CN1321887C - 聚硅酸盐微凝胶和二氧化硅基材料 - Google Patents
聚硅酸盐微凝胶和二氧化硅基材料 Download PDFInfo
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- CN1321887C CN1321887C CNB988059975A CN98805997A CN1321887C CN 1321887 C CN1321887 C CN 1321887C CN B988059975 A CNB988059975 A CN B988059975A CN 98805997 A CN98805997 A CN 98805997A CN 1321887 C CN1321887 C CN 1321887C
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- Prior art keywords
- ion
- polysilicate
- salt
- silicate
- aforementioned
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 99
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 239000000725 suspension Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920000620 organic polymer Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229920001131 Pulp (paper) Polymers 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 2
- 125000005587 carbonate group Chemical group 0.000 claims 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims 2
- 235000015076 Shorea robusta Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 description 18
- 239000000123 paper Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229960001866 silicon dioxide Drugs 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 229920006317 cationic polymer Polymers 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- 229910052910 alkali metal silicate Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 229920002907 Guar gum Polymers 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
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 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
- 229940037003 alum Drugs 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 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
- 238000004364 calculation method Methods 0.000 description 2
- 125000005626 carbonium group Chemical group 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010419 fine particle Substances 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
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001151 other effect Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 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 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 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
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 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
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007799 cork Substances 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
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- -1 sulfonium cation Chemical class 0.000 description 1
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Abstract
本发明涉及聚硅酸盐微凝胶、其制备方法及其在造纸和水净化中的应用,该聚硅酸盐微凝胶通过这样一种方法而得到,该方法包括(ⅰ)将盐AB的颗粒与硅酸盐或聚硅酸盐水溶液进行接触,或(ⅱ)在硅酸盐或聚硅酸盐水溶液的存在下将离子A与离子B进行接触,这样盐AB就沉淀在水相中,或(ⅲ)在硅酸盐或聚硅酸盐水溶液的存在下将离子A与离子B进行接触,这样离子A和B表示pKs值至少为4(在20℃的水中测定)的可沉淀盐AB的离子。本发明还涉及一种硅酸盐或聚硅酸盐水溶液、其制备方法及其作为聚硅酸盐微凝胶前体的应用。这种硅酸盐或聚硅酸盐水溶液包含离子A(钙或镁),其中SiO2∶B摩尔比小于2000∶1且高于1∶1;或离子B(碳酸根、硫酸根或磷酸根),其中SiO2∶B摩尔比小于2000∶1且高于1∶1。
Description
本发明一般涉及硅酸盐-和二氧化硅-基材料。更具体地说,本发明涉及聚硅酸盐微凝胶、其制备方法及其在造纸和水净化中的应用。本发明还涉及二氧化硅基材料、其制备方法及其作为聚硅酸盐微凝胶前体的应用。
背景技术
本领域已知聚硅酸盐微凝胶(可铝酸盐化的)可在纸和类似的纤维素产品的生产中用作助滤剂和助留剂。这些微凝胶包含甚小的初生二氧化硅基颗粒的溶液或分散体,这些颗粒一般粒径为1-2纳米且比表面积高,通常至少约1000米2/克,它们同时连接到各个链中以形成三维网状结构。
聚硅酸盐和铝酸盐化聚硅酸盐(aluminated polysilicate)的制备一般包括:使用酸或酸式离子交换剂来酸化碱金属硅酸盐的稀水溶液;将酸化的混合物熟化;然后将该熟化混合物进一步稀释至二氧化硅浓度不超过2%重量。二氧化硅基微凝胶通常稳定性不好,因此通常需要高度稀释才能避免微凝胶发生胶凝。由于与这些产品有关的稳定性问题,以及运输稳定但包含约0.5%重量或更低二氧化硅的极稀溶液时的抑制成本,因此聚硅酸盐微凝胶优选在具体应用场所,例如在造纸厂制备。本领域已知能够在造纸厂安装用于连续制备聚硅酸盐微凝胶的生产装置或发生器。因此,可制备出所得到的微凝胶并连续加入要进行滤水的包含纤维素纤维和填料的物料中。但生产装置中的任何故障,例如所得微凝胶在质量和/或数量上的差异将会改变产品的滤水和留着性能,这对造纸工艺产生不利影响,从而产生出质量不稳定的纤维素产品。
本发明
按照本发明,已经发现,聚硅酸盐微凝胶可通过将AB盐颗粒与硅酸盐或聚硅酸盐水溶液、或在硅酸盐或聚硅酸盐水溶液的存在下将A离子与B离子进行接触,以一种非常有利的方式来制备,其中AB盐表示一种可沉淀的盐,这样AB可形成并沉淀在水相中,而且将AB盐或A和B离子与硅酸盐或聚硅酸盐溶液进行接触有利于形成聚硅酸盐微凝胶。该方法可通过将A和B离子与硅酸盐或聚硅酸盐溶液作为三种单独组分进行混合来进行;也可通过将A离子加入硅酸盐或聚硅酸盐溶液中,然后将该溶液与B离子进行混合;或通过将B离子加入硅酸盐或聚硅酸盐溶液中,然后将该溶液与A离子进行混合来进行,这样AB盐可形成并沉淀在水相中并有利于形成聚硅酸盐微凝胶。更具体地说,本发明涉及一种制备聚硅酸盐微凝胶的方法,该方法包括将AB盐颗粒与硅酸盐或聚硅酸盐水溶液接触,或在硅酸盐或聚硅酸盐水溶液的存在下将A离子与B离子进行接触,从而AB盐在水相中沉淀,和/或A和B离子表示pKs值至少为4(在20℃的水中测定)的可沉淀盐AB的离子。因此,本发明涉及一种用于制备聚硅酸盐微凝胶的方法、微凝胶本身及其应用,这将在权利要求中进一步限定。
按照本发明,提供了一种采用高浓度的硅酸盐和聚硅酸盐溶液,即包含SiO2的溶液来制备聚硅酸盐微凝胶的方法。按照本发明,还提供了包含可沉淀盐的离子的高浓度硅酸盐和聚硅酸盐溶液。这种高浓度硅酸盐和聚硅酸盐溶液可用作聚硅酸盐微凝胶的前体。本发明的硅酸盐和聚硅酸盐溶液(可含有可沉淀盐的离子),即聚硅酸盐微凝胶前体的稳定性高,因此相对现有已知的聚硅酸盐微凝胶来说,容易制备并且可以较高的SiO2浓度来运输。本发明的高浓度二氧化硅基溶液可在为这种生产而设计的工厂中在受控条件下制备,然后作为浓缩产品以一种经济上有吸引力的方式运输到造纸厂。通过将AB颗粒或可沉淀盐AB的A和B离子与硅酸盐或聚硅酸盐溶液进行简单混合;或通过将可沉淀盐的抗衡离子B(例如,以水溶液的形式)加入包含离子A的高浓度产品中;或反过来操作,可制成备用(例如在造纸中用作助滤剂和助留剂)的聚硅酸盐微凝胶。在该应用中,用于高浓度聚硅酸盐微凝胶前体的储罐可安装在具体应用的地点,这相对于安装一个完整的聚硅酸盐微凝胶生产装置或发生器来说,在经济上更具有吸引力。因此,本发明具有明显的技术和经济效果。此外,包含本发明A离子的高浓度产品可加入包含所需抗衡离子和纤维素纤维的悬浮液,如造纸工艺中的再循环的白水中,这样在白水再循环到需滤水的纤维悬浮液中的同时,可以形成聚硅酸盐微凝胶。由于使用本发明高浓度二氧化硅基材料作为前体用于原位形成聚硅酸盐微凝胶,因此该应用是本领域的一种明显进步。
用于本发明方法中的硅酸盐或聚硅酸盐水溶液可选自任何水溶性硅酸盐,如硅酸钠或钾、或者钠或钾水玻璃。SiO2与Na2O或K2O的摩尔比是可以变化的,该摩尔比通常为1.5∶1-4.5∶1,最常见约2.5∶1-3.9∶1。碱金属硅酸盐优选是硅酸钠。碱金属硅酸盐的水溶液是碱性的,其pH值通常为约13或高于13。碱金属硅酸盐溶液的SiO2含量通常至少为1%重量。通常,SiO2含量为5-35%重量,适合在10%以上,优选15-30%重量。
用于本发明方法的硅酸盐或聚硅酸盐水溶液还可选自任何水溶性聚硅酸盐,如聚硅酸钠和钾,优选聚硅酸钠。水溶性聚硅酸盐是本领域已知的。所述聚硅酸盐可具有高的SiO2∶Na2O摩尔比范围,例如为3∶1-50∶1,适宜4∶1-30∶1,优选为4.5∶1或5∶1至20∶1。聚硅酸盐的SiO2∶M2O摩尔比范围为2∶1-50∶1,适宜为2.2∶1-30∶1,优选为3∶1-20∶1,其中M是碱金属,如Li、Na、K及其混合形式。所述聚硅酸盐水溶液的pH值一般低于14,适宜低于13,优选低于12。该pH值适合在9以上。
合适的聚硅酸盐可通过将(例如)上述的碱金属硅酸盐水溶液与二氧化硅基材料的水相进行混合而制备。合适的二氧化硅基材料可选自各种含硅材料(可任选铝酸盐化),其中包括分散二氧化硅,如二氧化硅基溶胶,例如包含二氧化硅、铝改性的二氧化硅或硅酸铝、气相法二氧化硅、硅胶、沉淀二氧化硅的胶体颗粒的碱稳定的水溶胶;碱金属硅酸盐(可铝酸盐化),如聚硅酸、聚多硅酸、活性或活化二氧化硅、可铝酸盐化的聚硅酸盐,如聚铝硅酸盐的酸化溶液;以及蒙脱石型含硅粘土的悬浮液。二氧化硅基材料的水溶液的pH值为1-11。在本发明的一个优选方面,二氧化硅基材料的水溶液的pH为1.5-4。在本发明的另一个优选方面,二氧化硅基材料的水溶液的pH值为4-11.0,一般从4.5、适合从6.5、最优选从7至最高11.0,优选至10.6。
所得聚硅酸盐溶液的SiO2含量一般为至少1%重量,通常为至少5%重量。合适的SiO2含量为至少10%重量,优选至少15%重量,最优选至少17.5%重量。其上限通常为约50%重量,适合约35%重量,大多数情况下约30%重量。如果需要,在制备之后,可将该聚硅酸盐水溶液进一步进行处理,如离子交换和/或浓缩。这样可有利地提供具有改进的储存稳定性和/或较高浓度的产品。可通过已知方法,例如通过膜法或水蒸发法来进行浓缩。
在本发明的一个优选实施方案中,将硅酸盐或聚硅酸盐水溶液与AB盐的颗粒进行接触。所述颗粒优选为胶体颗粒,即其粒径处于胶体范围内,如低于1μm,适合低于500nm,优选在100纳米-1纳米的范围内。AB的颗粒可以固体形式使用,尽管一般优选使用包含AB颗粒的水相,例如溶胶或悬浮液的形式。在本发明的另一优选实施方案中,在硅酸盐或聚硅酸盐水溶液的存在下将离子A和B进行接触。离子A和B可分别以盐AC和DB的形式加入混合区中。在本发明的再一优选实施方案中,盐AB的离子A或B之一(例如,以盐AC或盐DB的形式)存在于硅酸盐或聚硅酸盐溶液中。在将包含(例如)离子A的硅酸盐或聚硅酸盐溶液与离子B进行混合时,或反过来操作,可以形成一种沉淀AB。这可通过将盐AC加入硅酸盐或聚硅酸盐溶液中,然后将DB加入包含AC的溶液或混合物中来进行。包含离子A或离子B的硅酸盐或聚硅酸盐溶液的合适SiO2含量和pH值包括以上针对硅酸盐或聚硅酸盐水溶液所描述的那些。
所述的盐AB优选是一种pKs(在20℃水中测定)至少为4,适合至少为6,优选至少为8的盐。本文所用的术语“AB”包括盐和/或正离子A与负离子B的离子对。合适的AB包括无机盐,如磷酸、碳酸和硫酸的金属盐。合适的AB包括磷酸铝、碳酸铁、氢氧化铁、磷酸铁、硫酸镁、碳酸镁、氢氧化镁、磷酸镁、硫酸钙、碳酸钙、磷酸钙、硅酸钙、硫酸锶、碳酸锶和碳酸锌。碳酸钙和硫酸钙是特别优选的。合适的有机盐AB包括草酸镁和草酸锌。硅酸盐或聚硅酸盐水溶液还可与AB的颗粒进行接触,所述AB是具有带电基团A和抗衡离子B的微粒有机或无机聚合物,优选有机聚合物。聚合物颗粒优选具有如上所述的胶体范围粒径。阳离子有机聚合物的合适的A型带电基团包括铵和锍离子,而合适的B型抗衡离子包括上文所述的那些以及氯离子、溴离子和硫酸根离子。阴离子有机聚合物的合适的A型带电基团包括羧酸和磺酸,而合适的B型抗衡离子包括上文所述的那些以及质子和铵离子。
所述的盐AC优选是一种水溶性盐,且优选还可溶于硅酸盐或聚硅酸盐溶液。盐AC可作为一种固体物质或作为一种水溶液加入。本文所用的术语“AC”包括盐和/或正电离子A与负电离子C的离子对。合适的离子A包括上述的那些以及常见的钙和镁。合适的离子C包括氯离子、硝酸根、甲酸根和乙酸根。合适的AC包括氯化钙、硝酸钙、甲酸钙、甲酸镁、乙酸钙和乙酸镁。在(例如)硅酸盐或聚硅酸盐溶液包含盐AC时,可用一种配合剂来进行处理以避免含A的盐在与B接触之前发生沉淀。当A为金属离子,如Ca或Mg时,可以使用的合适配合剂的例子包括EDTA、柠檬酸、葡萄糖、蔗糖、多元醇、HEDP、DTPA等。通常,配合剂的用量要有效地避免离子A的盐发生沉淀。配合剂与A的摩尔比合适地为5∶1-1∶5,优选2∶1-1∶2。硅酸盐或聚硅酸盐溶液中或混合区(离子A和B在硅酸盐或聚硅酸盐溶液的存在下进行接触)中的SiO2∶A摩尔比可在较宽范围内变化,一般低于5000∶1,通常低于2000∶1,更常见的是低于1000∶1,且通常高于1∶1,在许多情况下其范围为从500∶1、适合从50∶1、优选从25∶1至1∶1、适合至2∶1、优选至5∶1。
所述的盐DB优选是一种水溶性盐,且优选还可溶于硅酸盐或聚硅酸盐溶液。盐DB可作为一种固体物质或作为一种水溶液加入。本文所用的术语“DB”包括盐和/或正离子D与负离子B的离子对。合适的离子D包括碱金属,如钠和钾。合适的离子B包括上述的那些以及常见的碳酸根、硫酸根和磷酸根。合适的DB包括碳酸钠、碳酸氢钠、硫酸钠、硫酸氢钠、磷酸钠和磷酸氢钠。合适的DB还可选自包含氢D和离子B的质子酸,如硫酸和磷酸。DB酸优选以酸的稀水溶液形式加入。离子B还可选自源自二氧化碳的碳酸根,二氧化碳可通过将溶液与二氧化碳(固体、液体或气态形式,可以是纯的或稀释的形式,例如从空气中吸收)进行接触而引入。硅酸盐或聚硅酸盐溶液中或在混合区(离子A和B在硅酸盐或聚硅酸盐溶液的存在下进行接触)中的SiO2∶B摩尔比可在较宽的范围内变化,一般低于5000∶1,通常低于2000∶1,更常见的是低于1000∶1,且通常高于1∶1,在许多情况下为从500∶1、适合从50∶1、优选从25∶1至1∶1、适合至2∶1、优选至5∶1。
所述的盐DC(在本发明方法中可通过加入AC和DB而形成)优选是一种水溶性盐,且优选还可溶于硅酸盐或聚硅酸盐溶液。本文所用的术语“DC”包括盐和/或正电离子D与负电离子C的离子对。合适的D和C包括上述的那些。
按照本发明的一个优选实施方案,在将AB颗粒与硅酸盐或聚硅酸盐溶液进行混合时,SiO2∶AB摩尔比可在较宽的范围内变化,一般低于5000∶1,通常低于2000∶1,更常见的是低于1000∶1,且通常高于1∶1,在许多情况下为从500∶1、适合从50∶1、优选从25∶1至1∶1、适宜至2∶1、优选至5∶1。按照本发明的一个优选实施方案,在将A与B在硅酸盐或聚硅酸盐溶液的存在下进行混合时,A和B的浓度要优选使得所得混合物中的摩尔浓度乘积([A]×[B])超过该混合物的溶解度乘积(Ks)。
按照本发明的混合步骤可在10-90℃,优选20-50℃下进行。在混合过程中,所得混合物的pH值可以等于、高于或低于硅酸盐或聚硅酸盐溶液的pH值,适合相等或较低、优选低于硅酸盐或聚硅酸盐溶液的pH值。合适的pH值范围可以是5-11。适用于该混合步骤以得到所需pH值或范围的酸包括常规的酸,如H2SO4、HCl等无机酸以及甲酸、乙酸等有机酸。
如上所述,离子A和B当然可以相反顺序加入到硅酸盐或聚硅酸盐溶液中,即首先将离子B(例如以盐DB的形式(任选与如上所述的配合剂结合使用)加入高浓度硅酸盐或聚硅酸盐溶液中,然后将离子A加入到包含B的该溶液中,这样可形成AB和聚硅酸盐微凝胶。
按照本发明方法的混合步骤适宜包括:将AB颗粒以甚细微粒材料的形式加入,或使AB盐形成并优选沉淀为一种甚细微粒材料,这样可促进形成聚硅酸盐微凝胶。AB的微沉淀物优选包含如上所述的胶体粒径的颗粒。据信,至少部分所加入和/或沉淀的AB微粒可被聚硅酸盐材料所覆盖,且AB微粒可用作形成二氧化硅微粒时的核。通过本发明方法得到的聚硅酸盐微凝胶可描述为:包含甚小颗粒(优选1-2纳米的直径)的二氧化硅基微粒材料的水分散体或水溶液(优选胶态的),这些颗粒优选在链中或网状结构中连接在一起以形成三维结构。含水的聚硅酸盐微凝胶还可含有较大的颗粒,这本质上取决于制备该微凝胶时所用的原料。聚硅酸盐微凝胶优选是阴离子性的。二氧化硅基微粒、微凝胶的比表面积适宜至少为1000米2/克,通常最高约1700米2/克。比表面积可通过用NaOH滴定,以已知方式来测定,如Sears在
分析 化学28(1956):12,1981-1982以及美国专利5,176,891中所述的方法。比表面积表示颗粒的平均比表面积。
通过该混合步骤得到的含水聚硅酸盐微凝胶的SiO2含量为0.1-10%重量。在本发明的一个优选实施方案中,该混合步骤是在需要使用聚硅酸盐微凝胶的场所(例如在造纸厂)进行的。在一个优选实施方案中,将硅酸盐或聚硅酸盐溶液(可任选含有可沉淀盐AB的一种离子,如适当地以上述DB形式加入该溶液中的碳酸盐、硫酸盐或磷酸盐的一种离子)与包含钙离子的白水进行混合。该白水可在与本发明硅酸盐或聚硅酸盐溶液接触之前,进行任何净化步骤,例如本领域常用的以去除纤维、填料、颗粒物、胶体和/或溶解的有机物质的任何这些步骤,如沉淀、沉降、浮选和过滤。然后,将所形成的聚硅酸盐微凝胶加入需虑水的纤维原料中。也可将硅酸盐或聚硅酸盐溶液直接加入需滤水或絮凝的水溶液或悬浮液中,只要能够原位形成AB盐。所述聚硅酸盐微凝胶还可以预混模式形成,其中将包含A的硅酸盐或聚硅酸盐水流与B的水流进行接触,这样将所得液流加入需滤水或絮凝的水溶液或悬浮液中。
本发明的聚硅酸盐微凝胶适于用作絮凝剂,例如在纸浆和纸的生产中和在水净化领域中,既可用于净化不同种类的废水,也可特定用于净化来自纸浆和造纸工业的白水。该聚硅酸盐微凝胶可与选自阴离子、两性离子、非离子和阳离子聚合物及其混合物的有机聚合物结合用作絮凝剂。这些聚合物作为絮凝剂的应用是本领域已知的。这些聚合物可来自天然或通过合成得到,且它们可以是直链或支链的。一般来说,合适的聚合物的例子包括阴离子、两性和阳离子淀粉,阴离子、两性和阳离子瓜耳胶以及阴离子、两性和阳离子丙烯酰胺-基聚合物以及阳离子聚(氯化二烯丙基二甲基铵)、阳离子聚亚乙基亚胺、阳离子聚胺、阳离子聚酰氨基胺、阳离子乙烯基酰胺-基聚合物、蜜胺-甲醛和脲醛树脂。该聚硅酸盐微凝胶适合与至少一种阳离子或两性聚合物、优选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。即使可以采用任意的加入顺序,但优选将一种或多种所述聚合物在二氧化硅基材料/聚硅酸盐微凝胶之前加入纸浆、原料或水中。
聚硅酸盐微凝胶与上述聚合物的结合使用可优选在纸的生产过程中用于提高滤水和/或留着性能,即在造纸中用作助滤剂和/或助留剂。本发明还涉及一种用于从纤维素纤维以及任选的填料的悬浮液中造纸的方法,该方法包括:将至少一种阳离子或两性有机聚合物和本文所述聚硅酸盐微凝胶加入该悬浮液中,在网上成形并将该悬浮液滤水。因此,本发明涉及一种如权利要求中进一步定义的方法。
在将聚硅酸盐微凝胶与上述一种主要机聚合物结合使用时,进一步优选使用至少一种阴离子废物捕剂(ATC)。ATC是本领域已知的,它可用作原料中有害阴离子物质的中和剂。因此,ATC可提高用于该方法中的其它添加剂的效力。因此,可与聚硅酸盐微凝胶共用的其它合适的聚合物组合包括:ATC结合高分子量聚合物,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结合阴离子聚丙烯酰胺。合适的ATC包括阳离子聚电解质,尤其是低分子量高度带电的阳离子有机聚合物,如聚胺、聚亚乙基亚胺、基于氯化二烯丙基二甲基铵、(甲基)丙烯酰胺和(甲基)丙烯酸酯的均聚物和共聚物。通常,将ATC在其它聚合物之前加入原料中。此外,ATC聚合物可与其它聚合物同时加入(可单独或以混合物的形式加入)。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。
聚硅酸盐微凝胶或二氧化硅基材料在原料或纤维素纤维悬浮液中的用量可在较宽的范围内变化,除了其它原因,这取决于原料种类、所用聚硅酸盐微凝胶的种类。该量一般至少为0.01千克/吨,通常至少为0.05千克/吨,这是以SiO2计算的并基于干原料体系(即纤维素纤维和任选的填料)。其上限可以是8千克/吨,适宜为5千克/吨。通常,二氧化硅基材料的用量在0.1-2千克/吨的范围内。
有机聚合物在原料中的用量可在较宽的范围内变化,除了其它原因,这取决于所用聚合物的种类以及是否需要其它效果,如纸的湿强度和干强度。通常每吨干纤维和任选的填料,使用至少0.005千克聚合物。对于合成的阳离子聚合物,如阳离子聚丙烯酰胺,通常使用的量至少为0.005千克/吨,这是以干纤维和任选填料为基础计算的干重,适宜为0.01-3千克/吨、优选0.03-2千克/吨。对于基于碳水化合物的阳离子聚合物,如阳离子淀粉和阳离子瓜耳胶,通常使用的量至少为0.05千克/吨,这是以干纤维和任选填料为基础计算的干重。对于这些聚合物,其量适合为0.1-30千克/吨,优选1-15千克/吨。
与至少一种上述有机聚合物以及至少一种含铝化合物结合使用,本发明的聚硅酸盐微凝胶优选用作助滤剂和/或助留剂。含铝化合物可用于进一步提高包含聚硅酸盐微凝胶的原料添加剂的滤水和/或留着性能。合适的铝盐包括明矾、铝酸盐、氯化铝、硝酸铝和聚合的含铝化合物(polyaluminium),如含氯离子的聚合的含铝化合物(polyaluminium chlorides)、含硫酸根离子的聚合的含铝化合物(polyaluminium sulphates)、同时包含氯根和硫酸根离子的聚合的含铝化合物、聚硅酸铝-硫酸铝(polyalumium silicate-sulphates)及其混合物。所述聚合的含铝化合物还可包含其它阴离子,如来自磷酸、有机酸,如柠檬酸和草酸的阴离子。优选的铝盐包括铝酸钠、明矾和聚合的含铝化合物。所述的含铝化合物可在加入二氧化硅基材料/聚硅酸盐微凝胶之前、同时或之后加入。在许多情况下,通常优选将含铝化合物早在其它添加剂之前搀入原料体系中。此外,所述含铝化合物可与二氧化硅基材料/聚硅酸盐微凝胶一起同时加入,可以是单独加入或与其以混合物的形式同时加入。
含铝化合物在悬浮液中的加入量取决于所用的含铝化合物的种类以及是否需要其它效果。例如,本领域已知可将含铝化合物用作松香基浆料的沉淀剂。含铝化合物在原料中的加入量应该适合为至少0.001千克/吨,这是以Al2O3计算的并基于干纤维和任选填料。该量适合为0.01-5千克/吨,优选0.05-1千克/吨。
按照本发明的造纸工艺可用于生产片状或网状纤维素产品,如浆粕(pulp sheets)和纸张。本发明方法优选用于纸的生产。本文所用的术语“纸”当然不仅包括纸及其制品,而且还包括其它的片状或网状制品,如板和纸板及其制品。按照本发明的造纸工艺可用于从包含纤维素纤维的不同种类悬浮液来生产片状或网状制品,且所述悬浮液或原料应该适合包含基于干物质至少50%重量的这种纤维。该悬浮液可以基于来自化学纸浆,如硫酸盐纸浆和亚硫酸盐纸浆、热机械纸浆、化学-热机械纸浆、精磨浆或磨木浆(来自硬木和软木)的纤维,且可用于基于回收纤维的悬浮液。该悬浮液还可包含常规种类的矿物填料,如高岭土、二氧化钛、石膏、滑石以及天然和合成的碳酸钙。该悬浮液的pH值为约3-10。该pH值适合在3.5以上,优选为4-9。所述原料当然还可包含常规种类的造纸添加剂,如温强度剂、基于松香的原浆料(stock sizes)、乙烯酮二聚物或链烯基琥珀酸酐等。
以下在实施例中进一步说明本发明,但本发明不限于此。除非另有所指,份数和百分数(%)分别是指重量份和重量百分数。
实施例1
按照本发明的聚硅酸盐微凝胶制备如下:
将包含10%SiO2的15克钠水玻璃水溶液放入烧杯中,然后在剧烈搅拌下加入52克1%的H2SO4。然后,在剧烈搅拌下加入22.4克0.1%的CaCl2水溶液。所得二氧化硅基材料的水溶液的pH值为10,SiO2含量为1.7%,且表面负电荷为约1100ueqv/g,这是利用Mutek微粒电荷测定仪(Mutek Particle Charge Detector)PCD 03M在其制备之后1小时测得的,表明形成了聚硅酸盐微凝胶。
实施例2
按照本发明的聚硅酸盐微凝胶制备如下:
将包含10%SiO2的120克钠水玻璃水溶液放入烧杯中,然后在剧烈搅拌下加入260克1%的H2SO4,然后用155克水将该混合物稀释。接着,在剧烈搅拌下加入179克0.1%的CaCl2水溶液。最后,将二氧化碳鼓入该混合物中,直到pH值为约10。所得二氧化硅基材料的水溶液的SiO2含量为1.7%,且表面负电荷为约1000ueqv/g(测定如上),这表明形成了聚硅酸盐微凝胶。
实施例3
为了对比,按照实施例1的步骤,只是没有加入CaCl2。如实施例1来评估产品的表面电荷,结果表面负电荷为约1800ueqv/g,这表明基本上没有形成聚硅酸盐微凝胶。
实施例4
在以下试验中,利用得自Akribi(瑞典)的动态滤水分析仪(DDA),以常规方式来评估按照实施例1和3制备的二氧化硅基材料的滤水和留着性能。
试验是使用基于70%纤维素纤维和30%白垩的配料进行的,所述纤维素纤维是基于漂白桦树/松树硫酸盐纸浆的混合物。原料的浓度为0.25%,导电率为0.45mS/cm,且pH值为8.5。在试验中,将二氧化硅基材料与阳离子聚合物结合一起进行试验,该阳离子聚合物Raisamyl 142是一种常规的中度-高度阳离子化淀粉(取代度为0.042),其在原料中的加入量为12千克/吨(以干原料体系计算的)。
将原料在DDA的隔板式罐中以1000rpm的速度进行搅拌,然后在加入二氧化硅基材料之前将阳离子聚合物加入到该原料中,然后将该原料滤水。表I给出了在采用不同用量(千克/吨,以SiO2计算且基于干原料体系)的二氧化硅基材料时,制备后约2小时所得到的结果。
表III
二氧化硅基材料 | 滤水时间(秒)/在不同的SiO2用量下的细粒留着率(%) | ||||
材料 | 0.5千克/吨 | 1.0千克/吨 | 1.5千克/吨 | 2.0千克/吨 | 3.0千克/吨 |
实施例1 | 9.8/51 | 7.2/69 | 6.5/77 | 6.2/75 | -/70 |
实施例3 | 12.5/19 | 10.2/27 | 9.5/32 | 9.2/24 | -/25 |
Claims (21)
1.一种用于制备含水聚硅酸盐微凝胶的方法,其特征在于,它包括(i)将盐AB的颗粒与酸以及硅酸盐或聚硅酸盐水溶液进行接触,或(ii)在硅酸盐或聚硅酸盐水溶液的存在下,将离子A与离子B以及酸进行接触,这样盐AB就沉淀在水相中,在20℃的水中测定的所述盐AB的pKs值至少为4。
2.一种用于制备含水聚硅酸盐微凝胶的方法,其特征在于,它包括(iii)在硅酸盐或聚硅酸盐水溶液的存在下,将离子A与离子B以及酸进行接触,这样离子A和B表示在20℃的水中测定的pKs值至少为4的可沉淀盐AB的离子。
3.一种用于制备含水聚硅酸盐微凝胶的方法,其特征在于,它包括在硅酸盐或聚硅酸盐水溶液的存在下,将离子A与包含离子B的质子酸进行接触,这样盐AB就沉淀在水相中,在20℃的水中测定的所述盐AB的pKs值至少为4。
4.一种用于制备含水聚硅酸盐微凝胶的方法,其特征在于,它包括在硅酸盐或聚硅酸盐水溶液的存在下,将离子A与包含离子B的质子酸进行接触,这样离子A和B表示在20℃的水中测定的pKs值至少为4的可沉淀盐AB的离子。
5.根据权利要求1的方法,其特征在于,它包括在硅酸盐或聚硅酸盐溶液的存在下将离子A与离子B以及酸进行接触。
6.根据前述权利要求任一项的方法,其特征在于所得含水聚硅酸盐微凝胶的比表面积至少为1000米2/克。
7.根据前述权利要求任一项的方法,其特征在于,它包括:提供一种包含离子A的硅酸盐或聚硅酸盐水溶液,然后将该溶液与离子B进行混合;或提供一种包含离子B的硅酸盐或聚硅酸盐水溶液,然后将该溶液与离子A进行混合。
8.根据前述权利要求任一项的方法,其特征在于,所述盐AB包含粒径处于胶体范围内的颗粒且SiO2∶AB摩尔比高于1∶1。
9.根据前述权利要求任一项的方法,其特征在于,所述盐AB的在20℃的水中测定的pKs值至少为8。
10.根据前述权利要求任一项的方法,其特征在于,所得含水聚硅酸盐微凝胶的SiO2含量为0.1-10%重量。
11.根据前述权利要求任一项的方法,其特征在于,所述盐AB选自碳酸的金属盐、硫酸的金属盐和磷酸的金属盐。
12.根据前述权利要求任一项的方法,其特征在于,所述盐AB选自碳酸钙、硫酸钙、磷酸钙、碳酸镁、硫酸镁或磷酸镁,且所述离子A为钙离子或镁离子,所述离子B为碳酸根、硫酸根或磷酸根。
13.根据前述权利要求任一项的方法,其特征在于,所述酸为硫酸。
14.根据前述权利要求任一项的方法,其特征在于,所述硅酸盐或聚硅酸盐水溶液包含离子A并且离子A为钙离子或镁离子,其中SiO2∶A摩尔比小于2000∶1且高于1∶1。
15.根据权利要求1-13任一项的方法,其特征在于,所述硅酸盐或聚硅酸盐水溶液包含离子B且离子B为碳酸根或磷酸根,其中SiO2∶B摩尔比小于2000∶1且高于1∶1。
16.根据前述权利要求任一项的方法,其特征在于,该溶液的SiO2∶Na2O摩尔比为1.5∶1-4.5∶1。
17.根据权利要求1-15任一项的方法,其特征在于,该溶液的SiO2∶Na2O摩尔比为4.5∶1-20∶1。
18.根据前述权利要求任一项的方法,其特征在于,它包含一种配合剂。
19.根据前述权利要求任一项的方法,其特征在于,所得含水聚硅酸盐微凝胶的pH值为5-11。
20.通过前述权利要求任一项的方法而得到的含水聚硅酸盐微凝胶作为絮凝剂结合至少一种阳离子或两性聚合物在纸浆和纸张的生产中以及在水净化过程中的应用。
21.一种用于从纤维素纤维和任选填料的悬浮液中生产纸张的方法,它包括向该悬浮液中加入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,将该悬浮液在网上成形并滤水,其特征在于,所述二氧化硅基材料是通过前述权利要求任一项的方法而得到的含水聚硅酸盐微凝胶。
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- 1998-06-08 AT AT98928775T patent/ATE550298T1/de active
- 1998-06-08 CN CNB988059975A patent/CN1321887C/zh not_active Expired - Fee Related
- 1998-06-08 CA CA002481870A patent/CA2481870C/en not_active Expired - Fee Related
- 1998-06-08 EP EP98928775A patent/EP0989956B1/en not_active Expired - Lifetime
- 1998-06-08 PT PT98928775T patent/PT989956E/pt unknown
- 1998-06-08 AU AU80489/98A patent/AU736396B2/en not_active Ceased
- 1998-06-08 JP JP50228699A patent/JP3487511B2/ja not_active Expired - Fee Related
- 1998-06-08 RU RU2000100335/12A patent/RU2189351C2/ru not_active IP Right Cessation
- 1998-06-08 BR BR9811257-0A patent/BR9811257A/pt not_active IP Right Cessation
- 1998-06-08 WO PCT/SE1998/001102 patent/WO1998056716A1/en active IP Right Grant
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1999
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989006637A1 (en) * | 1988-01-13 | 1989-07-27 | E.I. Du Pont De Nemours And Company | Polyaluminosilicate microgel process and composition |
EP0359552A2 (en) * | 1988-09-16 | 1990-03-21 | E.I. Du Pont De Nemours And Company | Polysilicate microgels as retention/drainage aids in papermaking |
Also Published As
Publication number | Publication date |
---|---|
BR9811257A (pt) | 2000-07-18 |
JP3487511B2 (ja) | 2004-01-19 |
KR20010013232A (ko) | 2001-02-26 |
CA2292577C (en) | 2005-02-08 |
AU736396B2 (en) | 2001-07-26 |
US20020179267A1 (en) | 2002-12-05 |
WO1998056716A1 (en) | 1998-12-17 |
PT989956E (pt) | 2012-06-25 |
NO996056L (no) | 2000-02-01 |
CA2481870A1 (en) | 1998-12-17 |
RU2189351C2 (ru) | 2002-09-20 |
ID23976A (id) | 2000-06-14 |
NO996056D0 (no) | 1999-12-08 |
CA2292577A1 (en) | 1998-12-17 |
EP0989956A1 (en) | 2000-04-05 |
KR100372358B1 (ko) | 2003-02-17 |
AU8048998A (en) | 1998-12-30 |
NO329169B1 (no) | 2010-09-06 |
US6673208B2 (en) | 2004-01-06 |
EP0989956B1 (en) | 2012-03-21 |
ES2383951T3 (es) | 2012-06-27 |
ATE550298T1 (de) | 2012-04-15 |
CN1259922A (zh) | 2000-07-12 |
CA2481870C (en) | 2009-05-05 |
JP2001506224A (ja) | 2001-05-15 |
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CA2292652C (en) | Polysilicate microgels | |
EP1242308B1 (en) | Silica-based sols | |
ZA200204344B (en) | Silica-based sols. |
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