dimethylamino)-2,2-dimethylpropyl] 2-methylprop-2-enoate Chemical compound CN(C)C(C(C)(C)C)OC(=O)C(C)=C NEGKNLJVKTUFJV-UHFFFAOYSA-N 0.000 description 1
- KNUSQTXJWATMLJ-UHFFFAOYSA-N [1-(dimethylamino)-2,2-dimethylpropyl] prop-2-enoate Chemical compound CN(C)C(C(C)(C)C)OC(=O)C=C KNUSQTXJWATMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000003289 ascorbyl group Chemical group [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical group C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- MENOBBYDZHOWLE-UHFFFAOYSA-N morpholine-2,3-dione Chemical compound O=C1NCCOC1=O MENOBBYDZHOWLE-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 125000002640 tocopherol group Chemical class 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B1/00—Sieving, screening, sifting, or sorting solid materials using networks, gratings, grids, or the like
- B07B1/46—Constructional details of screens in general; Cleaning or heating of screens
- B07B1/56—Heated screens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B1/00—Sieving, screening, sifting, or sorting solid materials using networks, gratings, grids, or the like
- B07B1/28—Moving screens not otherwise provided for, e.g. swinging, reciprocating, rocking, tilting or wobbling screens
- B07B1/40—Resonant vibration screens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B1/00—Sieving, screening, sifting, or sorting solid materials using networks, gratings, grids, or the like
- B07B1/46—Constructional details of screens in general; Cleaning or heating of screens
Definitions
- the present invention relates to a method for classifying a particulate water-absorbent resin by means of a sieving apparatus at a pressure reduced from the ambient pressure.
- Water-absorbent resins typically have a centrifuge retention capacity of 15 to 60 g / g, preferably at least 20 g / g, preferably at least 25 g / g, more preferably at least 30 g / g, most preferably at least 35 g / g.
- Centrifuge retention capacity is determined according to the EDANA (European Disposables and Nonwovens Association) recommended test method no. 441.2-02 "Centrifuge retention capacity".
- the preparation of water-absorbing resins usually comprises the steps of polymerization, drying, comminution, classification, postcrosslinking and, if appropriate, renewed classification.
- the object of the present invention was to find a simplified method for the classification of water-absorbing resins, which allows high screening performance and long equipment runtimes.
- this object is achieved by classifying water-absorbing resins at reduced pressure relative to the ambient pressure, preferably at a pressure of at most 950 mbar, preferably at a pressure of at most 900 mbar, particularly preferably at a pressure of at most 800 mbar preferably at a pressure of at most 700 mbar, wherein the resin is overflown during the classifying with a gas, and wherein the gas flow in front of the screening device has a temperature of at least 40 ° C.
- the pressure is usually at least 10 mbar, preferably at least 50 mbar, preferably at least 100 mbar, more preferably at least 200 mbar, most preferably at least 300 mbar.
- Another aspect of the present invention is the screening device for carrying out the classification method according to the invention.
- the screening devices which are suitable for the classification method according to the invention are not subject to any restrictions; plane sieve methods are preferred, tumble screening machines are very particularly preferred.
- the screening device is typically shaken to aid classification. This is preferably done so that the material to be classified is spirally guided over the sieve.
- This forced vibration typically has an amplitude of 0.7 to 40 mm, preferably 1.5 to 25 mm, and a frequency of 1 to 100 Hz, preferably of 5 to 10 Hz.
- the water-absorbent resin is overflowed during the classifying with a gas stream, particularly preferably air.
- the amount of gas is typically from 0.1 to 10 m 3 / h per m 2 screen area, preferably from 0.5 to 5 m 3 / h per m 2 screen area, particularly preferably from 1 to 3 m 3 / h per m 2 screen area, the gas volume being measured under standard conditions (25 ° C and 1 bar).
- the gas stream is before entering the screening device to a temperature of at least 40 ° C, preferably to a temperature of at least 50 ° C, preferably to a temperature of at least 60 ° C, more preferably to a temperature of at least 65 ° C, all more preferably at a temperature of at least 70 ° C.
- the temperature of the gas stream is usually less than 120 ° C, preferably less than 110 ° C, preferably less than 100 ° C, more preferably less than 90 ° C, most preferably less than 80 ° C.
- the water content of the gas stream is typically not more than 5 g / kg, preferably not more than 4.5 g / kg, preferably not more than 4 g / kg, more preferably not more than 3.5 g / kg, most preferably not more than 3 g / kg.
- a gas stream with a low water content can be generated, for example, by condensing a corresponding amount of water from the gas stream having a higher water content by cooling.
- the screening device can still be heated and / or thermally insulated, such as in EP-A-0 855 232 described.
- the screening device is operated at a temperature of 40 to 80 ° C.
- Suitable monomers i) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic acid esters. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
- Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
- Tocopherol is understood as meaning compounds of the following formula wherein R 1 is hydrogen or methyl, R 2 is hydrogen or methyl, R 3 is hydrogen or methyl and R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
- Preferred radicals for R 4 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids.
- the carboxylic acids may be mono-, di- or tricarboxylic acids.
- R 4 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
- the monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, particularly preferably around 50 ppm by weight, hydroquinone hemether, in each case on acrylic acid, wherein acrylic acid salts are mathematically taken into account as acrylic acid.
- an acrylic acid having a corresponding content of hydroquinone half-ether may be used to prepare the monomer solution.
- the water-absorbing polymers are crosslinked, ie the polymerization is carried out in the presence of compounds having at least two polymerisable groups which can be radically copolymerized into the polymer network.
- Suitable crosslinkers ii) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as in EP-A-0 530 438 described, di- and triacrylates, as in EP-A-0 547 847 . EP-A-0 559 476 . EP-A-0 632 068 . WO-A-93/21237 .
- WO-A-03/104299 WO-A-03/104300 .
- WO-A-03/104301 and in the German patent application with the file number 10331450.4 described, mixed acrylates containing in addition to acrylate groups further ethylenically unsaturated groups, as in the German patent applications with the file reference 10331456.3 and 10355401.7 or crosslinker mixtures, such as in DE-A-195 43 368 .
- DE-A-196 46 484 WO 90/15830 and WO-A-02/32962 described.
- Suitable crosslinkers ii) are, in particular, N, N'-methylenebisacrylamide and N, N'-methylenebismethacrylamide, esters of unsaturated monocarboxylic or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol diacrylate or methacrylate, and trimethylolpropane triacrylate and allyl compounds, such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in US Pat EP-A-0 343 427 are described.
- crosslinkers ii) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol and glycerol triallyl ethers, polyallyl ethers based on sorbitol, and ethoxylated variants thereof.
- Useful in the process according to the invention are di (meth) acrylates of polyethylene glycols, wherein the polyethylene glycol used has a molecular weight between 300 and 1000.
- crosslinkers ii) are di- and triacrylates of 3 to 20 times ethoxylated glycerol, 3 to 20 times ethoxylated trimethylolpropane, 3 to 20 times ethoxylated trimethylolethane, especially di- and triacrylates of 2 to 6-fold ethoxylated glycerol or trimethylolpropane, 3-fold propoxylated glycerin or trimethylolpropane, as well as the 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-fold ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, trimethylolethane or trimethylolpropane.
- Very particularly preferred crosslinkers ii) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in the earlier German application with file reference DE 10319462.2 are described.
- Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
- Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerin.
- acrylamide, methacrylamide, crotonic acid amide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate, and dimethylaminoneopentyl methacrylate are exemplified by ethylenically unsaturated monomers iii) copolymerizable with monomers i).
- water-soluble polymers iv) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
- the reaction is preferably carried out in a kneader, such as in WO-A-01/38402 described, or on a belt reactor, such as in EP-A-0 955 086 described, performed.
- the acid groups of the hydrogels obtained are usually partially neutralized, preferably from 25 to 95 mol%, preferably from 27 to 80 mol%, particularly preferably from 27 to 30 mol% or from 40 to 75 mol%, using the usual neutralizing agents may, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal hydrogencarbonates and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used. Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
- the neutralization is achieved by mixing the neutralizing agent as an aqueous solution, as a melt, or preferably as a solid.
- sodium hydroxide with a water content well below 50 wt .-% may be present as a waxy mass with a melting point above 23 ° C. In this case, a dosage as general cargo or melt at elevated temperature is possible.
- the neutralization can be carried out after the polymerization at the hydrogel stage. However, it is also possible to neutralize up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, of the acid groups before the polymerization by adding a part of the neutralizing agent already to the monomer solution and the desired final degree of neutralization only after the polymerization is adjusted at the level of the hydrogel.
- the monomer solution can be neutralized by mixing in the neutralizing agent.
- the hydrogel can be mechanically comminuted, for example by means of a meat grinder, wherein the neutralizing agent can be sprayed, sprinkled or poured over and then thoroughly mixed. For this purpose, the gel mass obtained can be further gewolfft for homogenization. Neutralization of the monomer solution directly to the final degree of neutralization is preferred.
- the neutralized hydrogel is then dried with a belt or drum dryer until the residual moisture content is preferably below 15 wt .-%, in particular below 10 wt .-%, wherein the water content according to the recommended by the EDANA (European Disposables and Nonwovens Association) Test Method no 430.2-02 "Moisture content" is determined.
- a fluidized bed dryer or a heated ploughshare mixer can be used for drying.
- it is advantageous in the drying of this gel to ensure rapid removal of the evaporating water.
- the dryer temperature must be optimized, the air supply and removal must be controlled, and it is in any case to ensure adequate ventilation.
- the drying is naturally simpler and the product is the whiter, if the solids content of the gel is as high as possible.
- the solids content of the gel before drying is therefore preferably between 30 and 80% by weight.
- Particularly advantageous is the ventilation of the dryer with nitrogen or other non-oxidizing inert gas.
- nitrogen or other non-oxidizing inert gas it is also possible simply to lower only the partial pressure of the oxygen during the drying in order to prevent oxidative yellowing processes.
- sufficient ventilation and removal of the water vapor also leads to an acceptable product.
- Advantageous in terms of color and product quality is usually the shortest possible drying time.
- the dried hydrogel is thereafter ground and classified, wherein for grinding usually one- or multi-stage roller mills, preferably two- or three-stage roller mills, pin mills, hammer mills or vibratory mills can be used.
- water-absorbent polymer particles are generally postcrosslinked. This postcrosslinking can be carried out in aqueous gel phase.
- ground and sieved polymer particles base polymer
- crosslinkers suitable for this purpose are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the hydrophilic polymer or which can crosslink at least two carboxyl groups or other functional groups of at least two different polymer chains of the base polymer.
- Suitable postcrosslinkers v) are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the polymers.
- Suitable compounds are, for example, alkoxysilyl compounds, polyaziridines, polyamines, polyamidoamines, di- or polyglycidyl compounds, as in EP-A-0 083 022 .
- EP-A-543,303 and EP-A-937 736 described polyhydric alcohols, as in DE-C-33 14 019 .
- mixed functionality such as glycidol, 3-ethyl-3-oxetanemethanol (trimethylolpropane oxetane), as in EP-A-1 199 327 described, aminoethanol, diethanolamine, triethanolamine or compounds which form a further functionality after the first reaction, such as ethylene oxide, propylene oxide, isobutylene oxide, aziridine, azetidine or oxetane.
- the post-crosslinking is usually carried out so that a solution of the postcrosslinker is sprayed onto the hydrogel or the dry base polymer particles. Subsequent to the spraying, it is thermally dried, whereby the postcrosslinking reaction can take place both before and during the drying.
- the spraying of a solution of the crosslinker is preferably carried out in mixers with agitated mixing tools, such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers.
- agitated mixing tools such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers.
- Vertical mixers are particularly preferred, plowshare mixers and paddle mixers are very particularly preferred.
- Suitable mixers are, for example, Lödige® mixers, Bepex® mixers, Nauta® mixers, Processall® mixers and Schugi® mixers.
- the thermal drying is preferably carried out in contact dryers, more preferably paddle dryers, very particularly preferably disk dryers.
- Suitable dryers include Bepex® dryers and, Nara® dryers.
- fluidized bed dryers can also be used.
- the drying can take place in the mixer itself, by heating the jacket or blowing hot air. Also suitable is a downstream dryer, such as a hopper dryer, a rotary kiln or a heatable screw. However, it is also possible, for example, to use an azeotropic distillation as the drying process.
- Preferred drying temperatures are in the range 50 to 250 ° C, preferably at 50 to 200 ° C, and particularly preferably at 50 to 150 ° C.
- the preferred residence time at this temperature in the reaction mixer or dryer is less than 30 minutes, more preferably less than 10 minutes.
- the classification method according to the invention is preferably carried out after the drying of the base polymer, before the post-crosslinking and / or after the post-crosslinking.
- the water content of the water-absorbing resin after drying of the base polymer or before post-crosslinking is typically from 2 to 10% by weight and after post-crosslinking typically below 1% by weight, preferably below 0.1% by weight.
- the temperature of the heating mantle was adjusted to the reaction temperature in the reactor by means of control.
- the crumbly gel finally obtained was then dried at 160 ° C for 3 hours in a convection oven. It was then ground and sieved to 250 to 850 microns.
- the water content was 2.7% by weight.
- the ground base polymer was added to the sieve at the indicated temperature.
- the sieve could be operated at reduced pressure.
- the screen was covered with preheated air with defined water vapor content. The amount of air was 2 m 3 / h per m 2 screen area.
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Combined Means For Separation Of Solids (AREA)
- Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005001789A DE102005001789A1 (de) | 2005-01-13 | 2005-01-13 | Verfahren zum Klassieren eines teilchenförmigen wasserabsorbierenden Harzes |
PCT/EP2005/014163 WO2006074816A1 (de) | 2005-01-13 | 2005-12-31 | Verfahren zum klassieren eines teilchenförmigen wasserabsorbierenden harzes |
Publications (3)
Publication Number | Publication Date |
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EP1838463A1 EP1838463A1 (de) | 2007-10-03 |
EP1838463B1 EP1838463B1 (de) | 2011-06-22 |
EP1838463B2 true EP1838463B2 (de) | 2019-08-14 |
Family
ID=36011074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP05821876.9A Active EP1838463B2 (de) | 2005-01-13 | 2005-12-31 | Verfahren zum klassieren eines teilchenförmigen wasserabsorbierenden harzes |
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US (1) | US8104621B2 (zh) |
EP (1) | EP1838463B2 (zh) |
JP (1) | JP2008526498A (zh) |
CN (1) | CN101102854B (zh) |
AT (1) | ATE513627T1 (zh) |
DE (1) | DE102005001789A1 (zh) |
TW (1) | TW200631676A (zh) |
WO (1) | WO2006074816A1 (zh) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090261023A1 (en) | 2006-09-25 | 2009-10-22 | Basf Se | Method for the Classification of Water Absorbent Polymer Particles |
CN101516531B (zh) * | 2006-09-25 | 2014-05-21 | 巴斯夫欧洲公司 | 吸水性聚合物颗粒的分级方法 |
CN101516530B (zh) * | 2006-09-25 | 2012-06-27 | 巴斯夫欧洲公司 | 吸水性聚合物颗粒的分级方法 |
US10099254B2 (en) * | 2007-03-26 | 2018-10-16 | Nippon Shokubai Co., Ltd. | Classification method of particulate water absorbent resin |
CN101970316B (zh) * | 2008-03-13 | 2013-06-12 | 株式会社日本触媒 | 吸水性树脂的制造方法 |
JP5710966B2 (ja) | 2008-03-28 | 2015-04-30 | 株式会社日本触媒 | 吸水性樹脂粉体の輸送方法 |
JP5390511B2 (ja) | 2008-04-11 | 2014-01-15 | 株式会社日本触媒 | 吸水性樹脂の表面処理方法および吸水性樹脂の製造方法 |
JP5560192B2 (ja) | 2008-09-16 | 2014-07-23 | 株式会社日本触媒 | 吸水性樹脂の製造方法および通液性向上方法 |
CN102655950B (zh) | 2009-02-18 | 2015-05-13 | 巴斯夫欧洲公司 | 制备吸水聚合物颗粒的方法 |
CN102378778A (zh) | 2009-03-31 | 2012-03-14 | 株式会社日本触媒 | 颗粒状吸水性树脂的制造方法 |
WO2011034147A1 (ja) | 2009-09-16 | 2011-03-24 | 株式会社日本触媒 | 吸水性樹脂粉末の製造方法 |
CN102574941B (zh) | 2009-10-09 | 2015-09-16 | 巴斯夫欧洲公司 | 用于再润湿表面后交联吸水性聚合物颗粒的方法 |
JP5587348B2 (ja) | 2010-01-20 | 2014-09-10 | 株式会社日本触媒 | 吸水性樹脂の製造方法 |
EP2535369B1 (en) | 2010-02-10 | 2021-03-24 | Nippon Shokubai Co., Ltd. | Process for producing water-absorbing resin powder |
WO2011111857A1 (ja) | 2010-03-12 | 2011-09-15 | 株式会社日本触媒 | 吸水性樹脂の製造方法 |
WO2011115221A1 (ja) | 2010-03-17 | 2011-09-22 | 株式会社日本触媒 | 吸水性樹脂の製造方法 |
EP2557095B1 (en) | 2010-04-07 | 2016-10-05 | Nippon Shokubai Co., Ltd. | Method for producing water absorbent polyacrylic acid (salt) resin powder, and water absorbent polyacrylic acid (salt) resin powder |
EP2565219B1 (en) | 2010-04-27 | 2018-06-27 | Nippon Shokubai Co., Ltd. | Method for producing polyacrylic acid (salt)-based water absorbent resin powder |
EP2700667B1 (en) | 2011-04-20 | 2017-08-09 | Nippon Shokubai Co., Ltd. | Process and apparatus for producing water-absorbable resin of polyacrylic acid (salt) type |
WO2013002387A1 (ja) | 2011-06-29 | 2013-01-03 | 株式会社日本触媒 | ポリアクリル酸(塩)系吸水性樹脂粉末及びその製造方法 |
CN103946248B (zh) * | 2011-11-16 | 2016-08-24 | 株式会社日本触媒 | 聚丙烯酸(盐)系吸水性树脂的制造方法 |
JP5996651B2 (ja) | 2012-08-01 | 2016-09-21 | 株式会社日本触媒 | ポリアクリル酸(塩)系吸水性樹脂の製造方法 |
JP5883948B2 (ja) | 2012-11-27 | 2016-03-15 | 株式会社日本触媒 | ポリアクリル酸(塩)系吸水性樹脂の製造方法 |
CN105593119B (zh) | 2013-09-30 | 2018-11-13 | 株式会社日本触媒 | 颗粒状吸水剂的填充方法和颗粒状吸水剂填充物的取样方法 |
JP6670822B2 (ja) * | 2015-02-24 | 2020-03-25 | 住友精化株式会社 | 吸水性樹脂製造装置 |
EP3279239B1 (en) * | 2015-04-02 | 2022-06-01 | Nippon Shokubai Co., Ltd. | Method for producing particulate water-absorbing agent that has polyacrylic acid (salt)-based water-absorbing resin as main component |
WO2017207330A1 (de) | 2016-05-31 | 2017-12-07 | Basf Se | Verfahren zur herstellung von superabsorbern |
EP3661662B1 (en) * | 2017-07-31 | 2024-09-11 | Basf Se | Classification process for superabsorbent polymer particles |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06126252A (ja) † | 1992-10-16 | 1994-05-10 | Ube Ind Ltd | フライアッシュの品質改善方法 |
EP0780424A1 (en) † | 1995-07-07 | 1997-06-25 | Nippon Shokubai Co., Ltd. | Water absorbent powder and process for the production thereof |
JPH11179187A (ja) † | 1997-12-24 | 1999-07-06 | Terunaito:Kk | 分散機構付き粉体供給機並びにそれを用いた高分子水溶液の調製方法及び廃水または高含水泥土の処理方法 |
WO2000010619A1 (en) † | 1998-08-18 | 2000-03-02 | Stockhausen Gmbh & Co. Kg | Superabsorbent polymers having anti-caking characteristics |
EP1178059A2 (en) † | 2000-08-03 | 2002-02-06 | Nippon Shokubai Co., Ltd. | Water-absorbent resin, hydropolymer, process for producing them, and uses of them |
US20030087983A1 (en) † | 2001-07-06 | 2003-05-08 | Katsuhiro Kajikawa | Water-absorbent resin powder and its production process and uses |
JP2003320308A (ja) † | 2002-04-30 | 2003-11-11 | Sumitomo Chem Co Ltd | 水硬性粉体の造粒物の篩別方法および装置 |
EP1367081A1 (en) † | 2002-05-30 | 2003-12-03 | Nippon Shokubai Co., Ltd. | Production process for particulate water-absorbent resin |
EP1462473A1 (en) † | 2003-03-14 | 2004-09-29 | Nippon Shokubai Co., Ltd. | Surface crosslinking method of water-absorbing resin powder |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1241774A (en) * | 1969-05-28 | 1971-08-04 | Simon Ltd Henry | Improvements in or relating to sieving |
US3948764A (en) * | 1974-09-23 | 1976-04-06 | Browning-Ferris Industries, Inc. | Catalyst screening unit |
US4261817A (en) * | 1978-05-26 | 1981-04-14 | Philip Edwards | Sieving |
US5122262A (en) * | 1990-01-12 | 1992-06-16 | Summers Thomas W | Separator screen with intermittent vacuum |
JP3077988B2 (ja) * | 1990-02-13 | 2000-08-21 | 株式会社日立製作所 | 湿式粉砕・混合および乾燥装置 |
ES2070369T3 (es) * | 1990-07-17 | 1995-06-01 | Sanyo Chemical Ind Ltd | Procedimiento para la fabricacion de resinas absorbentes de agua. |
USRE38444E1 (en) * | 1994-06-13 | 2004-02-24 | Nippon Shokubai Co., Ltd. | Absorbing agent, process of manufacturing same, and absorbent product containing same |
JP3875757B2 (ja) * | 1997-01-27 | 2007-01-31 | 株式会社日本触媒 | 粒子状親水性重合体の分級方法およびふるい分け装置 |
JP3822812B2 (ja) * | 2000-10-23 | 2006-09-20 | 株式会社日本触媒 | 吸水剤およびその製造方法 |
DE102005062929A1 (de) * | 2005-12-29 | 2007-07-05 | Basf Ag | Herstellung eines wasserabsorbierenden Harzes unter Einmischen eines wasserabsorbierenden Harzpulvers |
EP2013251B1 (en) * | 2006-03-27 | 2011-09-14 | Nippon Shokubai Co.,Ltd. | Water absorbing resin with improved internal structure and manufacturing method therefor |
-
2005
- 2005-01-13 DE DE102005001789A patent/DE102005001789A1/de not_active Withdrawn
- 2005-12-31 JP JP2007550714A patent/JP2008526498A/ja active Pending
- 2005-12-31 AT AT05821876T patent/ATE513627T1/de active
- 2005-12-31 CN CN200580046589.8A patent/CN101102854B/zh active Active
- 2005-12-31 WO PCT/EP2005/014163 patent/WO2006074816A1/de active Application Filing
- 2005-12-31 EP EP05821876.9A patent/EP1838463B2/de active Active
- 2005-12-31 US US11/813,306 patent/US8104621B2/en active Active
-
2006
- 2006-01-13 TW TW095101500A patent/TW200631676A/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06126252A (ja) † | 1992-10-16 | 1994-05-10 | Ube Ind Ltd | フライアッシュの品質改善方法 |
EP0780424A1 (en) † | 1995-07-07 | 1997-06-25 | Nippon Shokubai Co., Ltd. | Water absorbent powder and process for the production thereof |
JPH11179187A (ja) † | 1997-12-24 | 1999-07-06 | Terunaito:Kk | 分散機構付き粉体供給機並びにそれを用いた高分子水溶液の調製方法及び廃水または高含水泥土の処理方法 |
WO2000010619A1 (en) † | 1998-08-18 | 2000-03-02 | Stockhausen Gmbh & Co. Kg | Superabsorbent polymers having anti-caking characteristics |
EP1178059A2 (en) † | 2000-08-03 | 2002-02-06 | Nippon Shokubai Co., Ltd. | Water-absorbent resin, hydropolymer, process for producing them, and uses of them |
US20030087983A1 (en) † | 2001-07-06 | 2003-05-08 | Katsuhiro Kajikawa | Water-absorbent resin powder and its production process and uses |
JP2003320308A (ja) † | 2002-04-30 | 2003-11-11 | Sumitomo Chem Co Ltd | 水硬性粉体の造粒物の篩別方法および装置 |
EP1367081A1 (en) † | 2002-05-30 | 2003-12-03 | Nippon Shokubai Co., Ltd. | Production process for particulate water-absorbent resin |
EP1462473A1 (en) † | 2003-03-14 | 2004-09-29 | Nippon Shokubai Co., Ltd. | Surface crosslinking method of water-absorbing resin powder |
Also Published As
Publication number | Publication date |
---|---|
CN101102854A (zh) | 2008-01-09 |
EP1838463A1 (de) | 2007-10-03 |
DE102005001789A1 (de) | 2006-07-27 |
EP1838463B1 (de) | 2011-06-22 |
WO2006074816A1 (de) | 2006-07-20 |
TW200631676A (en) | 2006-09-16 |
CN101102854B (zh) | 2013-04-17 |
ATE513627T1 (de) | 2011-07-15 |
US20080202987A1 (en) | 2008-08-28 |
JP2008526498A (ja) | 2008-07-24 |
US8104621B2 (en) | 2012-01-31 |
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