CN103801405B - A kind of preparation method of titanium-silicon molecular sieve catalyst - Google Patents
A kind of preparation method of titanium-silicon molecular sieve catalyst Download PDFInfo
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- CN103801405B CN103801405B CN201210442966.1A CN201210442966A CN103801405B CN 103801405 B CN103801405 B CN 103801405B CN 201210442966 A CN201210442966 A CN 201210442966A CN 103801405 B CN103801405 B CN 103801405B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 38
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 230000008961 swelling Effects 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000004291 polyenes Chemical class 0.000 claims abstract description 10
- 238000000638 solvent extraction Methods 0.000 claims abstract description 10
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 2
- 229940125758 compound 15 Drugs 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZRJUCHNILNOEKV-UHFFFAOYSA-N hexan-2-one hydrate Chemical compound O.CCCCC(C)=O ZRJUCHNILNOEKV-UHFFFAOYSA-N 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of titanium-silicon molecular sieve catalyst.HTS powder, polymerization single polymerization monomer 1-chloro-4-methyl-benzene, polymerization single polymerization monomer polyene-based compound and perforating agent fully mix by the method, polymerisation is carried out under initator exists, the solid catalyst obtained is added to swelling in halogenated hydrocarbons after, after solvent extraction, drying, use sweller swelling again, then add aminated compounds to react, then after washing, obtain titanium-silicon molecular sieve catalyst.The catalyst of gained of the present invention is applicable to fixed bed alkene epoxidation and improves object selectivity of product.
Description
Technical field
The invention belongs to a kind of preparation method of HTS resin anion (R.A.) composite catalyst catalyst, be suitable for the epoxidation of alkene, especially propylene to prepare epoxy propane process.
Technical background
Nineteen eighty-three, Enichem company of Italy was first since synthesis of titanium silicon molecular sieve catalyst TS-1, become the focus of oxidation catalyst research due to the oxidation selectivity of its excellence and the reaction condition of gentleness, this discovery is regarded as a quantum jump of environment-friendly catalyst exploitation.
The HTS synthesized at present comprises the TS-1 with MFI structure; The TS-2 of MEL structure; With the MCM-22 with MWW structure and the TS-48 had compared with macroporous structure.HTS can the multiple organic oxidizing reaction of catalysis, as propylene prepares expoxy propane with hydrogen peroxide epoxidizing under titanium-silicon molecular sieve catalyst effect, phenol prepares benzenediol with hydrogen peroxide oxidation under HTS effect, and cyclohexanone carries out prepared by ammoxidation for cyclohexanone oxime with hydrogen peroxide under titanium-silicon molecular sieve catalyst effect.Free of contamination low concentration hydrogen peroxide can be used in course of reaction, there is energy-conservation, the feature such as economy, environmental friendliness.But at TS-1/H
2o
2in catalytic oxidation system, especially in epoxidation reaction owing to there is stronger acid centre in TS-1 molecular sieve, make epoxides can continue reaction and generate non-object product ether, alcohol etc., reduce the selective of object product.
The particle diameter of titanium-silicon molecular sieve catalyst is about 0.1 ~ 15.0 μm in actual applications simultaneously, but, particle diameter little like this brings great difficulty with being separated of product can to catalyst, although the existing various achievement in research about filtering material is applied to reality, but for being separated of titanium-silicon molecular sieve catalyst and product, the resistance produced when it filters also does not lie in the size in the duct of filtering material, but come from superfine little catalyst particle and occupy and block the duct of formed filter cake, especially the particle diameter catalyst particle that is less than 2 μm is the most unfavorable to filtration, cause production efficiency low like this, also the process of HTS industrial applications is had influence on.The catalyst of small particle diameter when filtering except blocking filter cake duct, part then runs off from the duct of filter medium, general turnover rate is about 5% ~ 8% of catalyst input amount, not only cause the unnecessary consumption of catalyst, and enter in product material and cause further side reaction, cause the increase of separation costs, affect product quality.The acidity that HTS presents in addition also causes oxidation reaction product further side reaction to occur, and reduces to object selectivity of product.
Expoxy propane (PO) is important basic petrochemical materials, it is the third-largest kind that in acryloyl derivative, output is only second to polypropylene and acrylonitrile, mainly for the production of polyethers, propane diols, isopropanolamine, allyl alcohol etc., and then produce the important source material such as unsaturated polyester resin, polyurethane, surfactant, be widely used in the industries such as chemical industry, light industry, medicine, food, weaving.
CN1256274A proposes the technique of propylene with hydrogen peroxide solution epoxidation continuous preparation of epoxypropane, in this process, catalyst exists with paste-like, although obtain good feed stock conversion and product yield, but because catalyst is slurry state, need after reaction to be separated from product, reuse.Which results in technological process loaded down with trivial details, and be unfavorable for large-scale industrial production, in addition in this process, catalyst also will have inevitable loss.Have by-product ether simultaneously, alcohol produces.
CN101172970A provides one with titanium silicon-silica for catalyst, with H
2o
2for oxidant, take acetonitrile as the preparation method of the epoxychloropropane of solvent, there is good yield, but owing to using silica to be forming agent, be difficult to Long-Time Service under moisture reaction condition, its catalyst life is shorter is difficult to commercial Application.
CN102451763A proposes the preparation method of a kind of titanium silicon and resin compounded catalyst, this catalyst is used for the technique of propylene, hydrogen peroxide epoxidation continuous preparation of epoxypropane, although obtain good feed stock conversion and product yield, but because HTS acidity is still stronger, the expoxy propane generated continues reaction and generates corresponding alcohol, ether under acid catalysed conditions, reduces the selective of object product propene oxide.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of the titanium-silicon molecular sieve catalyst for fixed bed reactors, active good, selective height, catalyst long service life.
The preparation method of titanium-silicon molecular sieve catalyst of the present invention, comprising:
(1) HTS, polymerization single polymerization monomer 1-chloro-4-methyl-benzene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, under initator exists, carry out polymerisation, obtain catalyst solid,
(2) above-mentioned catalyst solid is added to swelling in halogenated hydrocarbons after, then after solvent extraction, drying, obtain resin-HTS compound;
(3) dry thing sweller step (2) obtained is swelling, then adds aminated compounds and reacts, then after washing, obtains titanium-silicon molecular sieve catalyst of the present invention.
In the inventive method, preferably the catalyst solid that polymerisation obtains is processed into catalyst granules, and then swelling with halogenated hydrocarbons.According to the needs of practical application, crushing and screening method can be adopted, can also patterning method etc. be adopted, catalyst solid is processed into the catalyst granules of suitable size and shape (as stripe shape, spherical, class is spherical).Time such as epoxidation reaction, catalyst granules particle diameter is 8 ~ 16 orders.
Step (1) raw materials used addition is as follows with weight parts: HTS 5 ~ 30 parts, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 10 ~ 120 parts, is preferably 30 ~ 90 parts, polyene-based compound 15 ~ 120 parts, is preferably 20 ~ 80 parts, perforating agent 5 ~ 60 parts.
Polymeric reaction condition described in step (1) is as follows: at 60 ~ 150 DEG C, preferably 70 ~ 100 DEG C, reacts 3 ~ 10 hours, preferably 4 ~ 6 hours.
Polymerization single polymerization monomer polyene-based compound described in step (1) can be one or more in divinylbenzene, divinyl toluene, biethenyl-xylene.
Described perforating agent can be gasoline, C
5~ C
13n-alkane, C
4~ C
12one or more in fatty alcohol, preferably C
5~ C
13one or more in n-alkane.
Described initator can be benzoyl peroxide and/or azo two isobutanol, and addition is 0.5 ~ 1.5 part.
Described halogenated hydrocarbons can be C
1~ C
4halogenated hydrocarbons, wherein preferably 1,2-dichloroethanes.The volume ratio of described catalyst solid and halogenated hydrocarbons is 1:10 ~ 1:1, dissolved swollen 3 ~ 8 hours, preferably 5 ~ 6 hours.
Described extraction solvent can be one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, butanols etc.Described extractive reaction temperature is 30 ~ 60 DEG C, preferably 50 ~ 60 DEG C; Described extraction times is 2 ~ 8 hours, preferably 4 ~ 6 hours.Extracting number of times is 2-5 time.The volume ratio of extraction solvent and catalyst is 1:1 ~ 5:1.
Drying described in step (2) adopts vacuum drying, and its condition is as follows: 50 ~ 100 DEG C preferably 80 ~ 90 DEG C, drying time is 8 ~ 20 hours, preferably 10 ~ 16 hours, and described vacuum drying vacuum is 1 ~ 30kPa, preferably 1 ~ 3kPa.
Sweller described in step (3) is one or more in DMF, acetonitrile, chloromethyl ether etc.The consumption of described sweller is long-pending 3 ~ 15 times of drying objects that step (2) obtains, preferably 5 ~ 8 times.
Aminated compounds described in step (3) is one or more in methylamine, dimethylamine, trimethylamine, ethamine, ethylenediamine, butylamine, diethanol amine, methylethanolamine, α-amido pyridine etc.The addition of described aminated compounds is that step (1) polymerization single polymerization monomer 1-chloro-4-methyl-benzene and polymerization single polymerization monomer polyene-based compound add 5% ~ 50% of gross mass, is preferably 10% ~ 30%.
Reaction condition described in step (3) was as follows: 40 ~ 90 DEG C of reactions 1 ~ 8 hour.Described washing adopts deionized water washing, is washed till neutrality.
The catalyst that the inventive method obtains directly can load in fixed bed reactors and carries out the epoxidation of alkene, the hydroxylating of phenol, the catalytic reaction of the ammoxidation of ketone, and catalytic effect is excellent.
Compared with prior art, the inventive method has following feature:
1, after HTS and resin compounded, adopt aminated compounds process, the basic group on the one hand resin being introduced, under making HTS be in the atmosphere of alkalescence, the acidity of aminated compounds adjustable catalyst on the other hand, the method gained catalyst is used in hydrogen peroxide system epoxidization reaction process, has increased substantially the selective of object product in epoxidization reaction process, has decreased the generation of side reaction.
2, can adopt fixed bed reaction mode after shaping, the catalyst solving Ti-Si catalyst powder and reactant liquor are difficult to the problem be separated, and improve reaction efficiency.
3, in catalytic reaction process due to the diluting effect of a large amount of dispersant, make HTS with isolation form exist, so oxidation reaction fuel factor relax.
4, after HTS polymerization forming, high temperature (>500 DEG C) roasting is not needed to remove the perforating agent added in forming process, low temperature (< 150 DEG C) extracting is only needed to activate, can avoid causing framework of molecular sieve to cave in or titanium detaches skeleton, fully keep HTS active.
5, catalyst backbone is water-fast, is conducive at H
2o
2react in reaction atmosphere, catalyst life is long.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail; following examples are not limiting the scope of the invention; those skilled in the art is in conjunction with description of the present invention and can do suitable expansion in full, and these expansions should be all protection scope of the present invention.Wt% is mass fraction.
embodiment 1
In polymeric kettle, add HTS 7.5g, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 90g and divinylbenzene 30g, perforating agent liquid wax 60g, after being uniformly mixed, when warming-in-water is to 60 DEG C, add initator benzoyl peroxide 1.5g, 90 times polymeric reaction temperatures 6 hours, obtain titanium-silicon molecular sieve catalyst, then carry out broken granulation, choose the catalyst of suitable particle diameter after screening, add 1,2-dichloroethanes 250mL carries out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add ethyl acetate 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, then 80 DEG C, vacuum drying after 12 hours under 2KPa condition, with N, the swelling above-mentioned dry body 2h of dinethylformamide 300mL, adds tri-n-butylamine 50g and is warming up to 80 DEG C of reaction 2h, be washed till neutrality by deionized water, obtain titanium-silicon molecular sieve catalyst A, its physico-chemical property is in table 1.
Embodiment 2
In polymeric kettle, add HTS 15g, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 90g, divinyl toluene 15g, perforating agent C
5fatty alcohol 60g, after being uniformly mixed, when warming-in-water is to 80 DEG C, add initator azo two isobutanol 2.0g, be polymerized at 100 DEG C, react 6 hours, obtain titanium-silicon molecular sieve catalyst, then carry out broken granulation, the catalyst of suitable particle diameter is chosen after screening, adding 1,2-dichloroethanes 250mL carries out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add dimethylbenzene 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, then 80 DEG C, vacuum drying after 12 hours under 2kPa condition.With the swelling above-mentioned dry body 2h of DMF 300mL, add tri-n-butylamine 50g and be warming up to 80 DEG C of reaction 2h, be washed till neutrality by deionized water, obtain titanium-silicon molecular sieve catalyst B, its physico-chemical property is in table 1.
Embodiment 3
In polymeric kettle, add HTS 30g, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 90g, divinyl toluene 15g, perforating agent C
5fatty alcohol 60g, after being uniformly mixed, when warming-in-water is to 80 DEG C, add initator azo two isobutanol 2.0g, be polymerized at 100 DEG C, react 6 hours, obtain titanium-silicon molecular sieve catalyst, then carry out broken granulation, the catalyst of suitable particle diameter is chosen after screening, adding 1,2-dichloroethanes 250mL carries out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add dimethylbenzene 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, then 80 DEG C, vacuum drying after 12 hours under 2kPa condition.With the swelling above-mentioned dry body 2h of acetonitrile 300mL, add dimethylamine 40g and be warming up to 45 DEG C of reaction 3h, be washed till neutrality by deionized water, obtain titanium-silicon molecular sieve catalyst C, its physico-chemical property is in table 1.
Embodiment 4
Get the 45g of HTS, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 90g, divinyl toluene 15g, perforating agent C
5fatty alcohol 60g, after being uniformly mixed, when warming-in-water is to 80 DEG C, add initator azo two isobutanol 2.0g, be polymerized at 100 DEG C, react 6 hours, obtain titanium-silicon molecular sieve catalyst, then carry out broken granulation, the catalyst of suitable particle diameter is chosen after screening, adding 1,2-dichloroethanes 250mL carries out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add dimethylbenzene 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, then 80 DEG C, vacuum drying after 12 hours under 2kPa condition.With the swelling above-mentioned dry body 2h of acetonitrile 300mL, add dimethylamine 50g and be warming up to 45 DEG C of reaction 3h, be washed till neutrality by deionized water, obtain titanium-silicon molecular sieve catalyst D, its physico-chemical property is in table 1.
Embodiment 5
In polymeric kettle, add HTS 60g, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 90g and divinylbenzene 30g, perforating agent liquid wax 60g, after being uniformly mixed, when warming-in-water is to 60 DEG C, add initator benzoyl peroxide 1.5g, polymeric reaction temperature 6 hours at 90 DEG C, obtain titanium-silicon molecular sieve catalyst, then carry out broken granulation, choose the catalyst of suitable particle diameter after screening, add 1,2-dichloroethanes 250mL carries out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add ethyl acetate 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, then 80 DEG C, vacuum drying after 12 hours under 2kPa, with N, the swelling above-mentioned dry body 2h of dinethylformamide 300mL, adds trimethylamine 30g and is warming up to 65 DEG C of reaction 5h, be washed till neutrality by deionized water, obtain titanium-silicon molecular sieve catalyst E, its physico-chemical property is in table 1.
Embodiment 6
In polymeric kettle, add HTS 50g, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 90g and divinylbenzene 30g, perforating agent liquid wax 60g, after being uniformly mixed, when warming-in-water is to 60 DEG C, add initator benzoyl peroxide 1.5g, polymeric reaction temperature 6 hours at 90 DEG C, obtain titanium-silicon molecular sieve catalyst, then carry out broken granulation, choose the catalyst of suitable particle diameter after screening, add 1,2-dichloroethanes 250mL carries out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add ethyl acetate 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, then 80 DEG C, vacuum drying after 12 hours under 2kPa, with N, the swelling above-mentioned dry body 2h of dinethylformamide 300mL, adds ethylenediamine 30g and is warming up to 80 DEG C of reaction 4h, be washed till neutrality by deionized water, obtain titanium-silicon molecular sieve catalyst F, its physico-chemical property is in table 1.
Comparative example 1
In polymeric kettle, add HTS 7.5g, polymerization single polymerization monomer styrene 90g and divinylbenzene 30g, perforating agent liquid wax 60g, after being uniformly mixed, when warming-in-water is to 60 DEG C, add initator benzoyl peroxide 1.5g, at 90 DEG C, polymeric reaction temperature 6 hours, obtains titanium-silicon molecular sieve catalyst.Then carry out broken granulation, after screening, choose the catalyst of suitable particle diameter, add 1,2-dichloroethanes 250mL and carry out swelling, dissolved swollen 5 hours.After pouring out 1,2-dichloroethanes, then add ethyl acetate 200mL and carry out solvent extraction, extractive reaction temperature 55 DEG C, extraction times 4 hours, same method carries out three extractings, obtains titanium-silicon molecular sieve catalyst G, and its physico-chemical property is in table 1
The physico-chemical property of table 1 catalyst
| Catalyst | Specific area, m 2/g | Intensity, N/mm |
| A | 130.5 | 16.1 |
| B | 115.8 | 13.2 |
| C | 120.9 | 11.2 |
| D | 143.5 | 11.5 |
| E | 165.6 | 9.7 |
| F | 201.7 | 9.3 |
| G | 159.2 | 9.4 |
Embodiment 7
Catalyst B (particle diameter 8 ~ 12 order) 50mL of Example 2 loads diameter 20mm, in the fixed bed reactors of long 1200mm, carries out propylene ring oxidation reaction, reaction temperature 50 DEG C, and pressure 2.5MPa, propylene and H
2o
2mol ratio be 5: 1, methyl alcohol and H
2o
2mol ratio be 30: 1, reactant liquor phase volume air speed is 1.0h
-1condition under, H
2o
2conversion ratio can reach 100%, the selective > 99.8% of expoxy propane.
Comparative example 2
Get catalyst G(particle diameter 8 ~ 12 order of comparative example 1) 50mL loading diameter 20mm, in the fixed bed reactors of long 1200mm, carry out propylene ring oxidation reaction, reaction temperature 50 DEG C, pressure 2.5MPa, propylene and H
2o
2mol ratio be 5: 1, methyl alcohol and H
2o
2mol ratio be 30: 1, reactant liquor phase volume air speed is 1.0h
-1condition under, H
2o
2conversion ratio can reach 95%, the selective of expoxy propane is about 90%.
Embodiment 8
Catalyst C(particle diameter 8 ~ 12 order of Example 3) 50mL loads diameter 20mm, in the fixed bed reactors of long 1200mm, is that solvent carries out chloro propylene epoxidation reaction with methyl alcohol, reaction temperature 90 DEG C, pressure 0.5MPa, chloropropene and H
2o
2mol ratio be 7: 1, methyl alcohol and H
2o
2mol ratio be 30: 1, chloropropene volume space velocity is 0.6h
-1condition under, H
2o
2conversion ratio 100%, epoxy chloropropionate alkene selective 99.9%.
Embodiment 9
Catalyst E(particle diameter 8 ~ 12 order of Example 5) 50mL loading diameter 20mm, in the fixed bed reactors of long 1200mm, carry out the ammoxidation reaction of ketone, reaction temperature 75 DEG C, pressure 1.0MPa, the mol ratio of cyclohexanone and ammonia is 1: 2, cyclohexanone and H
2o
2mol ratio be 1: 1, toluene/water/cyclohexanone volume ratio is 1: 1: 1, cyclohexanone volume space velocity is 1.0h
-1condition under, the conversion ratio > 95% of cyclohexanone, the selective > 99.6% of cyclohexanone oxime.
Claims (15)
1. a preparation method for titanium-silicon molecular sieve catalyst, comprising:
(1) HTS, polymerization single polymerization monomer 1-chloro-4-methyl-benzene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, under initator exists, carry out polymerisation, obtain catalyst solid,
(2) above-mentioned catalyst solid is added to swelling in halogenated hydrocarbons after, then after solvent extraction, drying, obtain resin-HTS compound,
(3) dry thing sweller step (2) obtained is swelling, then adds aminated compounds and reacts, then after washing, obtains titanium-silicon molecular sieve catalyst;
Wherein, step (1) raw materials used addition is as follows with weight parts: HTS 5 ~ 30 parts, polymerization single polymerization monomer 1-chloro-4-methyl-benzene 10 ~ 120 parts, polyene-based compound 15 ~ 120 parts, perforating agent 5 ~ 60 parts;
Polymeric reaction condition described in step (1) is as follows: at 60 ~ 150 DEG C, reacts 3 ~ 10 hours;
The addition of the aminated compounds described in step (3) is that step (1) polymerization single polymerization monomer 1-chloro-4-methyl-benzene and polymerization single polymerization monomer polyene-based compound add 5% ~ 50% of gross mass;
Reaction condition described in step (3) was as follows: 40 ~ 90 DEG C of reactions 1 ~ 8 hour.
2. the polymerization single polymerization monomer polyene-based compound that in accordance with the method for claim 1, it is characterized in that described in step (1) is one or more in divinylbenzene, divinyl toluene, biethenyl-xylene.
3. in accordance with the method for claim 1, it is characterized in that described perforating agent is gasoline, C
5~ C
13n-alkane, C
4~ C
12one or more in fatty alcohol.
4. in accordance with the method for claim 3, it is characterized in that described perforating agent is C
5~ C
13one or more in n-alkane.
5. in accordance with the method for claim 1, it is characterized in that described initator is benzoyl peroxide and/or azo two isobutanol, addition is 0.5 ~ 1.5 part.
6. in accordance with the method for claim 1, it is characterized in that the catalyst solid of step (1) gained is processed into catalyst granules, particle diameter is 8 ~ 16 orders, then carries out step (2).
7. in accordance with the method for claim 1, it is characterized in that described halogenated hydrocarbons is C
1~ C
4halogenated hydrocarbons in one or more, the volume ratio of described catalyst solid and halogenated hydrocarbons is 1:10 ~ 1:1, dissolved swollen 3 ~ 8 hours.
8. in accordance with the method for claim 1, it is characterized in that described extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, butanols, described extractive reaction temperature is 30 ~ 60 DEG C, extraction times is 2 ~ 8 hours, extracting number of times is 2-5 time, and the volume ratio of extraction solvent and catalyst is 1:1 ~ 5:1.
9. in accordance with the method for claim 1, it is characterized in that the drying described in step (2) adopts vacuum drying, its condition is as follows: 50 ~ 100 DEG C, and drying time is 8 ~ 20 hours, and described vacuum drying vacuum is 1 ~ 30kPa.
10. in accordance with the method for claim 1, it is characterized in that the drying described in step (2) adopts vacuum drying, its condition is as follows: 80 ~ 90 DEG C, and drying time is 10 ~ 16 hours, and described vacuum drying vacuum is 1 ~ 3kPa.
11. in accordance with the method for claim 1, and the sweller that it is characterized in that described in step (3) is one or more in DMF, acetonitrile, chloromethyl ether.
12. according to the method described in claim 1 or 10, it is characterized in that the consumption of step (3) described sweller is long-pending 3 ~ 15 times of the drying objects that obtains of step (2).
13. in accordance with the method for claim 1, it is characterized in that the consumption of step (3) described sweller is long-pending 5 ~ 8 times of the drying objects that obtains of step (2).
14. in accordance with the method for claim 1, and the aminated compounds that it is characterized in that described in step (3) is one or more in methylamine, dimethylamine, trimethylamine, ethamine, ethylenediamine, butylamine, diethanol amine, methylethanolamine, α-amido pyridine.
15. according to the method described in claim 1 or 14, it is characterized in that the addition of the aminated compounds described in step (3) is that step (1) polymerization single polymerization monomer 1-chloro-4-methyl-benzene and polymerization single polymerization monomer polyene-based compound add 10% ~ 30% of gross mass.
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| CN102320619A (en) * | 2011-10-06 | 2012-01-18 | 大连理工大学 | Synthesis method of titanium silicalite TS-1 |
| CN102757407A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Allyl chloride epoxidation method for preparing epichlorohydrin |
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| CN102049304A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof |
| CN102757407A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Allyl chloride epoxidation method for preparing epichlorohydrin |
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