CN102341349B - The preparation method of layered silicate - Google Patents
The preparation method of layered silicate Download PDFInfo
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- CN102341349B CN102341349B CN201080010370.3A CN201080010370A CN102341349B CN 102341349 B CN102341349 B CN 102341349B CN 201080010370 A CN201080010370 A CN 201080010370A CN 102341349 B CN102341349 B CN 102341349B
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- mixture
- silicate
- ammonium compound
- sio
- water
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000000203 mixture Substances 0.000 claims abstract description 125
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 69
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 229910052645 tectosilicate Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000004760 silicates Chemical class 0.000 claims description 8
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 238000000465 moulding Methods 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
- -1 halide anions Chemical class 0.000 description 15
- 239000011148 porous material Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000005216 hydrothermal crystallization Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012711 adhesive precursor Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000011026 diafiltration Methods 0.000 description 2
- 229910001649 dickite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 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
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 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
- 239000004610 Internal Lubricant Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229930006000 Sucrose Natural products 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- RNUBFUJXCFSMQP-UHFFFAOYSA-N borol-2-one Chemical compound O=C1B=CC=C1 RNUBFUJXCFSMQP-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 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
- 239000006210 lotion Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000006250 specific catalysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of preparation method containing at least layered silicate of silicon and oxygen, it comprises (1) provides containing silicon-dioxide and/or at least one silica precursor, water, at least one tetraalkyl ammonium compound and at least one alkali, and the mixture of the suitable seed crystal material of optional at least one, described tetraalkyl ammonium compound is selected from the group of following composition, diethyl-dimethyl ammonium compound, triethyl methyl ammonium compound, and the mixture of diethyl-dimethyl ammonium and triethyl methyl ammonium compound; (2) mixture obtained according to (1) is heated to 120 DEG C to 160 DEG C under autogenous pressure (hydrothermal condition), reaches 5 to 10 days, obtain the suspension containing this layered silicate.
Description
The present invention relates to the preparation method containing at least layered silicate of silicon and oxygen, it comprises
(1) provide containing silicon-dioxide and/or at least one silica precursor, water, at least one tetraalkyl ammonium compound and at least one alkali, and the mixture of the suitable seed crystal material of optional at least one, described tetraalkyl ammonium compound is selected from the group of following composition, diethyl-dimethyl ammonium compound, triethyl methyl ammonium compound, and the mixture of diethyl-dimethyl ammonium and triethyl methyl ammonium compound;
(2) mixture obtained according to (1) is heated to 120 DEG C to 160 DEG C under autogenous pressure (hydrothermal condition), reaches 5 to 10 days, obtain the suspension containing this layered silicate.
Further, the present invention relates to that obtained by method of the present invention or obtainable layered silicate, and relate to the specific silicon hydrochlorate with novel texture.Meanwhile, the present invention relates to the tectosilicate (tectosilicate) can prepared from this layered silicate.In addition, the present invention relates to the specific end use of this layered silicate and/or this tectosilicate.
In the art, layered silicate is known.Such as, such as at J.Song, H.Gies; Studiesin Surface Science and Catalysis, the 15th volume, 2004, disclosed in 295-300 page, those materials can be mentioned.
In various technical field, such as, such as, catalysis or absorption, have the continuous needs to type material, especially silicate respectively, and allow manufacture for solving the needs of the novel process of the custom materials of specific catalysis or absorption problem.
Therefore, an object of the present invention is to provide the new process preparing layered silicate, it can be used for, such as, and above-mentioned field, or precursor is used as in tectosilicate preparation.Another object of the present invention is to provide new stratified material.Further, it is expected to, the material that can obtain from this novel process or this new stratified material can be used as starting raw material prepared by pillared silicates (pillard silicate).
Therefore, the present invention relates to the preparation method containing at least layered silicate of silicon and oxygen, it comprises
(1) provide containing silicon-dioxide and/or at least one silica precursor, water, at least one tetra-allkylammonium based compound and at least one alkali, and the mixture of the suitable seed crystal material of optional at least one, described tetra-allkylammonium based compound is selected from the group of following composition, diethyl-dimethyl ammonium compound, triethyl methyl ammonium compound, and the mixture of diethyl-dimethyl ammonium and triethyl methyl ammonium compound;
(2) mixture obtained according to (1) is heated to 120 DEG C to 160 DEG C under autogenous pressure (hydrothermal condition), reaches 5 to 10 days, obtain the suspension containing this layered silicate.
According to the present invention, except at least one tetraalkyl ammonium compound, also can use a kind of alkali being different from this compound.The example of these alkali is ammonium hydroxide NH
4oH, alkali metal hydroxide or alkaline earth metal hydroxides, such as sodium hydroxide or potassium hydroxide, or the mixture of two or more of these compounds.In this case, at least one tetraalkyl ammonium compound contains one or more suitable negatively charged ion, such as halide anions, such as fluorion or chlorion or bromide anion or iodide ion.
Preferably, this at least one tetraalkyl ammonium compound is containing with good grounds (1) alkali as negatively charged ion.Basic anion example in this article comprises, especially, and hydroxide ion or aluminate ion.Particularly preferred basic anion is hydroxide ion.
Therefore, the mixture provided in (1) preferably contains diethyl-dimethyl-ammonium hydroxide, triethyl methyl ammonium hydroxide, or the mixture of diethyl-dimethyl ammonium hydroxide and triethyl methyl ammonium hydroxide.
Especially preferably, the mixture provided in (1) is only containing a kind of tetraalkyl ammonium compound, more preferably a kind of tetra-alkyl ammonium hydroxide, especially diethyl-dimethyl ammonium hydroxide.
Due to this preferred embodiment, be preferably, be substantially devoid of according to the mixture of (1) and be different from Common Anions hydroxy, described Common Anions is typically used as the gegenion of tetraalkyl ammonium ion simultaneously.Preferably, the mixture according to (1) is substantially devoid of halide-ions, such as bromide anion or fluorion.In this article, the respective content that term " is substantially devoid of " the described negatively charged ion generally referred in described mixture is no more than 500ppm.
Any suitable compound all can be used as silicon-dioxide or silica precursor in principle.The term " silica precursor " used in this article refers to a kind of compound, and it is under selected reaction conditions, allows the silicate sturcture forming layered silicate.Tetraalkoxysilane, such as tetramethoxy-silicane, tetraethoxy-silicane or tetrapropoxysilane, can mode as an example, is mentioned as precursor compound.In processing method of the present invention, described silicon-dioxide particularly preferably uses.Such as, this type of silica source can be pyrogene (fumed), and soft silica, silicon dioxide gel is ludox etc. such as.Can be expected that, the mixture of the mixture of the mixture of two or more silica source or two or more silica precursors or at least one silica source and at least silica precursor also can use.Especially preferably soft silica.Further, preferred soft silica is as unique silica source.
Therefore, the invention still further relates to method as above, wherein according to (1), use soft silica.
In principle, any suitable soft silica can be used.Preferably use and there is 10-400m
2the soft silica of the specific surface area (BET, Brunauer-Emmet-Teller are detected at 77K by nitrogen adsorption method according to DIN 66131) of/g, preferred 10-100m
2/ g, particularly preferably 10-50m
2/ g.Other preferred scope is 50-100m
2/ g or 100-300m
2/ g or 300-400m
2/ g.
In the mixture of basis (1), silicon-dioxide and/or silica precursor, tetraalkyl ammonium compound, and the molar ratio of water, described silicon-dioxide and/or silica precursor are with SiO
2calculate, can select according to the layered silicate that will obtain.Surprisingly, find the specific hydrothermal condition according to (2), namely Tc is 120 to 160 DEG C, and when the crystallization phase is 5 to 10 days, allow for the preparation of novel material, this depends on the molar ratio of described material.In addition, if found except molar ratio, the change crystallization phase can obtain the novel material with these parameter particular combination.Therefore the flexible theory providing the many novel materials allowing synthesis this area the unknown in the Tc of 120-160 DEG C and the parameters combination of the crystallization phase of 5-10 days is believed.
With regard to this Tc, temperature range is 125 to 155 DEG C, more preferably from 130 to 150 DEG C, and more preferably from 135 to 145 DEG C.Especially, temperature range is 138 to 142 DEG C.
Other conceivable temperature range is, such as, and 120 to 130 DEG C or 130 to 140 DEG C or 140 to 150 DEG C or 150 to 160 DEG C.According to the present invention, during the crystallization of (2), also can use two or more different temperature.In this article, temperature can be regulated to certain value in above-mentioned scope, keep this temperature certain hour, then increase or reduce the temperature to another value in above-mentioned scope.With this step by step temperature regulate contrary or as a supplement, during hydrothermal crystallization, Tc can little by little reduce or improve.In general, the heating rate of applying, though be according to (1) heated mixt to Tc and/or during (2) heated mixt, all can carry out appropriate selection.Preferably, heating rate is 0.1 DEG C/min to 20 DEG C/min, preferably from 0.3 DEG C/min to 15 DEG C/min, especially from 0.5 DEG C/min to 10 DEG C/min.
With regard to above-mentioned silicon-dioxide and/or its precursor, tetraalkyl ammonium compound, with the molar ratio of water, it ranges preferably from 1: (0.3-0.7): (9-15), more preferably 1: (0.4-0.6): (9-15), and more preferably 1: (0.45-0.55): (9-15).Especially preferred is silicon-dioxide or its precursor: the molar ratio of tetraalkyl ammonium compound is 1: (0.48-0.52), especially 1: (0.49-0.51).
Therefore, the present invention relates to a kind of method as above, the mixture wherein obtained according to (1) contains with SiO
2the SiO of meter
2and/or its silica precursor, at least one tetraalkyl ammonium compound and water, its molar ratio is, SiO
2: tetraalkyl ammonium compound: water is 1: (0.3-0.7): (9-15), preferably 1: (0.4-0.6): (9-15), more preferably 1: (0.45-0.55): (9-15).
Therefore, in step (1), provide the mixture carrying out hydrothermal crystallization in step (2).In general, possible, the order can imagined with each, mixes single starting raw material.Preferably, silicon-dioxide or its precursor mix with the aqueous mixture containing tetraalkyl ammonium compound.After these structure directing reagent (structure directing agent) are added, preferably stir the mixture obtained, preferably carry out 0.1 to 10 hours, more preferably from 0.5 to 5 hours, and more preferably 1 to 2 hours.Preparing in the process of colloidal solution according to (1), temperature is preferably 10 to 40 DEG C, more preferably 15 to 35 DEG C, particularly preferably 20 to 30 DEG C.
Depend on the starting raw material molar ratio desireed, possible, suitably removing or interpolation suitable quantity of water.Such as, use rotatory evaporator or carefully heated mixt, all can realize the removal of water.Water is removed, and preferably carries out at 60 to 85 DEG C of temperature, more preferably at 65 to 80 DEG C, particularly preferably in 65 to 75 DEG C.If water is added into or removes, preferably, the mixture obtained stirs 0.1 to 5 hours, preferably 0.5 to 2 hours.
According to another embodiment of the present invention, according at least one provenance of mixture in addition containing at least one element of (1), described element is adapted at the isomorphous substitution carrying out Si atom at least partially in the layered silicate obtained according to the hydrothermal crystallization of (2).Preferred suitable element is selected from the group of following composition, Al, B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, and their two kinds or more of mixtures.Due to the existence of at least one provenance of at least one suitable element, the silicate sturcture formed in hydrothermal crystallization process, not only containing Si atom, also contains the suitable element as at least one of the isomorphous substitution of Si atom.
Such as, if introduce aluminium, be possiblely, except as except the tetraalkyl ammonium compound of starting raw material and silicon-dioxide and/or silica precursor, also use such as metallic aluminium or suitable aluminate, such as alkali metal aluminate, and aluminum alcoholate, such as aluminum isopropylate.Such as, if introduce boron, possible, except as except the tetraalkyl ammonium compound of starting raw material and silicon-dioxide and/or silica precursor, also use, such as free boric acid and/or borate and/or boric acid ester, such as triethyl borate.Such as, if introduce titanium, possible, except as except the tetraalkyl ammonium compound of starting raw material and silicon-dioxide and/or silica precursor, also use, such as titanium alcoholate, such as titanium ethanolate or titanium propanolate.Such as, if introduce tin, be possiblely, except as except the tetraalkyl ammonium compound of starting raw material and silicon-dioxide and/or silica precursor, also use, such as tin chloride and/or organo-metallic tin compound, such as tin spirit alcoholate or inner complex, such as acetopyruvic acid tin.Such as, if introduce zirconium, possible, except as except the tetraalkyl ammonium compound of starting raw material and silicon-dioxide and/or silica precursor, also use, such as zirconium chloride and/or zirconium alcoholate.Such as, if introduce vanadium or germanium or niobium, possible, except as except the tetraalkyl ammonium compound of starting raw material and silicon-dioxide and/or silica precursor, also use, such as vanadium chloride or germanium chloride or niobium chloride.
According to another embodiment of the present invention, at least one seed crystal material can be added and be used as crystallization auxiliary to the mixture according to (1).Can imagine that all compounds of the stratified material wanted that can cause are used as seed crystal material.For the synthesis of given layered silicate, preferably, add layered silicate and/or tectosilicate, be used as seed crystal material, layered silicate and/or tectosilicate obtain from by layered silicate that hereinafter described method obtains.Especially preferred, as seed crystal material, add layered silicate.The typical concentration of seed crystal material is the seed crystal material of 0.1 to 5 % by weight, and the silicon-dioxide existed in the mixture based on (1) or silica precursor, calculate with silicon-dioxide.
Then the mixture obtained carries out hydrothermal crystallization in step (2).Preferably, mixture is transferred in autoclave.In order to Tc being adjusted to one or more temperature wanted, use further preferably the autoclave being equipped with heating and/or cooling way, such as, such as, inner or indirect heating and/or cooling way, such as, such as, heating and/or cooling jacket.Simultaneously possible, shift autoclave in a certain environment, such as baking oven, such as circulated air oven, or similar permission synthetic mixture keeps the place wanting temperature.
For the crystallization according to (2), synthetic mixture preferably carries out suitable agitation.Simultaneously possible, turn the reaction vessel carrying out crystallization.
According to the first particularly preferred embodiment of the present invention, contain SiO according to the mixture that (1) obtains
2and/or with SiO
2the silica precursor of meter, at least one tetraalkyl ammonium compound and water, its molar ratio is, SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5), be more preferably 1: (0.47-0.53): (9.7-10.3), is more preferably 1: (0.49-0.51): (9.9-10.1).
Therefore, the invention still further relates to method as above, the mixture wherein obtained according to (1) contains SiO
2, or with SiO
2the silica precursor of meter, at least one tetraalkyl ammonium compound and water, its molar ratio is, SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5).In addition, the present invention relates to silicate that is obtainable by described method or that obtain.
For the first particularly preferred embodiment, further preferably, the mixture of heating steps (2) reaches 8.5 to 9.5 days, more preferably 8.5 to 9.0 days, even more preferably from 8.6 to 8.8 days.
From these specific processing condition, layered silicate preferably can obtain or obtain, and it has the X-ray diffractogram comprising at least following reflection:
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| (6.09-6.29) | (80.0-100.0) |
| (7.90-8.10) | (80.0-100.0) |
| (20.30-20.50) | (11.1-17.1) |
| (23.95-24.15) | (11.9-19.9) |
| (24.81-25.01) | (16.2-26.2) |
| (25.34-25.54) | (17.3-25.3) |
| (26.56-26.76) | (10.4-16.4) |
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
In addition, the invention still further relates to a kind of layered silicate, it has the X-ray diffractogram containing at least following reflection:
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| (6.09-6.29) | (80.0-100.0) |
| (7.90-8.10) | (80.0-100.0) |
| (20.30-20.50) | (11.1-17.1) |
| (23.95-24.15) | (11.9-19.9) |
| (24.81-25.01) | (16.2-26.2) |
| (25.34-25.54) | (17.3-25.3) |
| (26.56-26.76) | (10.4-16.4) |
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
For the first particularly preferred embodiment, further preferably, the mixture of heating steps (2) reaches 5.5 to 6.5 days, more preferably 5.7 to 6.3 days, even more preferably from 5.9 to 6.1 days.
From these specific processing condition, layered silicate preferably can obtain or obtain, and it has the X-ray diffractogram comprising at least following reflection:
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| (5.65-5.85) | 100 |
| (18.79-18.99) | (14.10-22.10) |
| (20.62-20.82) | (14.70-22.70) |
| (22.06-22.26) | (14.30-22.30) |
| (22.95-23.15) | (17.80-27.80) |
| (23.37-23.57) | (15.10-23.10) |
| (25.93-26.13) | (15.20-25.20) |
| (31.08-31.28) | (14.30-22.30) |
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
In addition, the invention still further relates to a kind of layered silicate, it has the X-ray diffractogram containing at least following reflection:
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| (5.65-5.85) | 100 |
| (18.79-18.99) | (14.10-22.10) |
| (20.62-20.82) | (14.70-22.70) |
| (22.06-22.26) | (14.30-22.30) |
| (22.95-23.15) | (17.80-27.80) |
| (23.37-23.57) | (15.10-23.10) |
| (25.93-26.13) | (15.20-25.20) |
| (31.08-31.28) | (14.30-22.30) |
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
For the first particularly preferred embodiment, in addition preferably, the mixture of heating steps (2) reaches 6.7 to 7.5 days, more preferably 6.8 to 7.3 days, even more preferably from 6.9 to 7.1 days.
Therefore, the invention still further relates to the layered silicate that can be obtained by method of the present invention or obtain, the mixture wherein obtained according to (1) contains SiO
2and/or with SiO
2the silica precursor of meter, at least one tetraalkyl ammonium compound and water, its molar ratio is, SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5), and wherein according to step (2), mixture is carried out heating 6.7 to 7.5 days, preferably 6.8 to 7.3 days, even more preferably 6.9 to 7.1 days.Preferably, this layered silicate obtains by the following method or can obtain, the aqueous solution wherein used according to (1) contains diethyl-dimethyl ammonium hydroxide, triethyl methyl ammonium hydroxide, or the mixture of diethyl-dimethyl ammonium hydroxide and triethyl methyl ammonium hydroxide, more preferably, described solution contains diethyl-dimethyl-ammonium hydroxide.In particularly preferred embodiments, according to (2) heated mixt to 130 to 150 DEG C, preferably 135 to 145 DEG C.Most preferably, this layered silicate obtains from the mixture according to (1) or can obtain, described mixture is soft silica, the mixture of diethyl-dimethyl ammonium hydroxide and water, its molar ratio is 1: (0.49-0.51): (9.9-10.1), it is heated 164 to 172 hours at 139 to 141 DEG C according to (2).
According to the second particularly preferred embodiment of the present invention, contain SiO according to the mixture that (1) obtains
2and/or with SiO
2the silica precursor of meter, at least one tetraalkyl ammonium compound and water, its molar ratio is, SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (12.0-13.0), be more preferably 1: (0.47-0.53): (12.3-12.9), is more preferably 1: (0.49-0.51): (12.5-12.7).
Therefore, the invention still further relates to method as above, the mixture wherein obtained according to (1) contains SiO
2and/or with SiO
2the silica precursor of meter, at least one tetraalkyl ammonium compound and water, its molar ratio is, SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (12.0-13.0).In addition, the present invention relates to silicate that is obtainable by described method or that obtain.
For the second particularly preferred embodiment, further preferably, the mixture of heating steps (2) reaches 7.5 to 8.5 days, more preferably 7.7 to 8.3 days, even more preferably from 7.9 to 8.1 days.
From these specific processing condition, layered silicate preferably can obtain or obtain, and it has the X-ray diffractogram comprising at least following reflection:
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| (6.02-6.22) | 100 |
| (18.80-19.00) | (7.0-11.0) |
| (19.47-19.67) | (6.0-10.0) |
| (22.74-22.94) | (10.4-16.4) |
| (23.74-23.94) | (7.2-11.2) |
| (26.45-26.65) | (6.3-10.3) |
| (31.05-31.25) | (8.7-14.7) |
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
In addition, the invention still further relates to a kind of layered silicate, it has the X-ray diffractogram containing at least following reflection:
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| (6.02-6.22) | 100 |
| (18.80-19.00) | (7.0-11.0) |
| (19.47-19.67) | (6.0-10.0) |
| (22.74-22.94) | (10.4-16.4) |
| (23.74-23.94) | (7.2-11.2) |
| (26.45-26.65) | (6.3-10.3) |
| (31.05-31.25) | (8.7-14.7) |
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
According to the preferred embodiment of the inventive method, the layered silicate comprised in its mother liquor, by suitable method, at least one step, is separated in the suspension obtained from (2).This separation can be passed through, and such as, filter, ultrafiltration, the means of diafiltration (diafiltration) or centrifuging are carried out, or pass through, and such as, spraying dry and Spray granulation method are carried out.Means preferably by spraying dry or filtration are separated.
Therefore, the invention still further relates to method as above, it comprises in addition
(3) from the suspension obtained according to (2), this silicate is separated.
According to an embodiment of the inventive method, the crystallization according to (2) stops by suitable quenching.Here, particularly preferably be, add water in suspension, the temperature of described water is in the temperature being suitable for stopping crystallization.
According to the preferred embodiment of the inventive method, at least one silicate carrying out as mentioned above being separated is carried out washing and/or drying.
Therefore, the invention still further relates to method as above, it comprises in addition
(4) wash
And/or
(5) dry
According to the silicate obtained according to (3).
After separation, can then carry out at least one washing step and/or at least one drying step, wherein possiblely be, in at least two washing lotion steps, use identical or different washing composition or detergent mixture, and at least two drying step, use identical or different drying temperature.
If carried out at least one washing step, preferably, wash isolated silicate until the pH of washing water is 6 to 8, preferably 6.5 to 7.5, it is measured by normal glass electrode.
Here drying temperature is preferably room temperature to 180 DEG C, more preferably 75 DEG C to 170 DEG C, more preferably 90 DEG C to 160 DEG C, particularly preferably 100 DEG C to 150 DEG C.
Therefore, the invention still further relates to method as above, it comprises in addition
(3) from the suspension obtained according to (2), this silicate is separated.And comprise further
(4) wash, the pH to isolated silicate is 6.5 to 7.5, and
(5) isolated and that optionally washing is crossed silicate is carried out drying in the scope of 100 to 150 DEG C.
Spendable washing composition is, such as, and water, alcohol, such as methyl alcohol, ethanol or propyl alcohol, or they two or more mixture.The example of mixture is the mixture of two or more alcohol, such as methyl alcohol and ethanol or methyl alcohol and propyl alcohol or ethanol and propyl alcohol or methyl alcohol and ethanol and propyl alcohol, or the mixture of water and at least one alcohol, such as water and methyl alcohol or water and ethanol or water and propyl alcohol or water and methyl alcohol and ethanol or water and methyl alcohol and propyl alcohol or water and ethanol and propyl alcohol or water and methyl alcohol and ethanol and propyl alcohol.The mixture of preferably water or water and at least one alcohol, preferably water and ethanol, water particularly preferably can as unique washing composition.
According to method of the present invention, obtain a kind of silicate, especially layered silicate, wherein the atom of Si at least partially of this silicate sturcture is by optional isomorphous substitution.Therefore the present invention also relates to that obtained by method as above or obtainable a kind of silicate, especially layered silicate, optionally, and a kind of layered silicate of isomorphous substitution.
According to another embodiment, the invention still further relates to method as above, it comprises in addition and carries out suitable aftertreatment to isolated and optionally washing and/or dried silicate, thus element suitable for the atom of the Si at least partially at least one in burnt silicate is carried out isomorphous substitution.Preferred suitable element is selected from the group of following composition, Al, B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, and their two kinds or more of mixtures.No matter whether layered silicate is the layered silicate crossed of isomorphous substitution, and this type of aftertreatment of layered silicate all can be carried out.
According to the another embodiment of the inventive method, the layered silicate obtained according to (2), at least one additional step, is calcined according to (6).In principle, possible, include the suspension of layered silicate, the mother liquor namely containing layered silicate, is directly calcined.Preferably, this silicate is separated before being calcined from suspension, according to (3) as above.Before being calcined, the silicate be separated from suspension can carry out at least one washing step as above (4) and/or at least one drying step as above (5).
The calcining carried out according to (6) of the silicate obtained according to (2) and/or (3) and/or (4) and/or (5) preferably carrying out at 700 DEG C at the most, obtains tectosilicate.More preferably, calcining temperature is 300 to 700 DEG C, more preferably from 300 to 600 DEG C.
Therefore, according to the preferred embodiment of the inventive method, the heating of this layered silicate is carried out at the temperature of room temperature to maximum 700 DEG C, heating rate more preferably 0.1 to 12 DEG C/h, more preferably from 1 to 11 DEG C/h, particularly preferably 5 to 10 DEG C/h.
According to one of the inventive method possible embodiment, this calcining is carried out step by step at the temperature of order.In the present invention, term " at the temperature of order step by step " refers to a calcination process, wherein to be heated to a specified temp by the silicate calcined, keep specified time at such a temperature, and be heated at least one other temperature from this specified temp, and again keep this temperature to reach a specified time.If carried out calcining step by step, preferably to be reached 4 by the silicate calcined, more preferably reach 3, particularly preferably keep at 2 temperature.
This calcining can be carried out in any suitable atmosphere, such as air, poor air (lean air), nitrogen, steam, synthetic gas or carbonic acid gas.Calcining is preferably carried out in atmosphere.
Calcining can be carried out in the device of this object any being applicable to.This calcining preferably at swivel pipe, banded calcining furnace, retort furnace, or wish that the device situ of purposes carries out, such as, as molecular sieve or for Another Application occasion as described below by being used for it subsequently at silicate.Here particularly preferably swivel pipe and banded calcining furnace.
According to method of the present invention, obtain a kind of silicate, especially tectosilicate.
Therefore, the invention still further relates to method as above, it comprises in addition
(6) calcined by the silicate obtained according to (2) or (3) or (4) or (5), calcining is preferably carried out at 300 to 700 DEG C, more preferably 300 to 600 DEG C.
After calcining, according to another embodiment, the invention still further relates to method as above, it comprises in addition and carries out suitable aftertreatment to burnt silicate, thus element suitable for the atom of the Si at least partially at least one in burnt silicate is carried out isomorphous substitution.Preferred suitable element is selected from the group of following composition, Al, B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, and their two kinds or more of mixtures.No matter before calcination, whether layered silicate is the layered silicate crossed of isomorphous substitution, and this type of aftertreatment of calcined silicate all can be carried out.Depend on the atomic type being incorporated into lattice, can form so electronegative skeleton, it makes such as positively charged ion to be loaded into silicate becomes possibility.Especially, the structure directing reagent of ammonium ion tetra-allkylammonium, platinum, palladium, rhodium or ruthenium positively charged ion, Jinyang ion, alkali metal cation, such as sodium or potassium ion, or alkaline earth metal cation, such as magnesium or calcium ion, can use.
Therefore the present invention also relates to by the obtainable silicate of method described above, especially tectosilicate, and described method comprises the calcining according to (6), optionally carries out isomorphous substitution thereafter.
In many engineer applied, user wishes to use finished layered silicate and/or tectosilicate to be molded usually, instead of the silicate of itself form.This type of mouldings is required, especially in many industrial processes, such as, such as, to carry out the operation of separate substance from mixture easily, in tubular reactor.
Therefore the present invention also relates to containing crystal described above, the mouldings of micropore layered silicate and/or tectosilicate.The present invention also comprises the mouldings containing, for example upper layered silicate.
In general, this mouldings can comprise all other compounds imaginabale, and except layered silicate of the present invention and/or tectosilicate, its prerequisite is the application scenario that mouldings that it guarantees to obtain is applicable to want.
In the present invention, preferably in mouldings is produced, at least one proper adhesive material is employed.In the preferred embodiment, it is further preferred that prepared the mixture of layered silicate and/or tectosilicate and at least one tackiness agent.Suitable tackiness agent is on all bases that can be introduced in physical adsorption when not having tackiness agent between tectosilicate particle that will be combined in principle and exceedes the bonding of physical adsorption when not having tackiness agent and/or the compound of gathering.The example of this type of tackiness agent is metal oxide, such as SiO
2, Al
2o
3, TiO
2, ZrO
2or MgO, or the mixture of two or more of clay or these compounds.As Al
2o
3tackiness agent, particularly preferably clay mineral and natural or borolon, such as α-, β-, γ-, δ-, η-, κ-, χ-or θ-aluminum oxide and their inorganic or Organometallic precursor compounds, such as gibbsite (gibbsite), bayerite (bayerite), boehmite (boehmite), pseudobochmite (pseudoboehmite) or aluminic acid tri-alkoxy ester (trialkoxyaluminate), such as three aluminium isopropylates.Preferred tackiness agent is amphiphilic cpds and the graphite with polarity and nonpolar moieties further.Other tackiness agent is such as clay, such as polynite, kaolin, wilkinite (bentonite), halloysite (halloysite), dickite (dickite), nakrite (nacrite) or anaxite.These tackiness agents can use with the form of himself.Also can use such compound within the scope of the present invention, in the production in mouldings, at least one other step, form tackiness agent by these compounds.These adhesive precursor examples are tetraalkoxysilanes, four alkoxy titanates, four alkoxy zirconium esters, or the mixture of two or more different tetraalkoxysilanes, or the mixture of two or more different four alkoxy titanates, or the mixture of two or more different four alkoxy zirconium esters, or the mixture of at least one tetraalkoxysilane and at least one four alkoxy titanates, or the mixture of at least one tetraalkoxysilane and at least one four alkoxy zirconium ester, or the mixture of at least one four alkoxy titanates and at least one four alkoxy zirconium ester, or the mixture of at least one tetraalkoxysilane and at least one four alkoxy titanates and at least one four alkoxy zirconium ester.In the present invention, can use wholly or in part by SiO
2or SiO
2the tackiness agent of precursor composition, described precursor forms SiO in mouldings is produced at least one other step
2.In this article, colloidal silica and so-called " wet silica " and so-called " dry silica " can be used.Silicon-dioxide is particularly preferably unbodied silicon-dioxide, and wherein the size of silicon dioxide granule is such as 5-100nm, and the surface-area of silicon dioxide granule is 50-500m
2/ g.Colloidal silica, preferably with the form of alkaline solution and/or ammonia solution, more preferably with the form of ammonia solution, especially can conduct
or
obtain." wet method " silicon-dioxide especially can as such as
or
obtain." dry method " silicon-dioxide especially can such as conduct
or
obtain.The consumption of tackiness agent preferably makes final mouldings have maximum tackiness agent of 80 % by weight, more preferably 5-80 % by weight, more preferably 10-70 % by weight, more preferably 10-60 % by weight, more preferably 15-50 % by weight, more preferably 15-45 % by weight, particularly preferably 15-40 % by weight, in each case based on final mouldings total weight.The term " final mouldings " that uses in this article represents the mouldings obtained from drying as described below and calcination stage (IV) and/or (V), preferably from the mouldings that (V) obtains.
Other compound of at least one can mix with the mixture of tackiness agent or adhesive precursor and zeolitic material, for further processing and for the formation of plastic material.Particularly, preferably pore former can be mentioned here.In the methods of the invention, operable pore former is all compounds that can provide particular bore size and/or particular bore distribution of sizes and/or particular bore volume in final mouldings.The pore former used in the methods of the invention preferably can be disperseed, suspended and/or be emulsifiable in the polymkeric substance in water or aequeous solvent mixture.Preferred polymkeric substance is polyvinyl compound, such as polyalkylene oxide is as polyethylene oxide, polystyrene, polyacrylic ester, polymethacrylate, polyolefine, polymeric amide and polyester, carbohydrate such as Mierocrystalline cellulose or derivatived cellulose are as methylcellulose gum, or sucrose or natural fiber.Other suitable pore former is, such as paper pulp or graphite.If employ pore former in the mixture preparation in step (I), then pore former, preferred polymers, content in (I) in obtained mixture is preferably in 5 ~ 90 % by weight scopes, preferably in 15 ~ 75 % by weight scopes, particularly preferably in 25 ~ 55 % by weight scopes, be all the gauge based on the novel tectosilicate in the mixture in step (I) in often kind of situation.If in order to produce the pore size distribution needs that will reach, the mixture of two or more pore formers can also be used.In the particularly preferred embodiment of the inventive method, as described below, by calcining removing pore former in step (V), thus obtain porous mouldings.
In similar preferred embodiment of the present invention, prepare in the process of mixture in basis (I) and add at least one paste agent (pasting agent).As paste agent, all compounds being suitable for this object can be used.These preferably organically, particularly hydrophilic polymer, as Mierocrystalline cellulose, derivatived cellulose is as methylcellulose gum, and starch is as yam starch, wallpaper is stuck with paste, polyacrylic ester, polymethacrylate, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene or polytetrahydrofuran.Therefore, especially, can use also as the compound of pore former as paste agent.In particularly preferred the inventive method embodiment, as described below, these paste agents are removed by the calcining in step (V), obtain porous mouldings.
According to another embodiment of the present invention, at least one acid additives can be added during preparing mixture according to (I).Very particularly preferably, can by calcining removing organic acidity compound in preferred steps (V) as described below.Particularly preferably carboxylic acid, such as formic acid, oxalic acid and/or citric acid.Also the mixture of two or more these acidic cpds can be used.
The order of addition containing each component in the mixture of layered silicate and/or tectosilicate according to (I) is not crucial.Can first add at least one tackiness agent, then at least one pore former, at least one acidic cpd is added, finally add at least one paste agent, also can exchange the order of at least one tackiness agent, at least one pore former, at least one acidic cpd and at least one paste agent.
Add tackiness agent in layered silicate and/or tectosilicate solid (if to properly adding above-mentioned at least one compound to it) after, according to the general homogenizing 10-180 minute of the mixture of (I).Especially, kneader, pan mill or forcing machine are particularly preferred for homogenizing.Mixture is preferably mediated.At industrial scale, the process in pan mill is preferred for homogenizing.Carry out under the temperature of homogenizing generally between about 10 DEG C of boiling points to paste agent and normal atmosphere or a little higher than atmospheric pressure.If properly, at least one above-claimed cpd can be added subsequently.The mixture of acquisition like this carries out homogenizing, preferably mediates, until form extrudable plastic material.
According to more preferred of the present invention, the mixture of homogenizing is molded.In the present invention, preferred method of moulding be wherein in conventional extruders by extruding those methods of carrying out, such as obtain diameter and be preferably 1 ~ 10mm, be particularly preferably the extrudate of 2 ~ 5mm.Such extrusion equipment is such as at Ullmann ' s
der Technischen Chemie, the 4th edition, the 2nd volume, the 295th page is risen, described by having in 1972.Except using screwe-type xtruder, plunger type extruder (plunge-type extruder) is also preferably used to be molded.But, all known and/or suitable kneadings and molding equipment and method can be used in principle to carry out shaping.These especially comprise: briquetting (briquetting), namely add or do not add extra adhesive material and carry out mechanical compaction; Granulation (pelleting), is namely compressed by circumference and/or rotary motion; Sintering, namely heat-treats the material that will be molded.The profile of the mouldings that will manufacture according to the present invention can be selected as required.Especially, except spherical, ellipse, right cylinder or plates are also possible.
In the present invention, preferably then step (III) carries out at least one drying step.
In the present invention, preferably then step (IV) carries out at least one calcining step.Generally speaking, calcine and carry out at 300 to 700 DEG C, more preferably carry out from 300 to 600 DEG C.Calcining can be carried out in any suitable atmosphere, preferred air and/or poor air.In addition, calcining, preferably at retort furnace, is carried out in rotary kiln and/or banded calcining baking oven.Possible, in calcining step, temperature remained constant, or continuous or discontinuous change.If calcine twice or usually more times, calcining temperature can be identical or different in each step.
Therefore, the invention still further relates to the method for producing mouldings as above, it comprises the steps
(I) prepare a kind of mixture, it contains layered silicate as above and/or tectosilicate, or or the layered silicate that obtain obtainable by method described above and/or tectosilicate, and optional at least one tackiness agent;
(II) kneaded mixture;
(III) mixture of kneading is carried out being molded obtain at least one mouldings;
(IV) this at least one mouldings dry;
(V) mouldings that this at least one of calcination is dried.
Before the drying and/or afterwards, and/or before being calcined and/or afterwards, this at least one mouldings can, if properly, process with the concentrated or Broenstedt acid of dilution or the mixture of two or more Broenstedt acid.Suitable acid is, such as, and hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or carboxylic acid, dicarboxylic acid or oligomeric or poly carboxylic acid, such as nitrilotriacetic acid(NTA), sulphosalicylic acid or ethylenediamine tetraacetic acid (EDTA).If properly, after at least one process carried out with at least one Broenstedt acid, carry out at least one drying step and/or at least one calcining step, it carries out in every case under conditions, as described above.
According to the another embodiment of the inventive method, passable according to the mouldings that the present invention obtains, in order to better sclerosis, carry out steam-treated, preferably carry out at least again dry after which and or calcine at least again.Such as, after at least one drying step and at least one follow-up calcining step, this calcined mouldings carries out steam treatment, and then drying once and/or is at least again calcined once at least again.
The present invention relates to the use of silicate of the present invention in addition, the use of particularly novel tectosilicate, and/or the use of mouldings of the present invention, as molecular sieve, catalyzer, support of the catalyst or its tackiness agent, as sorbent material, pigment, the additive of washing composition, the additive of material of construction, thixotropic property is provided for giving paint slurry and finish paint, with the application as outside and internal lubricant, as fireproofing agent, the auxiliary agent of paper product and filler, sterilization and/or fungicidal and/or in herbicidal composition, for ion-exchange, for Production of Ceramics, at polymkeric substance, electrically, in optics or electro-optical components and in switching element or sensor.
Preferably, layered silicate of the present invention, and/or the inventive method obtains or obtainable layered silicate, and/or tectosilicate of the present invention, can be used as catalyzer, support of the catalyst or its tackiness agent, sorbent material, for ion-exchange, for Production of Ceramics, or use in the polymer.
In addition, according to layered silicate of the present invention, the starting raw material that pillared silicates manufactures can be used as.
The present invention comes to explain in more detail with reference to the following examples, figure and table.
Accompanying drawing explanation
Fig. 1 shows the X-ray diffractogram of the layered silicate of the drying obtained respectively according to embodiment 1 to 4 to 4.The figure that Fig. 1 further comprises RUB-36 structure comes for contrast.Powder x-ray diffraction figure uses monochromatic Cu K α-1 radiation record on Siemens D-5000, wherein uses capillary sample support to avoid preferred orientation.Diffraction data uses and collects from the position sensing Sensitive Detector of Braun, and in 8-96 degree (2 θ) scope, step-length is 0.0678 degree.The exponentiate service routine Treor90 of powder pattern carries out, and in powder-X, (Treor90 is common program, can freely be obtained by URL http://www.ch.incr.org/sincris-top/logiciel in enforcement.In the drawings, 2 θ angles in units of spending are drawn along transverse axis, and intensity is drawn along the longitudinal axis.
Fig. 5 shows each scanning electronic microscope (SEM) image of the dry layered silicate obtained according to embodiment 4.
Embodiment:
Embodiment 1: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 % by weight) solution of 1139.7g is weighed, and adds beaker, substep add 238.9g soft silica (
), stir the mixture 2 hours, obtain yellowish suspension.
Then use rotatory evaporator to remove 188.6g water from the mixture obtained, stir concentrated mixture 1 hour.Then 172.5g mixture is weighed, add high-pressure digestion container (pressuredigestion vessel), then wherein under hydrothermal conditions, 140 DEG C of heating 208 hours.
Then by centrifugation, luminous for the silvery white obtained suspension is separated, cleans to pH7 with distilled water, and 120 DEG C of dryings 24 hours, obtain the white powder of 31.8g thus.
The product of synthesis has the reflection shown in table 1 in X-ray diffractogram (Cu K α 1).
Table 1: the X-ray color collection of illustrative plates of novel lamellar silicate
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| 6.19 | 98.5 |
| 8.00 | 100.0 |
| 10.47 | 1.7 |
| 12.34 | 1.5 |
| 12.69 | 3.1 |
| 14.18 | 3.0 |
| 16.00 | 3.2 |
| 17.18 | 8.1 |
| 17.95 | 4.0 |
| 18.98 | 3.8 |
| 19.62 | 4.4 |
| 20.40 | 14.1 |
| 21.22 | 7.4 |
| 22.53 | 5.6 |
| 22.88 | 10.2 |
| 23.36 | 7.2 |
| 24.05 | 15.9 |
| 24.91 | 21.2 |
| 25.44 | 22.3 |
| 26.23 | 9.1 |
| 26.66 | 13.4 |
| 26.98 | 10.3 |
| 27.76 | 6.4 |
| 28.56 | 5.3 |
| 29.75 | 4.6 |
| 31.15 | 8.8 |
| 32.93 | 2.9 |
| 34.47 | 3.3 |
| 35.22 | 3.0 |
| 36.45 | 3.6 |
| 37.13 | 3.7 |
| 38.39 | 3.6 |
| 40.60 | 5.2 |
| 42.18 | 3.8 |
| 44.20 | 3.6 |
| 45.17 | 5.9 |
| 46.10 | 4.6 |
| 46.53 | 4.0 |
| 47.14 | 3.9 |
| 48.39 | 5.7 |
| 49.57 | 5.9 |
| 50.75 | 4.4 |
Embodiment 2: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 % by weight) solution of 976.9g is weighed, and adds beaker, substep add 204.7g soft silica (
), stir the mixture 1 hour, obtain yellowish suspension.
Then use rotatory evaporator to remove 161.6g water from the mixture obtained, stir concentrated mixture 30 minutes.Then 121.5g mixture is weighed, add high-pressure digestion container, then under hydrothermal conditions, 140 DEG C of heating 144 hours, therefore obtain the white solid of pasty state wherein.
Then add in china bowl by the white suspension obtained, at 120 DEG C, drying 24 hours, therefore obtains the buff powder of 35.8g.
The product of synthesis has the reflection shown in table 2 in X-ray diffractogram (Cu K α 1).
Table 2: the X-ray color collection of illustrative plates of novel lamellar silicate
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| 5.75 | 100.00 |
| 7.95 | 4.80 |
| 10.48 | 10.70 |
| 10.85 | 7.50 |
| 11.53 | 8.10 |
| 13.05 | 6.80 |
| 13.30 | 6.50 |
| 15.17 | 7.40 |
| 15.87 | 12.10 |
| 17.17 | 11.00 |
| 18.33 | 17.40 |
| 18.57 | 17.00 |
| 18.89 | 18.10 |
| 19.97 | 15.30 |
| 20.72 | 18.70 |
| 21.16 | 15.10 |
| 21.85 | 17.50 |
| 22.16 | 18.30 |
| 22.40 | 16.30 |
| 23.05 | 22.80 |
| 23.47 | 19.10 |
| 24.43 | 14.00 |
| 24.71 | 16.00 |
| 25.16 | 12.20 |
| 26.03 | 20.20 |
| 26.94 | 15.60 |
| 27.37 | 12.70 |
| 27.99 | 12.70 |
| 28.87 | 11.20 |
| 29.25 | 13.40 |
| 30.31 | 13.30 |
| 30.87 | 14.40 |
| 31.18 | 18.30 |
| 33.75 | 7.60 |
| 34.43 | 9.20 |
| 36.34 | 7.30 |
| 37.00 | 7.60 |
| 37.93 | 7.50 |
| 39.24 | 7.10 |
| 39.72 | 7.80 |
| 40.88 | 6.90 |
| 42.07 | 8.60 |
| 43.03 | 7.30 |
| 44.64 | 7.70 |
| 45.83 | 8.50 |
| 48.60 | 8.10 |
Embodiment 3: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 % by weight) solution of 1628.2g is weighed, and adds beaker, substep add 341.2g soft silica (
), stir the mixture 2 hours, obtain yellowish suspension.
The mixture obtained is put into high-pressure digestion container, places 24 hours, subsequently under hydrothermal conditions, 140 DEG C of heating 192 hours.The luminous suspension of the silvery white obtained has the pH value of 12.57.
Then by suction filtration, separate solid reaction product, first washs with filtrate, then carries out washing until conductance is 105 μ s/cm with 9 liters of distilled water.Then by product 120 DEG C of dryings 24 hours, obtain the white powder of 205.0g thus.
The product of synthesis has the reflection shown in table 3 in X-ray diffractogram (Cu K α 1).
Table 3: the X-ray color collection of illustrative plates of novel lamellar silicate
| Diffraction angle 2 θ/° [Cu K (α 1)] | Intensity (%) |
| 6.12 | 100.0 |
| 7.97 | 3.1 |
| 10.44 | 4.0 |
| 11.09 | 2.3 |
| 12.28 | 2.4 |
| 12.97 | 2.6 |
| 13.65 | 2.6 |
| 16.04 | 4.4 |
| 16.78 | 5.8 |
| 17.43 | 5.3 |
| 18.46 | 5.2 |
| 18.90 | 9.0 |
| 19.57 | 8.0 |
| 20.09 | 7.4 |
| 20.61 | 7.2 |
| 22.44 | 7.8 |
| 22.84 | 13.4 |
| 23.84 | 9.2 |
| 24.15 | 7.6 |
| 24.76 | 4.3 |
| 25.39 | 7.0 |
| 26.10 | 7.8 |
| 26.55 | 8.3 |
| 27.39 | 4.5 |
| 27.87 | 4.9 |
| 28.48 | 5.8 |
| 29.32 | 4.6 |
| 29.64 | 4.6 |
| 31.15 | 11.7 |
| 31.58 | 4.9 |
| 32.85 | 2.7 |
| 34.24 | 2.2 |
| 35.07 | 3.3 |
| 36.38 | 3.3 |
| 36.97 | 3.8 |
| 38.06 | 2.6 |
| 39.12 | 2.7 |
| 39.77 | 2.7 |
| 40.73 | 3.5 |
| 42.00 | 3.5 |
| 43.38 | 3.1 |
| 43.89 | 3.2 |
| 45.00 | 3.1 |
| 45.57 | 3.2 |
| 48.02 | 3.8 |
| 48.90 | 4.1 |
Embodiment 4: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 % by weight) solution of 651.6g is weighed, and adds beaker, substep add 136.5g soft silica (
), stir the mixture 1 hour, obtain yellowish suspension.
Then use rotatory evaporator to remove 107.8g water from the mixture obtained, stir concentrated mixture 30 minutes, then obtain the suspension of pH 15.14.
171.4g mixture is weighed, adds high-pressure digestion container, then under hydrothermal conditions, 140 DEG C of heating 168 hours, obtain the pasty solid in the solution of pH 14.45 wherein.
Then by suction filtration, separate solid reaction product, carrying out washing to conductance with 2.5 liters of distilled water is 45.4 μ s/cm.Then by product 120 DEG C of dryings 24 hours, obtain the white powder of 24.9g thus.
Claims (22)
1. contain a layered silicate at least silicon and oxygen, its X-ray diffractogram comprises reflection at least as follows:
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
2. contain a layered silicate at least silicon and oxygen, its X-ray diffractogram comprises reflection at least as follows:
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
3. contain a layered silicate at least silicon and oxygen, its X-ray diffractogram comprises reflection at least as follows:
Wherein, 100% is relevant to the intensity at the maximum peak in X-ray diffractogram.
4. the preparation method containing at least layered silicate of silicon and oxygen any one of claim 1-3, it comprises
(1) provide containing silicon-dioxide and/or at least one silica precursor, water, at least one tetraalkyl ammonium compound and at least one alkali, and the mixture of the suitable seed crystal material of optional at least one, described tetraalkyl ammonium compound is selected from the group of following composition, diethyl-dimethyl ammonium compound, triethyl methyl ammonium compound, and the mixture of diethyl-dimethyl ammonium and triethyl methyl ammonium compound;
(2) mixture obtained according to (1) is heated to 120 DEG C at autogenous pressures to 160 DEG C, reaches 5 to 10 days, obtain the suspension containing this layered silicate,
The SiO that the mixture wherein obtained according to (1) contains
2and/or with SiO
2the silica precursor of meter, the molar ratio of at least one tetraalkyl ammonium compound and water is, SiO
2: tetraalkyl ammonium compound: water is 1:(0.3-0.7): (9-15).
5. the method for claim 4, the mixture wherein used according to (1) contains diethyl-dimethyl ammonium hydroxide, triethyl methyl ammonium hydroxide, or the mixture of diethyl-dimethyl ammonium hydroxide and triethyl methyl ammonium hydroxide.
6. the method for claim 4 or 5, the SiO that the mixture wherein obtained according to (1) contains
2and/or with SiO
2the silica precursor of meter, the molar ratio of at least one tetraalkyl ammonium compound and water is, SiO
2: tetraalkyl ammonium compound: water is 1:(0.4-0.6): (9-15).
7. the method for claim 4, the SiO that the mixture wherein obtained according to (1) contains
2and/or with SiO
2the silica precursor of meter, the molar ratio of at least one tetraalkyl ammonium compound and water is, SiO
2: tetraalkyl ammonium compound: water is 1:(0.45-0.55): (9.5-10.5).
8. the method for claim 7, wherein heats and reaches 8.5 to 9.5 days according to the mixture of (2).
9. the method for claim 7, wherein heats and reaches 5.5 to 6.5 days according to the mixture of (2).
10. the method for claim 7, wherein heats and reaches 6.7 to 7.5 days according to the mixture of (2).
The method of 11. claims 4, the SiO that the mixture wherein obtained according to (1) contains
2and/or with SiO
2the silica precursor of meter, the molar ratio of at least one tetraalkyl ammonium compound and water is, SiO
2: tetraalkyl ammonium compound: water is 1:(0.45-0.55): (12.0-13.0).
The method of 12. claims 11, wherein heats and reaches 7.5 to 8.5 days according to the mixture of (2).
The method of 13. claims 4 or 5, wherein according to (2), heated mixt is to 130-150 DEG C.
The method of 14. claims 4 or 5, wherein according to (1), uses soft silica.
The method of 15. claims 4 or 5, wherein according at least one provenance of mixture in addition containing at least one element of (1), described element is adapted at the isomorphous substitution carrying out Si atom at least partially in layered silicate.
The method of 16. claims 4, it comprises in addition
(3) from the suspension obtained according to (2), be separated this silicate, and optionally comprise further
(4) washing isolated silicate to pH is 6.5 to 7.5, and/or
(5) in the temperature range of 100 to 150 DEG C, isolated and that optionally washing is crossed silicate is carried out drying.
The method of 17. claims 16, it comprises further and carries out aftertreatment to isolated and optionally washing and/or dried silicate, thus element suitable for the atom of the Si at least partially at least one in layered silicate is carried out isomorphous substitution.
The method of 18. claims 4, it comprises in addition
(6) silicate obtained according to (2) is calcined.
The method of 19. claims 16, it comprises in addition
(6) silicate obtained according to (3) or (4) or (5) is calcined.
The method of 20. claims 18 or 19, it comprises further and carries out aftertreatment to burnt silicate, thus element suitable for the atom of the Si at least partially at least one in burnt silicate is carried out isomorphous substitution.
21. tectosilicates obtained according to the method for claim 18 or 19.
The application of 22. layered silicates as claimed in one of claims 1-3 or tectosilicate according to claim 21, it is as molecular sieve, catalyzer, support of the catalyst or its tackiness agent, and sorbent material, for ion-exchange, for Production of Ceramics, or use in the polymer.
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| US6756030B1 (en) * | 2003-03-21 | 2004-06-29 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-8 |
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