CN1205117C - 聚硅酸盐微凝胶 - Google Patents
聚硅酸盐微凝胶 Download PDFInfo
- Publication number
- CN1205117C CN1205117C CNB988059983A CN98805998A CN1205117C CN 1205117 C CN1205117 C CN 1205117C CN B988059983 A CNB988059983 A CN B988059983A CN 98805998 A CN98805998 A CN 98805998A CN 1205117 C CN1205117 C CN 1205117C
- Authority
- CN
- China
- Prior art keywords
- polysilicate microgels
- water
- silica
- sio
- require
- 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.)
- Expired - Fee Related
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 125000002091 cationic group Chemical group 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 10
- 229920000620 organic polymer Polymers 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 19
- 159000000013 aluminium salts Chemical class 0.000 claims description 17
- 230000014759 maintenance of location Effects 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 229920002472 Starch Polymers 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229920003043 Cellulose fiber Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000011859 microparticle Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000008346 aqueous phase Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000008394 flocculating agent Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 20
- -1 silica-based sols Chemical compound 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- 239000000123 paper Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 229960001866 silicon dioxide Drugs 0.000 description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 12
- 235000019353 potassium silicate Nutrition 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 229920006317 cationic polymer Polymers 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 229920002401 polyacrylamide Polymers 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 230000003311 flocculating effect Effects 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 235000011128 aluminium sulphate Nutrition 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 241001343274 Dichrostachys spicata Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 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 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0056—Preparation of gels containing inorganic material and water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/545—Silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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Abstract
本发明涉及聚硅酸盐微凝胶。本发明尤其涉及一种将碱金属硅酸盐水溶液与pH值为11或低于11的二氧化硅基材料含水相相混合来制备水性聚硅酸盐微凝胶的方法,涉及聚硅酸盐本身及其作为絮凝剂在造纸工业及水净化处理中的应用;本发明还涉及一种由含纤维素纤维和任选填料的悬浮液造纸的方法,该方法包括向悬浮液添加至少一种阳离子或两性有机聚合物及聚硅酸盐微凝胶,使该悬浮液在造纸网上成形和滤水。
Description
一般来说,本发明涉及聚硅酸盐微凝胶,更具体地说,本发明涉及聚硅酸盐微凝胶及其制备方法和在造纸工业与水净化处理中的用途。
技术背景
聚硅酸盐微凝胶(任选铝酸盐化)可在纸和类似纤维制品的制造中用作助滤剂和助留剂,这在技术上是已知的。该微凝胶包括粒径很小(通常粒径为1~2纳米,比表面很高,一般为至少约1000米2/克)的二氧化硅基原微粒的溶液或分散体,而这些原微粒又连接成单个链段并形成三维网状结构。
聚硅酸盐和铝酸盐化聚硅酸盐微凝胶的制备步骤一般包括:以酸或酸性离子交换剂酸化碱金属硅酸盐的水性稀溶液,陈化经酸化的混合物,然后稀释该陈化混合物至二氧化硅浓度不高于2(重量)%。通常,二氧化硅基微凝胶的稳定性很差,因此,为了避免微凝胶发生胶凝作用,溶液必须极稀。由于这类产品存在稳定性问题,为保证运输稳定,产品浓度又极稀(溶液含约0.5(重量)%或以下的二氧化硅),因而需要极高的运输费用,因此,聚硅酸盐微凝胶最好在使用现场(如造纸厂)制备。可安装在造纸厂用于连续制备聚硅酸盐微凝胶的生产装置或发生器在技术上是已知的,由此可制得微凝胶并可连续地导入贮有待排放的纤维素纤维和填料的贮罐中。但是,生产装置的任何波动如制成微凝胶的质量和/或数量的变化都会改变产品的助滤性和助留性,而不利于纸的制造,从而会制造出质量不均匀的纤维素制品。
本发明详细说明
根据本发明业已发现,可通过将碱性碱金属硅酸盐与二氧化硅基材料相混合的很方便的方法来制备聚硅酸盐微凝胶,因而有可能制得高浓度聚硅酸盐微凝胶和铝酸盐化聚硅酸盐微凝胶以及微凝胶前体。更具体地说,本发明涉及一种包括将碱金属硅酸盐的水溶液与pH值优选为11或低于11的二氧化硅基材料的含水相相混合来制造水性聚硅酸盐微凝胶的方法。因此,本发明涉及如权利要求书中进一步规定的制备聚硅酸盐微凝胶的方法,聚硅酸盐微凝胶本身以及它们的用途。
本发明的聚硅酸盐微凝胶具有很高的稳定性,因而,与已知的聚硅酸盐微凝胶相比,制备更容易并可在二氧化硅浓度高得多的情况下装运。本发明的高浓度聚硅酸盐微凝胶可在打算生产该产品的工厂内在可控条件下制备,因而作为浓的产品可经济地向造纸厂运送。因此,许多造纸厂就不再需要安装生产聚硅酸盐微凝胶助滤剂和助留剂的制备装置或发生器,从而能给用户带来显著的技术和经济效益。
根据需要,本发明的高浓度聚硅酸盐微凝胶在使用例如用作造纸助滤剂和助留剂前可用水或酸性水溶液稀释,以便于二氧化硅基材料配入稀的纤维浆料中。就这一点来说,本发明的高浓度聚硅酸盐微凝胶可看作是可通过添加水(任选经酸化)而形成的低浓度聚硅酸盐微凝胶的前体。对于这种用途而言,在使用现场配置贮存高浓度聚硅酸盐微凝胶的贮罐较配置整套聚硅酸盐微凝胶的制备装置或发生器更经济。当然,也可通过将高浓度二氧化硅基产品作为高性能添加剂掺混到水性相中而在现场形成低浓度聚硅酸盐微凝胶,例如,将高浓度微凝胶产品添加到造纸过程中待滤水的纤维素纤维悬浮液或待净化的废水中。作为现场形成低浓度聚硅酸盐微凝胶的前体的本发明高浓度聚硅酸盐微凝胶的实际应用是技术上的重大进步。
用来制备本发明聚硅酸盐微凝胶的碱金属硅酸盐可以是任何一种水溶性硅酸盐如硅酸钠或硅酸钾,或者钠或钾水玻璃。可买到的这些水溶性硅酸盐有不同的SiO2与Na2O(或K2O)摩尔比,该摩尔比通常为1.5∶1-4.5∶1,最常见的为约2.5∶1-3.9∶1。优选的碱金属硅酸盐是硅酸钠。碱金属硅酸盐的水溶液呈碱性,通常的pH值为约13或13以上。碱金属硅酸盐溶液中二氧化硅浓度通常为5-35(重量)%,适宜为高于10(重量)%,而优选为15-30(重量)%。
根据本发明与碱金属硅酸盐溶液相混合的二氧化硅基材料可选自各种含硅材料,其中包括各种分散的二氧化硅如二氧化硅基溶胶、煅制二氧化硅、硅胶、沉淀二氧化硅、酸化的碱金属硅酸盐溶液以及含二氧化硅的蒙脱石型粘土的悬浮液。二氧化硅基材料含水相的pH值可为1-11。在本发明的一个优选方面中,含水二氧化硅基材料的pH值为1.5-4。在本发明另一个优选方面中,含水二氧化硅基材料的pH值为4-11,通常为从4.5,适宜为6.5、而最优选为7至高达11.0、优选高达10.6。
在本发明的一个优选实施方案中,用来与碱金属硅酸盐溶液相混合的二氧化硅基材料是二氧化硅基溶胶,适宜为碱稳定性的硅溶胶。这类溶胶在技术上是已知的,通常包含水相和二氧化硅(即SiO2)基微粒。优选的微粒是胶态微粒,即其尺寸为胶体范围的微粒。这类微粒包括胶态二氧化硅、铝改性的胶态二氧化硅及胶态硅酸铝。二氧化硅基溶胶的pH值的规定同上,通常至少为4。适用的二氧化硅基微粒溶胶包括已公开在美国专利4388150、4961825、4980025、5368833、5447604及5603805中的那些二氧化硅基溶胶,这些专利的公开内容已列入本文供参考。
溶胶中所含的二氧化硅基微粒的平均颗粒尺寸小于约100纳米,适宜为小于约50纳米。在本发明的优选实施方案中,二氧化硅基溶胶微粒的平均颗粒尺寸小于约30纳米,优选为约1-15纳米。按常规二氧化硅化学来说,粒度是指原微粒的平均尺寸,这些原微粒可能呈聚集状或非聚集状。溶胶中二氧化硅基微粒应具有的适宜比表面积为至少50米2/克。比表面积可借助已知的NaOH滴定法如Sears在分析化学(Analytical Chemistry),28(1956):12,1981-1983和美国专利5176891中所述方法来测定,测得的比表面积代表微粒的平均比表面积。适宜的比表面积为50-1200米2/克,而优选为70-1000米2/克。
在本发明的另一优选实施方案中,与碱金属硅酸盐溶液混合所用的二氧化硅基材料是酸化的碱金属硅酸盐。适用的酸化碱金属硅酸盐包括多硅酸、聚合的硅酸、活性的或经活化的二氧化硅以及聚硅酸盐(任选经铝酸盐化)。可按已知方法通过酸化碱金属硅酸盐水溶液来制备酸化的碱金属硅酸盐溶液,其中碱金属硅酸盐可以是任何一种水溶性硅酸盐如硅酸钠或硅酸钾,或者钠或钾水玻璃,优选为硅酸钠。可买到的适用碱金属硅酸盐具有不同的SiO2与NaO(或K2O)摩尔比,该摩尔比通常为1.5∶1-4.5∶1,最常见为约2.5∶1-3.9∶1。酸化的碱金属硅酸盐溶液的pH值的规定同上。可用许多方法实施酸化作用例如采用酸性离子交换剂、无机酸(如硫酸、盐酸或磷酸)、酸式盐或酸性气体,适宜为离子交换剂或无机酸或它们结合物,任选地与铝盐相结合来实施。对于需要SiO2与Na2O之比率较高的场合,最好采用酸性离子交换树脂。适用的酸化的碱金属硅酸盐包括公开在美国专利4388150、4954220、5127994、5279807、5312595及5503820中的那些酸化的碱金属硅酸盐,这些专利的公开内容已列入本文供参考。
适用的酸化的碱金属硅酸盐溶液也可选自既经酸化又经铝酸盐化的碱金属硅酸盐。铝酸盐化作用可与酸化作用同时实施或在酸化作用之后实施。适用的铝酸盐化和酸化的碱金属硅酸盐包括铝酸盐化聚硅酸盐或聚硅铝酸盐,例如公开在美国专利5176891、5470435、5482693、5543014、及5626921中的那些物质,这些专利的公开内容已列入本文供参考。
适用于本发明方法的酸化的和任选经铝酸盐化的碱金属硅酸盐应具有适当高的比表面积,适宜为1000米2/克以上。该比表面积可为1000-1700米2/克,优选为1050-1600米2/克。比表面积可按上述方法测定。
本发明方法包括使碱性碱金属硅酸盐与二氧化硅基材料相混合。混合过程可在0-300℃,适宜为5-150℃而优选为约10-约100℃下混合。该方法可借助搅拌通过将二氧化硅基材料添加到碱金属硅酸盐水溶液中来实施,优选在强烈混合下将二氧化硅基材料缓慢地添加到碱金属硅酸盐中去。二氧化硅基材料含水相中的二氧化硅浓度,根据所用材料类型可为0.1-60(重量)%。当采用二氧化硅基溶胶如碱稳定化溶胶时,SiO2含量可为5-60(重量)%,优选为10-50(重量)%。当采用如本文中所述的酸化的碱金属硅酸盐时,SiO2含量可为0.1-10(重量)%,优选为0.5-6(重量)%。因此,制得的聚硅酸盐微凝胶中的SiO2是由碱金属硅酸盐和二氧化硅基材料共同提供的。实施混合,要使制得的聚硅酸盐微凝胶中的5-95(重量)%,适宜为15-85(重量)%SiO2,源自碱金属硅酸盐,而95-5(重量)%,适宜为85-15(重量)%的SiO2源自二氧化硅基材料。
根据需要,在本方法制得的混合物中还可混入其它化合物。适用的附加化合物包括各种盐(如铝盐及其它金属盐)和各种酸。这些附加化合物具有提高微凝胶贮存稳定性和/或助滤性能和/或助留性能的作用。适用的铝盐包括明矾、铝酸盐、氯化铝、硝酸铝,以及聚铝化合物(如聚氯化铝、聚硫酸铝、含氯和硫酸根离子的聚铝化合物、聚硅酸铝-聚硫酸铝),以及它们的混合物。聚铝化合物也可含其它阴离子如源自磷酸、有机酸(如柠檬酸和草酸)的阴离子。优选的铝盐包括铝酸盐如铝酸钠或铝酸钾,优选为铝酸钠。可掺混到聚硅酸盐微凝胶中的铝盐量相当于SiO2∶Al2O3摩尔比为1500∶1-5∶1,适宜为750∶1-6∶1。除铝盐外的其它适用的金属盐包括碱金属和碱土金属(如Li、K、Mg和Ca)盐。适用的阴离子可选自氢氧化物、硼酸盐、硝酸盐、氯化物、甲酸盐、乙酸盐等。这些附加化合物的一般混入量应达到Na与所加金属盐中的附加金属之比大于1,优选为大于5。适用的酸包括有机酸,优选为二元酸(如二元羧酸和二磺酸),例如草酸、丙二酸、丁二酸、戊二酸和己二酸以及有机多元酸(如含羧酸和磺酸基团的聚合物),例如聚丙烯酸。混入聚硅酸盐微凝胶的附加酸的适宜用量要足以提高微凝胶的稳定性,其适宜用量至多可达10(重量)%。即使混合顺序或添加顺序是可随意的,但优选是将这些附加化合物混入碱金属硅酸盐和二氧化硅基材料的混合物中,更优选的混合顺序是在二氧化硅基材料与碱金属硅酸盐溶液混合前将酸添加到酸化的碱金属硅酸盐溶液中。
制得的聚硅酸盐微凝胶或微粒二氧化硅基材料的水性溶液或水分散体(任选经铝酸盐化)的SiO2含量通常为至少5(重量)%。SiO2含量取决于几种因素例如所用的原料及其SiO2含量,铝盐的掺入量等。适宜的SiO2含量为至少10(重量)%,优选为至少15(重量)%而最优选为至少17.5(重量)%,通常SiO2含量的上限为约50(重量)%,适宜为约35(重量)%,而在大多数情况为约30(重量)%。根据需要,在制备后,该水性聚硅酸盐微凝胶还可经如离子交换和/或浓缩处理。这种处理可有利于提高产品的贮存稳定性和/或产品的浓度。可采用已知方法如膜技术或水的蒸发实施浓缩作用。
得到的聚硅酸盐微凝胶中SiO2∶Na2O摩尔比为从3∶1至高达50∶1,适宜为从4∶1至高达30∶1、而优选为5∶1至20∶1。这一比率可随若干因素,例如原料的类型、原料的酸化类型、附加金属盐等而有所不同。SiO2∶M2O的摩尔比也取决于这些因素,其中M是碱金属如Li、Na、K及它们的混合物。聚硅酸盐微凝胶中SiO2∶M2O摩尔比为从2∶1至高达50∶1、适宜为从2.2∶1至高达30∶1、而优选为从3∶1至高达20∶1。优选的聚硅酸盐微凝胶性质上是阴离子型的。得到的水性聚硅酸盐微凝胶或二氧化硅基微粒材料的pH值通常低于14,适宜为低于13,而优选为低于12,通常,pH值高于6,适宜为高于9。
本发明的高浓度聚硅酸盐微凝胶可在使用前或使用中用水性溶液或悬浮液稀释或与其混合,从而可形成低浓度聚硅酸盐微凝胶,因此本发明高浓度聚硅酸盐微凝胶可用作低浓度聚硅酸盐微凝胶的前体。在优选的实施方案中,将高浓度聚硅酸盐微凝胶与pH值低于高浓度微凝胶的水性溶液或悬浮液相混合,从而使高浓度微凝胶的pH值发生改变。适用的水性溶液和悬浮液包括含酸、纤维素纤维和任选填料,以及酸性铝盐的水性溶液或悬浮液。
由本方法制得的聚硅酸盐微凝胶可称为包含很小微粒(优选直径为1-2纳米)的二氧化硅基微粒材料,而这些微粒又连接成链或网络并形成三维结构。该水性聚硅酸盐微凝胶也可因为,尤其是由于制备微凝胶所用原料的不同会有较大的颗粒。二氧化硅基微粒、微凝胶的比表面积适宜至少为1000米2/克,通常高达约1700米2/克。测定比表面的方法已在上文作了说明。
本发明的聚硅酸盐微凝胶适用作絮凝剂,例如可用于纸浆、纸的生产以及用于水净化领域中、不同种类废水的特别的净化处理和制浆、造纸工业中白水的特别的净化处理。聚硅酸盐微凝胶还能与可选自阴离子、两性、非离子和阳离子聚合物以及它们混合物的有机聚合物相结合用作絮凝剂。这些聚合物作为絮凝剂的用途在技术上是众所周知的,它们可来自天然或由合成方法制成聚合物,可以是线形的或支链聚合物。一般来说适用的聚合物实例包括阴离子、两性和阳离子淀粉、阴离子、两性和阳离子瓜耳胶及阴离子、两性和阳离子丙烯酰胺基聚合物,以及阳离子聚(二烯丙基二甲基氯化铵),阳离子聚乙烯亚胺,阳离子聚胺,聚酰胺基胺和乙烯基酰胺基聚合物,三聚氰胺甲醛树脂和脲甲醛树脂。聚硅酸盐微凝胶适于与至少一种阳离子或两性聚合物(优选为阳离子聚合物)结合使用。阳离子淀粉和阳离子聚丙烯酰胺是特别优选的聚合物,它们可单独使用、互相共同使用或与其它聚合物(如其它阳离子聚合物或阴离子聚丙烯酰胺)一起使用。尽管添加顺序是可随意的,但优选是先于聚硅酸盐微凝胶之前将聚合物添加到纸浆、浆料或水中。
与上述聚合物相结合的聚硅酸盐微凝胶的最佳用途是用于改善造纸浆料的滤水性和/或留着率,即用作造纸助滤剂和/或助留剂。本发明还涉及由含纤维素纤维和任选填料的悬浮液造纸的方法,该方法包括向悬浮液添加至少一种上述阳离子或两性有机聚合物和聚硅酸盐微凝胶,使悬浮液在造纸网上成形和滤水。因此,本发明还涉及按权利要求书所规定的一种方法。
当采用聚硅酸盐微凝胶与如上所述的有机聚合物的结合时,使用至少一种阴离子废屑收集剂(ATC)是更优选的。ATC可作为浆料中有害的阴离子物质的中和剂。因而能提高用于本方法中的其它添加剂的使用效果,这在技术上是已知的。因此,能与本发明聚硅酸盐微凝胶共用的聚合物的适用结合体还包括ATC与高分子量聚合物(如阳离子淀粉和/或阳离子聚丙烯酰胺、阴离子聚丙烯酰胺以及阳离子淀粉和/或阳离子聚丙烯酰胺与阴离子聚丙烯酰胺相结合)的结合体。适用的ATC包括阳离子聚电解质,特别是低分子量高荷电的阳离子有机聚合物如聚胺、聚乙烯亚胺、以二烯丙基二甲基氯化铵、(甲基)丙烯酰胺及(甲基)丙烯酸酯为主要成分的均聚物和共聚物。通常,ATC是先于其它聚合物被添加到浆料中的,或者,ATC聚合物可或与其它聚合物同时但各自地或以混合物被添加到浆料中,如欧洲专利申请752496中所公开。该专利内容已列入本文供参考。包含ATC聚合物和高分子量阳离子聚合物的混合物是特别优选的。
添加到浆料中或纤维素纤维悬浮液中的聚硅酸盐微凝胶的用量尤其是可随浆料类型、所用聚硅酸盐微凝胶的类型有很大的不同。一般用量为至少0.01千克/吨,常常是至少0.05千克/吨(以SiO2及干浆体系即纤维素纤维和任选填料计)。用量的上限为8千克/吨,适宜为5千克/吨。通常,聚硅酸盐微凝胶的配量为0.1-2千克/吨。
添加到浆料中的有机聚合物配量尤其是可随所用各种聚合物的类型以及是否有其它要求(如对纸的干、湿强度要求)而有很大的不同。通常,聚合物的用量是每吨干纤维和任选填料为至少0.005千克聚合物。对合成阳离子聚合物来说,如阳离子聚丙烯酰胺的用量通常为至少0.005千克/吨(以干聚合物和干纤维及任选填料计),适宜为0.01-3千克/吨而优选为0.03-2千克/吨。对以碳水化合物为主要成分的阳离子聚合物来说,如阳离子淀粉和阳离子瓜耳胶的用量为至少0.05千克/吨(以干聚合物和干纤维及任选填料计)。对于这些聚合物来说,适宜量为0.1-30千克/吨,而优选为1-15千克/吨。
在本发明的一个优选实施方案中,将聚硅酸盐微凝胶与至少一种如上所述的有机聚合物和至少一种铝化合物相结合用作助滤剂和/或助留剂。铝化合物可用来进一步改进包括聚硅酸盐微凝胶和铝酸盐化聚硅酸盐微凝胶在内的浆料添加剂的滤水性能和/或留着性能。适用的铝盐包括明矾,铝酸盐,氯化铝,硝酸铝及聚铝化合物(如聚氯化铝、聚硫酸铝、含氯和硫酸根离子的聚铝化合物、聚硅酸铝-聚硫酸铝),以及它们的混合物。聚铝化合物也可含其它阴离子例如源自磷酸、有机酸(如柠檬酸和草酸)的阴离子。优选的铝盐包括铝酸钠、明矾和聚铝化合物。铝化合物可在添加聚硅酸盐微凝胶之前或之后或与聚硅酸盐微凝胶同时添加到浆料中。在许多情况下,将铝化合物在该方法前期先加到浆料中例如先于其它添加剂被加到浆料中常常是适宜的。另一方面,或者是铝化合物与聚硅酸盐微凝胶或各自地在大体上同一位置同时或以两者混合物被添加到浆料中,如欧洲专利申请748897中所公开的那样方式,该专利内容已列入本文供参考。将聚硅酸盐微凝胶和铝化合物同时添加到浆料中是本发明优选实施方案。
添加到悬浮液的铝化合物量随所用铝化合物类型和是否有其它要求而有所不同。利用铝化合物作为松香基施胶剂的沉淀剂是技术上众所周知的例子。添加到浆料中铝化合物的适宜用量为至少0.001千克/吨(以Al2O3及干的纤维和任选填料计),用量的适宜范围为0.01-5千克/吨,优选为0.05-1千克/吨。
根据本发明的造纸方法可用于制造片状或纸幅状纤维素产品如浆板和纸,该方法优选用于纸的制造。本文所用名词“纸”当然不仅包括纸张及其制品,也包括其它片状或纸幅状产品例如板材和纸板及其制品。根据本发明的造纸方法可用于以不同类型的含纤维素纤维的悬浮液来制造片状或纸幅状产品,而这种悬浮液或浆料应含至少50(重量)%纤维素纤维(以干物料计)。悬浮液可以化学浆(如硫酸盐浆和亚硫酸盐浆)、预热机械浆、化学-预热机械浆、阔叶木和针叶木的圆盘磨浆或磨木浆纤维为主要成分,也可以回收纤维为主要成分。悬浮液也可含常规矿物填料如高岭土、二氧化钛、石膏、滑石以及天然和合成碳酸钙。悬浮液的pH值可为约3-约10,适宜为高于3.5,优选为4-9。浆料当然还可含常规造纸添加剂如湿强剂、松香基浆用施胶剂、乙烯酮二聚物或链烯基琥珀酸酐等。
用下列实施例对本发明作进一步的说明,然而,这些实施例并不意味着对本发明的限制。除非另有说明,份额和%分别指重量份和重量%。
实施例1
在50℃和强烈搅拌下将二氧化硅基溶胶缓慢地加入到SiO2含量约28(重量)%、SiO2∶Na2O摩尔比为约3.3的钠水玻璃(下文称硅酸钠)中制得本发明聚硅酸盐微凝胶。在某些试验中,还将水和/或附加碱金属盐、或硼酸钾(KBO2(水溶液),57%活性)和/或氢氧化锂(LiOH(水溶液),97%LiOH·H2O)加入到所得混合物中。所用二氧化硅基溶胶类型如下:
A:美国专利4388150中介绍的胶态二氧化硅溶胶,该溶胶经碱稳定化至SiO2∶Na2O摩尔比为约40,溶胶的pH值为约8-9,SiO2含量为约15(重量)%,SiO2微粒的比表面积为约500米2/克。
B:二氧化硅含量为40(重量)%、二氧化硅微粒比表面积为220米2/克的胶态二氧化硅溶胶。该溶胶购自Eka Chemicals,品名为BindzilTM 40/220。
C:美国专利4961825和4980025中介绍的铝改性的硅酸型溶胶,该溶胶的pH值为约8-9、SiO2含量为约15(重量)%,SiO2微粒比表面积为约500米2/克。
表1列出了用于本方法中的原料数量(Amt(g))和所得水性聚硅酸盐微凝胶中SiO2,Na2O与SiO2∶M2O的摩尔比(SiO2∶Na2O/SiO2∶M2O),其中M是碱金属(Na+K+Li)及SiO2含量,(SiO2(重量)%)。
表I
产品 硅酸钠 SiO2溶胶 KBO2(水溶液) LiOH(水溶液) SiO2∶Na2O/ SiO2
No. Amt.(g) Type/Amt.(g) Amt(g) Amt.(g) SiO2∶M2O (%)
1 300 A/319 18.8 11.7 5.0/3.4 19.5
2 300 A/319 - 11.7 5.0/3.8 19.5
3 500 A/150 - - 3.8/3.8 24.1
4 500 B/180 30.4 18.9 5.0/3.4 23.0
5 500 B/180 - 18.9 5.0/3.8 23.0
6 400 B/231 - 18.4 6.0/4.3 23.0
7 300 C/325 - 11.7 5.0/3.8 19.4
8 300 C/325 - 17.2 5.0/3.4 16.1
9 300 C/325 - 11.7 5.0/3.8 19.0
10 500 C/153 - - 3.8/3.8 19.6
实施例2
实施例1的聚硅酸盐微凝胶稳定性是通过测定制得微凝胶后的1、3、5或10天的该微凝胶粘度来评价的。粘度是在20℃下用RTV型布鲁克菲尔德(Brookfield)粘度计(转子61,60转/分)测定的。结果列于表II中。
表II
产品 SiO2 粘度(厘泊) 20℃
No. (%) 1天 3天 5天 10天
1 19.5 - 14 14 13
2 19.5 - 11 11 11
3 24.1 - 55 58 61
4 23.0 29 - 52 -
5 23.0 19 - 28 -
6 23.0 27 - 34 -
7 19.4 11 - 6 -
8 16.1 6 - 6 -
9 19.0 7 - 7 -
10 19.6 12 - 12 -
实施例3
下述试验中对实施例1的聚硅酸盐微凝胶的滤水性能和留着性能进行了试验。滤水性能是借助动态滤水分析仪(Dynamic DrainageAnalyser(DDA),购自Akribi,Sweden)进行评价的,该仪器测量当移去塞子并在造纸网另一侧施以真空时一定体积浆料通过造纸网滤除其中水分的时间。留着性能是借助浊度计,通过测定浆料经滤水后的滤出液(白水)的浊度来评价的。
试验是用pH值为8、纤维素纤维(60%漂白的桦木/40%松木硫酸盐浆)浓度为0.25%、白垩含量为30%,并添加有0.3克/升Na2SO4·10H2O的碱性浆料进行的。在本试验中,是聚硅酸盐微凝胶连同阳离子聚合物(Raisamyl 142)一起进行试验的,该阳离子聚合物是取代度为0.042的普通中等-高度阳离子化的淀粉,在浆料中的添加量为12千克/吨(以干物料和干浆体系计)在浆料中还添加有0.2千克/吨(以Al2O3和干浆体系计)的铝盐(铝酸钠)。
在整个试验过程中,在有导流片的容器中以每分钟1500转浆料进行搅拌,并按如下步骤向浆料添加化学添加剂:
i)添加阳离子淀粉,随后搅拌30秒钟,
ii)同时但分别添加聚硅酸盐微凝胶和铝盐,随后搅拌15秒钟,
iii)对浆料进行滤水试验,同时自动记录滤水时间。
表III列出了采用不同聚硅酸盐微凝胶配量(千克/吨,以SiO2和干浆体系计)所得的试验结果。未添加化学添加剂时,浆料的滤水时间为19.5秒,浊度为93NTU。
表III
产品 不同SiO2配量下的滤水时间(秒)/浊度(NTU)
No. 0.5kg/ton 0.8kg/ton 1.2kg/ton 1.7kg/ton 2.2kg/ton
1 15.0/- 10.5/53 8.7/56 7.2/48 6.2/48
2 16.5/- 12.3/73 9.9/61 9.1/62 8.9/60
3 15.2/- 14.5/- 12.8/- 12.0/- 12.0/-
4 14.3/- 10.9/69 8.0/55 6.5/52 6.2/48
6 14.6/- 10.3/65 8.2/60 7.5/55 7.7/54
8 17.2/- 15.0/- 13.1/- 11.5/- 10.7/-
实施例4
本发明的聚硅酸盐微凝胶是通过下述步骤制备的:在室温下将SiO2含量为约23(重量)%、SiO2∶Na2O摩尔比约3.3的钠水玻璃(下面称硅酸钠)与经酸性离子交换剂处理过的SiO2含量为约5-6(重量)%、pH值为约2.5的硅酸钠溶液(Acid SiO2)相混合,使该混合物的SiO2∶Na2O摩尔比达到约4.0,随后在强烈搅拌下缓慢地加入含约2.5(重量)%Al2O3的铝酸钠溶液(NaAl(水溶液)或加入其它碱土金属盐的水溶液(或乙酸镁(M:1.5%Mg(乙酸)2)或硝酸钙(C:2.5%Ca(NO3)2)。
表IV列出了本方法中所用原料的量(Amt(g))、以及制得的聚硅酸盐微凝胶的pH值和二氧化硅含量(重量%)。
表IV
产品 硅酸钠 Acid SiO2 NaAl(水溶液) 盐(水溶液) pH SiO2
No. Amt.(g) Amt.(g) Amt(g) Type/Amt.(g) (%)
11 320 237 34.3 - 11.3 18.8
12 140 250 - M/57 10.9 12.1
13 129 100 - C/21 11.5 13.9
实施例5
按实施例3对实施例5的聚硅酸盐微凝胶进行滤水性能和留着性能试验,试验用浆料为pH值8.4与实施例3相似的浆料、添加的阳离子淀粉、铝盐、剂量及添加顺序同实施例3。
表V列出了采用不同聚硅酸盐微凝胶用量(千克/吨)(以SiO2和干浆体系计)时得到的试验结果。未加化学添加剂时,浆料的滤水时间为21.2秒,浊度为104NTU。
表V
产品 不同SiO2配量下的滤水时间(秒)/浊度(NTU)
No. 0.5kg/ton 0.8kg/ton 1.2kg/ton 1.7kg/ton
11 15.2/84 12.0/74 11.6/66 7.9/-
12 13.9/82 11.1/70 9.9/62 7.5/-
13 15.7/81 11.1/72 9.7/64 7.0/-
实施例6
本发明铝酸盐化聚硅酸盐微凝胶是通过下述步骤制备的:将SiO2含量为约23(重量)%、SiO2∶Na2O摩尔比约3.3的钠水玻璃与经酸性离子交换剂处理过的SiO2含量为约5-6(重量)%、pH值为约2.5的硅酸钠溶液相混合,使该混合物的SiO2∶Na2O摩尔比达到约10∶1,随后在搅拌下加入含约2.5(重量)%Al2O3的稀铝酸钠溶液(NaAl(水溶液))。
表VI列出了所得产品中SiO2和Al2O3含量以及它们的稳定性和SiO2∶Na2O摩尔比。稳定性是在制备约一周后以目视法评价的。
表VI
产品 SiO2 Al2O3 稳定性 SiO2∶Na2O
No. (%) (%) (摩尔比)
14 10.7 0.4 好 7.5
15 10.7 0.6 好 6.2
实施例7
按实施例3对实施例6的聚硅酸盐微凝胶进行滤水性能和留着性能试验,试验采用与实施例3类似的、pH值为8.4、浓度为0.27%的浆料,除不向浆料添加铝盐外,本试验中所用的阳离子淀粉以及添加顺序都同实施例3。
表VII列出了加入不同量的聚硅酸盐微凝胶(千克/吨)以SiO2和干浆体系计)时所得的试验结果。未添加化学添加剂时,浆料的滤水时间为21.5秒,浊度为97NTU。
表VII
产品 不同SiO2配量下的滤水时间(秒)/浊度(NTU)
No. 0.3kg/ton 0.6kg/ton 1.0kg/ton 1.5kg/ton 2.0kg/ton
14 16.5/81 12.0/83 9.0/56 8.0/47 7.5/-
15 16.0/72 12.2/- 9.0/54 7.5/49 7.5/44
Claims (30)
1.一种制备水性聚硅酸盐微凝胶的方法,其特征在于该方法包括(i)碱金属硅酸盐水溶液与(ii)pH值为11或低于11的二氧化硅基材料含水相以及(iii)除铝盐外的金属盐或有机酸的附加化合物相混合。
2.根据权利要求1的方法,其特征在于(i)碱金属硅酸盐水溶液的pH值高于13。
3.权利要求1或2的方法,其特征在于(ii)pH值为11或低于11的二氧化硅基材料含水相是酸化的碱金属硅酸盐水溶液。
4.根据权利要求1、2或3的方法,其特征在于(ii)二氧化硅基材料含水相的pH值范围为1.5-4。
5.根据权利要求1、2或3的方法,其特征在于二氧化硅基材料含水相的pH值范围为7-11。
6.根据上述权利要求任何一项的方法,其特征在于(ii)二氧化硅基材料含水相是二氧化硅基溶胶。
7.根据上述权利要求任何一项的方法,其特征在于将(iii)附加化合物加入(i)碱金属硅酸盐水溶液与(ii)二氧化硅基材料含水相的混合物中。
8.根据上述权利要求任一项的方法,其特征在于附加化合物是除铝盐外的金属盐。
9.根据上述权利要求任一项的方法,其特征在于金属盐是基于碱金属或碱土金属盐。
10.根据上述权利要求任一项的方法,其特征在于金属盐是硼酸盐。
11.根据权利要求1-7任一项的方法,其特征在于附加化合物是有机酸。
12.根据权利要求1-7和11任一项的方法,其特征在于在与(i)碱金属硅酸盐水溶液混合之前,将有机酸加入(ii)为酸化的碱金属硅酸盐水溶液的二氧化硅基材料的水相。
13.根据权利要求1-7、11和12任一项的方法,其特征在于有机酸是有机多酸。
14.根据权利要求13的方法,其特征在于有机多酸选自包含羧酸基和磺酸基的聚合物。
15.根据权利要求13或14的方法,其特征在于有机多酸是聚丙烯酸。
16.根据上述权利要求任一项的方法,其特征在于制得的聚硅酸盐微凝胶中SiO2∶M2O摩尔比为3∶1与20∶1之间,其中M是碱金属。
17.根据上述权利要求任一项的方法,其特征在于制得的水性聚硅酸盐微凝胶中SiO2含量为至少5重量%。
18.根据上述权利要求任一项的方法,其特征在于制得的水性聚硅酸盐微凝胶中SiO2含量为至少17.5重量%。
19.根据上述权利要求任一项的方法,其特征在于制得的水性聚硅酸盐微凝胶包含粒径约1-2纳米的二氧化硅基微粒,而这些微粒又连接成链段或网状并形成三维结构。
20.根据上述权利要求任一项的方法,其特征在于聚硅酸盐微凝胶的比表面积为至少1000米2/克。
21.根据前述权利要求任一项的方法,其特征在于二氧化硅基材料含铝。
22.根据权利要求1-21任一项的方法制得的水性聚硅酸盐微凝胶,其比表面积为至少1000米2/克。
23.根据权利要求1的方法制得的水性聚硅酸盐微凝胶,其SiO2含量为至少17.5重量%,SiO2与Na2O的摩尔比为5∶1-20∶1。
24.根据权利要求23的水性聚硅酸盐微凝胶,其特征在于该聚硅酸盐微凝胶包含粒径约1-2纳米的二氧化硅基微粒,而这些微粒又连接成链或网状而形成三维结构。
25.根据权利要求23或24的水性聚硅酸盐微凝胶,其特征在于聚硅酸盐微凝胶的比表面积为至少1000米2/克至至多1700米2/克。
26.根据权利要求22-25任一项的聚硅酸盐微凝胶或根据权利要求1-21任何一项的方法制备的聚硅酸盐微凝胶与至少一种阳离子或两性聚合物结合作为絮凝剂在制浆、造纸工业以及水净化处理中的用途。
27.根据权利要求26的用途,其中聚硅酸盐微凝胶用作改进造纸浆料滤水和/或留着性能的絮凝剂。
28.根据权利要求26或27的用途,其中聚硅酸盐微凝胶是与阳离子淀粉和/或阳离子丙烯酰胺基聚合物结合使用的。
29.一种由含纤维素纤维和任选填料的悬浮液造纸的方法,其特征在于该方法包括向该悬浮液添加至少一种阳离子或两性有机聚合物和二氧化硅基微粒材料,使悬浮液在造纸网上成形和滤水,其特征在于二氧化硅基材料是根据权利要求22-25任一项的或根据权利要求1-21任一项方法制备的聚硅酸盐微凝胶。
30.根据权利要求29的方法,其特征在于该方法还包括向悬浮液添加铝盐。
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NZ503602A (en) | 1997-09-30 | 2001-03-30 | Nalco Chemical Co | Synthetic amorphous borosilicates and their use in the production of paper |
US6083997A (en) | 1998-07-28 | 2000-07-04 | Nalco Chemical Company | Preparation of anionic nanocomposites and their use as retention and drainage aids in papermaking |
US7169261B2 (en) * | 1999-05-04 | 2007-01-30 | Akzo Nobel N.V. | Silica-based sols |
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1998
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