CN1142028C - Solid-form acid catalyst and its prepn - Google Patents
Solid-form acid catalyst and its prepn Download PDFInfo
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- CN1142028C CN1142028C CNB011184434A CN01118443A CN1142028C CN 1142028 C CN1142028 C CN 1142028C CN B011184434 A CNB011184434 A CN B011184434A CN 01118443 A CN01118443 A CN 01118443A CN 1142028 C CN1142028 C CN 1142028C
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- acid
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- 239000003377 acid catalyst Substances 0.000 title claims description 16
- 239000002253 acid Substances 0.000 claims abstract description 117
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- -1 silester Chemical compound 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002895 organic esters Chemical class 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000012429 reaction media Substances 0.000 abstract description 2
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 239000000499 gel Substances 0.000 description 17
- 230000009257 reactivity Effects 0.000 description 15
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 14
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 238000002479 acid--base titration Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000029936 alkylation Effects 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 235000013847 iso-butane Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002821 scintillation proximity assay Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a solid acid catalyst and a preparation method thereof. The solid acid catalyst is characterized in that the catalyst contains 1 to 80 wt% of liquid acid and 99 to 20 wt% of solid substances used for wrapping the liquid acid, wherein the liquid acid is hydrosulfate or hydrophosphate having one C1 to C10 alkyl and selectively contains sulphuric acid or phosphoric acid, and the proportion of the sulphuric acid or the phosphoric acid to the hydrosulfate or the hydrophosphate is 0 to 95:100 to 5. The acid centers of the solid acid catalyst provided by the present invention are multiple and are uniformly distributed, and the activity center keeps the characteristics of the liquid acid. The solid acid catalyst has the shape of solids, also has the reaction performance of the liquid acid, and is suitable for the low temperature reactions of nonpolar reaction media.
Description
Technical field
The present invention relates to acid catalyst of a kind of solid form and preparation method thereof.
Background technology
H
2SO
4, H
3PO
4, catalyst such as HF is the acid catalyst of industrial extensive use, process that some are important such as alkylation, esterification, isomerization etc. were all once used these catalyst or were still being used.Though these acid catalysts all have good catalytic activity, but because these catalyst all carry out catalytic action under homogeneous phase condition, compare with heterogeneous reaction, bring many shortcomings aborning, as on technology, being difficult to realize continuous production, catalyst is difficult for separating with product with raw material, and equipment corrosion etc.In these more external important chemical processes, above-mentioned acid catalyst also brings a large amount of accessory substances.Turn to example with alkyl, traditional handicraft prepares detergent alkylate with sulfuric acid or hydrofluoric acid as catalyst, has serious equipment corrosion and problem of environmental pollution; The technical process of benzene alkylation with propylene synthesizing iso-propylbenzene is former to be catalyst with alchlor also, and there are critical defects such as equipment corrosion, high pollution and operating difficulties in this method; In iso-butane/butene alkylation with sulfuric acid or hydrofluoric acid as catalyst, outside the problems such as depollution, corrosion, 1 ton of product of every production, will by-product 100 kilograms spent acid; In the Beckmann rearrangement of producing nylon-6 raw material caprolactam, 1 ton of caprolactam of every production is wanted 2.3 tons of sulphur ammoniums of by-product or the like.In order to overcome these shortcomings, many research work are all attempted to substitute these traditional acid catalysts with solid acid catalyst.Two methods commonly used, the one, these liquid acid appendix on carrier, or are adopted the solid acid catalyst of acidic oxide such as molecular sieve, amorphous silicon aluminium etc. " really ", but this two classes catalyst all there are some shortcomings, last class be since liquid acid be difficult to immobilized, very easy loss; Back one class catalyst is then owing to the acid site skewness, and the activated centre is few, and needs higher reaction temperature, therefore needs in the reaction of strong acid or low temperature at some, is difficult to substitute liquid acid in the alkylated reaction as iso-butane and butylene.In fact in this class reaction, even solid super-strong acid also can't reach the reactivity of liquid acid as 95% sulfuric acid, though the acid strength of solid super-strong acid is far above the acid strength of sulfuric acid.This is because liquid acid has more and mobile activated centre is arranged, and the acid site of solid acid is fixed, in case be capped, has just lost activity.
Summary of the invention
The purpose of this invention is to provide acid catalyst of a kind of solid form that contains liquid acid and preparation method thereof, this catalyst had both had the shape of solid, had the reactivity worth of liquid acid again.
The acid catalyst of solid form provided by the invention contains 1～80 weight %, the liquid acid of preferred 2～70 weight % and 99～20 weight %, the solid matter that is used to wrap up this liquid acid of preferred 98～30 weight %; Wherein said liquid acid is for having a C
1-C
10The sulfuric acid hydrogen ester of alkyl or phosphoric acid hydrogen ester, and optionally contain sulfuric acid or phosphoric acid, acid (sulfuric acid or phosphoric acid) is acid with the ratio of ester (sulfuric acid hydrogen ester or phosphoric acid hydrogen ester): ester=(0～95): (100～5), preferred acid: ester=(5～90): (95～10).
Said sulfuric acid hydrogen ester or phosphoric acid hydrogen ester are by sulfuric acid or phosphoric acid and have C in the acid catalyst of solid form provided by the invention
1-C
10The fatty alcohol of alkyl carries out condensation reaction and the ester that forms, and it can be by sulfuric acid or phosphoric acid and a kind of C of having
1-C
10The fatty alcohol of alkyl carries out condensation reaction and the ester that forms, perhaps also can be to have C by sulfuric acid or phosphoric acid and two or more different
1-C
10The fatty alcohol of alkyl carries out condensation reaction and the mixture of the ester that forms; This sulfuric acid hydrogen ester or phosphoric acid hydrogen ester optionally are wrapped in the said solid matter as the liquid acid activated centre with sulfuric acid or phosphoric acid; Said liquid acid can be that total concentration is 70～100 weight % according to the different requirements of concrete catalytic reaction in the catalyst prod, the aqueous solution of preferred 85～100 weight %.
The said solid matter that is used for wrapping up liquid acid can be any solid matter that liquid acid can be wrapped in wherein and be not easy to run off in liquid phase reactor liquid acid wherein in the acid catalyst of solid form provided by the invention, the gel-like solid matter that for example has cross-linked structure, the hydroxide with cross-linked structure or the oxide that comprise silicon, titanium, zirconium etc., wherein silicon gel most preferably.
The preparation method of the acid catalyst of solid form provided by the invention comprises:
(1). with a kind of organic esterified compound, for example the organic esterified compound of silicon, titanium or zirconium etc. mixes with the alcohols with 1-10 carbon atom and makes solution, and add entry when needed, be 5-100 weight % then with concentration, sulfuric acid or the phosphoric acid of preferred 10-80 weight % join in the gained solution, make that the weight ratio of said organic ester and said alcohol, acid and water is an ester in the gained mixture: alcohol: sour (with H
2SO
4Or H
3PO
4Meter): water=1: (0.1-5.0): (0.1-4): (0.1-4), preferred ester: alcohol: acid: water=1: (0.1-2.0): (0.5-3): (0.1-3), in room temperature to reflux temperature, preferably under reflux temperature stirring reaction 0.1-10 hour to forming gel;
(2). with (1) gained mixture under normal pressure or reduced pressure in room temperature to 150 ℃, handled 2-80 hour down for preferred 40-140 ℃;
Its precursor condition is: when the said reaction temperature of step (1) was lower than 100 ℃, the said treatment temperature of step (2) should be 100～150 ℃, so that generate sulfuric acid hydrogen ester or phosphoric acid hydrogen ester to the sulfuric acid of small part or phosphoric acid and pure condensation.
According to existing knowledge, the condensation reaction of sulfuric acid or phosphoric acid and alcohol generally could take place more than or equal to 100 ℃ the time.Therefore, when the said reaction temperature of step (1) has reached 100 ℃, condensation reaction has taken place with alcohol and has formed ester in sulfuric acid or phosphoric acid in step (1), the said treatment temperature of step (2) this moment can be lower than 100 ℃ (can certainly be higher than 100 ℃), and the effect of step this moment (2) mainly is to remove residual alcohol and liquid acid wherein is concentrated into needed concentration; When the said reaction temperature of step (1) is lower than 100 ℃, sulfuric acid or phosphoric acid do not form ester with alcohol generation condensation reaction in step (1), the said treatment temperature of step (2) this moment should be higher than 100 ℃, so that generate sulfuric acid hydrogen ester or phosphoric acid hydrogen ester to the sulfuric acid of small part or phosphoric acid and pure condensation, remove residual alcohol simultaneously and liquid acid wherein is concentrated into needed concentration.
Said organic esterified compound is silicic acid, metatitanic acid or zirconic acid and C in the method provided by the invention
1-C
4, preferred C
1-C
3Pure formed ester class, its object lesson comprises, but be not limited to methyl silicate, silester, silicic acid propyl ester, isopropyl silicate, tetraethyl titanate, titanium propanolate, isopropyl titanate, butyl titanate, iso-butyl titanate, zirconic acid propyl ester, zirconic acid isopropyl ester, tetrabutyl zirconate, zirconic acid isobutyl ester etc.Butyl ester, iso-butyl titanate, zirconic acid propyl ester, zirconic acid isopropyl ester, tetrabutyl zirconate, zirconic acid isobutyl ester etc.
The alcohols of the said 1-10 of a having carbon atom comprises in the method provided by the invention, but be not limited to, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol etc., or their mixture.
When the total amount of said alcohol in the reaction system is chemical when excessive with respect to sulfuric acid or phosphoric acid, be mainly sulfuric acid hydrogen ester or phosphoric acid hydrogen ester according to said liquid acid in the catalyst of the present invention; When sulfuric acid in the reaction system or phosphoric acid are chemical when excessive with respect to the total amount of said alcohol, be the mixture of sulfuric acid hydrogen ester or phosphoric acid hydrogen ester and sulfuric acid or phosphoric acid according to said liquid acid in the catalyst of the present invention.
Solid acid catalyst provided by the invention is a crosslinked skeleton structure of utilizing the synthetic middle hydrolysis of support oxide to form, liquid acid is wrapped in the carrier, make carrier sclerosis and liquid acid is concentrated through heat treatment again, form the solid acid of activated centre coated, can keep the character of its original liquid acid simultaneously to a certain extent.Solid acid provided by the invention is characterised in that, the acid site number is many and be evenly distributed, and the activated centre keeps the characteristics of liquid acid, has both had the shape of solid, has the reactivity worth of liquid acid again, is applicable to the low-temp reaction of nonpolar reaction medium; In addition, owing to sulfuric acid or phosphoric acid to small part are formed sulfuric acid hydrogen ester or phosphoric acid hydrogen ester by condensation, improved the stability of liquid acid in catalytic reaction.The result of embodiment from behind as can be seen, the acid catalyst of solid form provided by the invention has the reactivity worth suitable with liquid acid, simultaneously through wherein sour more stable after the liquid phase reactor, is not easy loss.Like this,, both avoided shortcomings such as product separation, equipment corrosion, environmental pollution, can reach the reaction effect of liquid acid catalyst again substantially by the present invention.
The acid catalyst of solid form provided by the invention can be used for adopting in sulfuric acid or the reaction of phosphoric acid as catalyst, for example can be used in the reactions such as alkylation, esterification, isomerization.
The specific embodiment
The following examples will the present invention is described further.Ammonia determination of adsorption method surface acid amount is (referring to Gabriele Centi and Siglinda Perathoner etc., " Therole of ammonia adspecies on the pathways of catalytic transformation at mixedmetal oxide surfaces ", Catal.Rev.-Sci.Eng., 40 (1﹠amp; 2), p175-208 (1998)); With the actual institute of determination of acid-basetitration solid acid acid content (referring to " Experiment of Analytical Chemistry ", second edition, the chief editor of Wuhan University, Higher Education Publishing House, 1985).
Acid strength H
0Measure according to the Hammett indicator method, concrete assay method is as follows: get the dry about 0.5g of sample and be placed on the little surface plate, use the indicator corresponding to different acid strengths to drip on sample, observation sample change color situation.If corresponding to the indicator generation change color of a certain acid strength, show that then sample has this acid strength.Indicator is to be the corresponding solution of 0.3 heavy % of solvent preparation with dried cyclohexane.
The reactivity worth of solid acid is investigated with iso-butane/butene alkylation.Employed reaction raw materials is pure iso-butane and pure 1-butylene (Beijing Analytical Instrument Factory's gas distribution station), and said alkane alkene is than the actual weight ratio that is meant isoparaffin and monoolefine in the mixed raw material.Reaction is to carry out in cover fixed bed reactors, and the fixed bed reaction system comprises feeding part, reactive moieties, separating part, analysis part:
Feeding part: feed pump is the SP-D2505 trace feed pump that Japanese exact science Co., Ltd. produces, and reaction material enters before the reactor earlier by a drying tube that molecular sieve desiccant is housed, and reaction mass is dewatered to the 20ppm;
Reactive moieties: comprise reactor, accurate pressure control and temperature regulating device, the reactor loading amount is 10ml; Control section can be controlled at reacting system pressure ± 0.01MPa, and reaction temperature is controlled at ± and 0.1 ℃;
Separating part: the material that has reacted separates with the low pressure separator of product through a 0.1MPa, and product is collected by the outlet of separator again and analyzes, and tail gas is separated the back sample analysis;
Analysis part: fluid product is analyzed by HP5890, and chromatographic column is the long OV-01 of 50m; Tail gas is analyzed by a HP5880, and chromatographic column is that refinery gas is analyzed chromatographic column specially.
Reaction condition: except as otherwise noted, alkylated reaction is all at 1MPa, carries out under 15 ℃, and reaction velocity is 3 hours
-1, material alkane alkene ratio is 25.
Comparative Examples 1:
Alkylated reaction with the concentrated sulfuric acid (98%wt) homogeneous catalysis carries out in still, and concrete operations are as follows: in the still of earlier the 5 gram concentrated sulfuric acids being packed into, still is sealed, reinstalled 30 gram reaction masses, material alkane alkene ratio is 25, charges into nitrogen, makes reaction pressure reach 0.7MPa.Reacted 2 hours, tail gas is answered in negate, isolates product, analyzes.Reaction result sees Table 1.
Table 1
| Olefin conversion/weight % | C 5 +Product composition/weight % | |||
| C 7Following content | C 8Content | C 9Above content | Trimethylpentane (TMP) content | |
| 100％ | 13.4 | 73.39 | 13.21 | 46.42 |
Comparative Examples 2:
With solid super-strong acid SO
4 2-/ ZrO
2Be catalyst, this catalyst press document Solid Catalyst Treatedwith Anion (Applied Catalysis, V59,1990,205-212) make H
0＜-14.6, measure the acid amount and be 0.032mmol/g.Estimate its alkylation activity in the fixed bed reaction system, reaction temperature is 30 ℃, and pressure is 15MPa, and material alkane alkene ratio is 30, and the charging air speed is 2 hours
-1, react 8 hours the results are shown in Table 2.
Table 2
| Olefin conversion/weight % | C 5 +Product composition/weight % | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 41％ | 13.4 | 40.44 | 46.16 | 20.38 |
Comparative Examples 3:
With carried heteropoly acid HPW/SiO
2Be catalyst, heteropoly acid HPW load capacity 25%, concrete preparation method is as follows: 3.3g is dissolved in the 30ml water with phosphotungstic acid (brief note is HPW, and Beijing Chemical Plant's system is analyzed pure), adds 10 gram 20-40 order SiO again
2(gross porosity, specific area are 488m
2/ g, Haiyang Chemical Plant, Qingdao produces), dipping stirred evaporate to dryness after 2 hours in 60 ℃ of water-baths, made the HPW appendix at SiO
2On, 100 ℃ of oven dry 4 hours, make heteropoly acid appendix amount and be 25% catalyst then.Handled acid strength H 2 hours for 175 ℃
0Reach-13.75, the acid amount is 0.23mmol/g.The alkylation activity of catalyst is estimated in the fixed bed reaction system, and reaction temperature is 30 ℃, and pressure is 15MPa, and material alkane alkene ratio is 30, and the charging air speed is 2 hours
-1, react 8 hours the results are shown in Table 3.
Table 3
| Olefin conversion/weight % | C 5 +Product composition/weight % | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 60.3％ | 13.6 | 48.13 | 38.27 | 20.25 |
Comparative Examples 4
With dry method barium white is loaded on the silica gel, according to document Applied Catalysis A:General180 (1999) p359-366 preparation, the solid acid acid strength H that makes
0＜-12, acid amount 2.7mmol/g, reactivity worth is estimated in the fixed bed reaction system, and 8 hours reaction result sees Table 4.Sour load capacity 10 weight % before the reaction, reacting the acid amount of measuring after 8 hours is 2 weight %.
Table 4
| Olefin conversion/weight % | C 5 +Product composition/weight % | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 8.63 | 61.52 | 29.83 | 27.26 |
Embodiment 1
100 gram ethyl orthosilicates and 50 gram ethanol are mixed in the there-necked flask that has reflux condensing tube of 250ml, the 15 gram concentrated sulfuric acids are joined rapidly in the gained mixed solution, stir and be heated to 100 ℃, generated gel after refluxing about 1 hour.The gel that forms is told, put into vacuum drying oven, vacuumize in 50 ℃ and handle 48 hours (vacuum is mmHg, down together), obtain silica-based solid acid, in drier, preserve.Record acid strength H
0Be-12, the acid amount is 3mmol/g, and reactivity worth is estimated in the fixed bed reaction system, and 8 hours reaction result sees Table 5.The solid acid that present embodiment obtains is 50% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 5
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 14.3 | 70.0 | 15.7 | 40.1 |
Embodiment 2
10 gram ethyl orthosilicates and 10 gram methyl alcohol are mixed in the there-necked flask burning that has reflux condensing tube of 100ml.6 gram SPAs are added in the above-mentioned mixed solution rapidly, stir and be heated to 100 ℃, above-mentioned colloidal sol forms even gel after refluxing about 0.5 hour.The gel that forms is told, put into vacuum drying oven, vacuumize following 100 ℃ and handled 24 hours, obtain silica-based solid acid, preserve in the drier.Record its acid strength H
0Be-10, measure the acid amount and be 2.8mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 6.The solid acid that present embodiment obtains is 70% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 6
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 13.4 | 72.9 | 13.7 | 42.1 |
Embodiment 3
100 gram aluminic acid esters and 30 gram ethanol are mixed in the there-necked flask that has reflux condensing tube of 250ml, be heated to boiling, add 12 grams, 20% sulfuric acid in the above-mentioned mixed solution rapidly again, reflux and stirred 1 hour down, the gel that forms is told, put into vacuum drying oven, vacuumize following 100 ℃ and handled 48 hours, obtain aluminium base solid acid, preserve in the drier.Recording acid strength is-12, measures the acid amount and is 1.8mmol/g, and reactivity worth is estimated in the fixed bed reaction system, and 8 hours reaction result sees Table 7.The solid acid that present embodiment obtains is 15% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 7
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 12.4 | 73.9 | 13.7 | 35.4 |
Embodiment 4
50 gram zirconates and 3 gram ethanol are mixed in the there-necked flask that has reflux condensing tube of 100ml, be heated to boiling, add 12 grams, 40% sulfuric acid in the above-mentioned mixed solution rapidly again, reflux and stirred 1 hour down, the gel that forms is told, put into vacuum drying oven, vacuumize following 120 ℃ and handled 48 hours, obtain Zirconium-base solid acid, preserve in the drier.Record acid strength H
0Be-12, measure the acid amount and be 1.8mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 8.The solid acid that present embodiment obtains is 25% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 8
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 15.0 | 63.8 | 21.2 | 30.1 |
Embodiment 5
10 gram titanate esters and 3 gram ethanol are mixed in the there-necked flask that has reflux condensing tube of 100ml, be heated to boiling, add 6 grams, 80% sulfuric acid in the above-mentioned mixed solution rapidly again, the stirring down that refluxes had gel to generate in about 20 minutes, the gel that forms is told, put into vacuum drying oven, vacuumize following 100 ℃ and handled 60 hours, obtain slightly brown, translucent solid acid, need in drier, to preserve.Record acid strength H
0Be-12, measure the acid amount and be 1.8mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 9.The solid acid that present embodiment obtains is 60% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 9
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 14.2 | 65.8 | 20.0 | 35.8 |
Embodiment 6
10 gram titanium propanolates and 5 gram octanols and 5 gram water are mixed in the there-necked flask burning that has reflux condensing tube of 100ml, add 9 grams, 98% sulfuric acid in the above-mentioned mixed solution rapidly, be heated to boiling, reflux and stirred 30 minutes down, the gel that forms is told, put into vacuum drying oven, vacuumize following 100 ℃ and handled 48 hours, preserve in the drier.Record acid strength H
0Be-12, measure the acid amount and be 3.6mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 10.The solid acid that present embodiment obtains is 70% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 10
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 12.4 | 69.9 | 17.7 | 39.4 |
Embodiment 7
35 gram methyl silicates and 20 gram isoamyl alcohol are mixed in the there-necked flask that has reflux condensing tube of 100ml, add 5 grams, 10% sulfuric acid in the above-mentioned mixed solution rapidly, be heated to boiling, the stirring down that refluxes had gel to generate in about 3 hours, the gel that forms is told, put into vacuum drying oven, vacuumize following 60 ℃ and handled 60 hours, the silica-based solid acid that obtains is preserved in drier.Record its acid strength H
0Be-12, measure the acid amount and be 0.8mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 11.The solid acid that present embodiment obtains is 5% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 11
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 10.3 | 70.5 | 19.2 | 33.2 |
Embodiment 8
10 gram ethyl orthosilicates and 7 gram ethanol are mixed in the there-necked flask that has reflux condensing tube of 100ml, be heated to boiling, add 12 grams, 80% sulfuric acid in the above-mentioned mixed solution rapidly again, being stirred to gel under refluxing generates, the gel that forms is told, put into vacuum drying oven, vacuumize following 100 ℃ and handled 10 hours, preserve in the drier.Record its acid strength H
0Be-12, measure the acid amount and be 1.8mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 12.The solid acid that present embodiment obtains is 65% weight in the acid amount of the forward and backward determination of acid-basetitration of reaction.
Table 12
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 11.8 | 75.9 | 12.3 | 37.3 |
Embodiment 9
10 gram aluminic acid esters and 10 gram isopropyl alcohols are mixed in the 100ml there-necked flask, be heated to boiling, again the acid of 12 grams, 40% phosphoric acid is added in the above-mentioned mixed solution, being stirred to gel under refluxing generates, the gel that forms is told, put into vacuum drying oven, vacuumize following 100 ℃ and handled 30 hours, preserve in the drier.Record its acid strength H
0Be-12, measure the acid amount and be 2.0mmol/g that reactivity worth is estimated in the fixed bed reaction system, 8 hours reaction result sees Table 13.The solid acid that present embodiment obtains is 60% weight in the solid acid institute acid content of the forward and backward determination of acid-basetitration of reaction.
Table 13
| Olefin conversion/% weight | C 5 +Product composition/% weight | |||
| C 7Following content | C 8Content | C 9Above content | TMP content | |
| 100％ | 11.8 | 68.2 | 20.0 | 23.3 |
Embodiment 10
This embodiment is in order to investigate the stability of catalyst provided by the invention in nonaqueous solvents.Accurately take by weighing 5 sulfuric acid contents that obtain of gram embodiment 1 and be 50% solid acid, place tool plug triangular flask, add 30 milliliters of isopentane again, 30 ℃ were stirred 24 hours, leave standstill 1 hour after, accurately pipette 10 milliliters of supernatant liquors, add 10 ml deionized water, stir, extract after 30 minutes, detect institute's acid content in the water with acid-base titration, testing result shows, does not contain acid in the water; Wherein solid acid accurately takes by weighing 3 grams 50 ℃ of oven dry 5 hours, and with wherein acid amount of determination of acid-basetitration, the result shows that institute's acid content does not become.
Claims (17)
1, a kind of acid catalyst of solid form is characterized in that this catalyst contains the liquid acid of 1～80 weight % and the gel-like solid matter with cross-linked structure that is used to wrap up this liquid acid of 99～20 weight %; Wherein said liquid acid is for having a C
1-C
10The sulfuric acid hydrogen ester of alkyl or phosphoric acid hydrogen ester, and optionally contain sulfuric acid or phosphoric acid, the ratio of sulfuric acid or phosphoric acid and sulfuric acid hydrogen ester or phosphoric acid hydrogen ester is acid: ester=(0～95): (100～5).
2,, it is characterized in that this catalyst contains the liquid acid of 2～70 weight % and the solid matter that is used to wrap up this liquid acid of 98～30 weight % according to the catalyst of claim 1.
3, according to the catalyst of claim 1, wherein the ratio of sulfuric acid or phosphoric acid and sulfuric acid hydrogen ester or phosphoric acid hydrogen ester is acid: ester=(5～90): (95～10).
4, according to the catalyst of claim 1, wherein said sulfuric acid hydrogen ester or phosphoric acid hydrogen ester are by sulfuric acid or phosphoric acid and a kind of C of having
1-C
10The fatty alcohol of alkyl carries out condensation reaction and the ester that forms, or has C by sulfuric acid or phosphoric acid and two or more different
1-C
10The fatty alcohol of alkyl carries out condensation reaction and the mixture of the ester that forms.
5, according to the catalyst of claim 4, the alcohols of the wherein said 1-10 of having carbon atom comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol or n-octyl alcohol, or their mixture.
6, according to the catalyst of claim 1, wherein said liquid acid is that total concentration is the aqueous solution of 70～100 weight %.
7, according to the catalyst of claim 6, wherein said liquid acid is that total concentration is the aqueous solution of 85～100 weight %.
8, according to the catalyst of claim 1, the wherein said solid matter that is used to wrap up liquid acid is the hydroxide or the oxide of silicon, titanium or zirconium with cross-linked structure.
9, according to the catalyst of claim 8, the said solid matter that is used to wrap up liquid acid is the silicon gel.
10, the described Preparation of catalysts method of claim 1 is characterized in that this method comprises:
(1). with a kind of acid and C
1-C
4Pure formed organic esterified compound mix with the alcohols with 1-10 carbon atom and make solution, and add entry when needed, the sulfuric acid or the phosphoric acid that with concentration are 5-100 weight % then join in the gained solution, make that the weight ratio of said organic ester and said alcohol, acid and water is an ester in the gained mixture: alcohol: acid is (with H
2SO
4Or H
3PO
4Meter): water=1: (0.1-5.0): (0.1-4): (0.1-4), room temperature to the reflux temperature stirring reaction 0.1-10 hour to forming gel;
(2). (1) gained mixture was handled 2-80 hour down in room temperature to 150 ℃ under normal pressure or reduced pressure;
Its precursor condition is: when the said reaction temperature of step (1) was lower than 100 ℃, the said treatment temperature of step (2) should be 100～150 ℃, so that generate sulfuric acid hydrogen ester or phosphoric acid hydrogen ester to the sulfuric acid of small part or phosphoric acid and pure condensation.
11, according to the method for claim 10, wherein said organic esterified compound is the organic esterified compound of silicon, titanium or zirconium.
12, according to the method for claim 11, wherein said organic esterified compound is silicic acid, metatitanic acid or zirconic acid and C
1-C
4Pure formed ester class.
13, according to the method for claim 12, wherein said organic esterified compound comprises methyl silicate, silester, silicic acid propyl ester, isopropyl silicate, tetraethyl titanate, titanium propanolate, isopropyl titanate, butyl titanate, iso-butyl titanate, zirconic acid propyl ester, zirconic acid isopropyl ester, tetrabutyl zirconate or zirconic acid isobutyl ester.
14, according to the method for claim 10, the alcohols of the wherein said 1-10 of having carbon atom comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol or n-octyl alcohol, or their mixture.
15, according to the method for claim 10, wherein said sulfuric acid or the phosphoric acid concentration before adding is 10-80 weight % in the step (1).
16, according to the method for claim 10, wherein in the step (1) in the said mixture weight ratio of organic ester and said alcohol, acid and water be ester: alcohol: acid: water=1: (0.1-2.0): (0.5-3): (0.1-3).
17, according to the method for claim 10, wherein the temperature of said processing is 40-140 ℃ in the step (2).
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