CN102755910A - Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof - Google Patents
Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof Download PDFInfo
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- CN102755910A CN102755910A CN2011101050536A CN201110105053A CN102755910A CN 102755910 A CN102755910 A CN 102755910A CN 2011101050536 A CN2011101050536 A CN 2011101050536A CN 201110105053 A CN201110105053 A CN 201110105053A CN 102755910 A CN102755910 A CN 102755910A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 title abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 18
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000000805 composite resin Substances 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 11
- 150000004291 polyenes Chemical class 0.000 claims abstract description 11
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims description 35
- 229920005989 resin Polymers 0.000 claims description 35
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical class CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000012644 addition polymerization Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006735 epoxidation reaction Methods 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 16
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 150000002924 oxiranes Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HLFSDGLLUJUHTE-SNVBAGLBSA-N Levamisole Chemical compound C1([C@H]2CN3CCSC3=N2)=CC=CC=C1 HLFSDGLLUJUHTE-SNVBAGLBSA-N 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229960001614 levamisole Drugs 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- Epoxy Compounds (AREA)
Abstract
The invention discloses a titanium silicon molecular sieve and resin composite modified catalyst and a preparation method thereof. According to the invention, titanium silicon molecular sieve powder, a polymerization monomer styrene, a polymerization monomer polyene-based compound, and a pore-forming agent are sufficiently mixed; under the existence of an initiator, a polymerization reaction is carried out; an obtained block-shaped solid catalyst is processed into solid particles; the particles are swelled in halogenated hydrocarbon; and the material is extracted by using a solvent, such that a titanium silicon molecular sieve catalyst precursor is obtained. The catalyst precursor is subjected to ammonia and nitrogen mixed gas heat treatment, such that the catalyst provided by the invention is obtained. When the catalyst provided by the invention is adopted in catalytic reaction processes of a fixed bed styrene epoxidation method for preparing styrene oxide, and a fixed bed allyl chloride epoxidation method for preparing epichlorohydrin, excellent catalytic effects are provided. With the catalyst provided by the invention, a problem of separation difficulty of titanium silicon catalyst powder and a reaction liquid is solved, and reaction efficiency is improved.
Description
Technical field
The invention belongs to a kind of HTS and resin compounded modified catalyst and preparation method thereof.The epoxidation of styrene that catalyst of the present invention is suitable for fixed-bed process prepares in the catalytic reaction process of Styryl oxide, preparing epichlorohydrin by chloropropene epoxidation.
Background technology
From Italian Enichem company nineteen eighty-three first since the synthesis of titanium silicon molecular sieve catalyst TS-1; Owing to its excellent oxidation selectivity and gentle reaction condition become the focus that oxidation catalyst is studied, this discovery is regarded as a quantum jump of environment-friendly catalyst exploitation.
Titanium-silicon molecular sieve catalyst has important effect aspect the organic compound selective oxidation; Like preparing epoxypropane by epoxidation of propene; Preparing epichlorohydrin by chloropropene epoxidation; Epoxidation of styrene prepares Styryl oxide, and phenol prepares benzenediol with hydrogen peroxide oxidation under the HTS effect, and cyclohexanone carries out ammoxidation with hydrogen peroxide and prepares cyclohexanone oxime etc. under the titanium-silicon molecular sieve catalyst effect.In commercial Application, titanium-silicon molecular sieve catalyst shows the good type of selecting catalytic performance, and general particle diameter is more little; Catalyst activity is high more, and selectivity is good more, and the particle diameter of titanium-silicon molecular sieve catalyst is about 0.1-15.0 μ m in the practical application; Yet so little particle diameter can be given catalyst and bring great difficulty separating of product, though existing various achievements in research about filtering material are applied to reality; But for separating of titanium-silicon molecular sieve catalyst and product; The resistance that produces when it filters does not also lie in the size in the duct of filtering material, and to occupy and stop up duct, the especially particle diameter of formed filter cake the most unfavorable to filtering less than the catalyst particle of 2 μ m but come from superfine little catalyst particle; Cause production efficiency low like this, also have influence on the process of HTS industrial applications.The catalyst of small particle diameter when filtering except that stopping up the 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 causes the unnecessary consumption of catalyst, and causes further side reaction in the entering product material; Cause the increase of separation costs, influence product quality.
Epoxychloropropane is a kind of important chemical material and synthetic intermediate, and the output of epoxychloropropane is only second to oxirane and expoxy propane in epoxide.Its purposes very extensively mainly is used for the synthetic epoxy resin chlorohydrin rubber; It also is the primary raw material of epoxy resin, nitroglycerine, fiberglass, electric insulation goods; Also can be used as the raw material of producing medicine, agricultural chemicals, coating, surfactant, adhesive, ion exchange resin, plasticizer, glycerol derivatives, glycidyl derivatives and chlorohydrin rubber.
At present, the industrial process of epoxychloropropane mainly contains propylene high-temperature chloridising and propylene acetate method, and the former accounts for 90%.The propylene high-temperature chloridising is had relatively high expectations to the decay resistance of reactor, and energy consumption is bigger, and consumption chlorine is more, and accessory substance is more, needs purified treatment, and environmental pollution is serious; The propylene acetate method has adopted the acetoxylation technology, and reaction condition is gentle, and the chlorine consumption reduces half the, and accessory substance is less, but this method step is many, and technological process is long, and three wastes discharge amount is big.Because oil price rise causes the industrial chemicals price to increase considerably, seek more economical route production epoxychloropropane and receive much concern.With the HTS is catalyst, H
2O
2As the oxygen source of epoxidation reaction, its active o content is higher than ROOH, in addition H
2O
2Self changes H into after epoxidation reaction
2O is not difficult to the byproduct handled, so this method is environment amenable, the process route of cleaning more.
CN1534030A has proposed a kind of epoxychloropropane preparation method; Comprise: chloropropene, hydrogen peroxide solution, solvent and titanium-silicon molecular sieve catalyst particle are put into agitated reactor and are reacted; Solvent and unreacted chloropropene directly turn back to agitated reactor through fractionator, the slurries in the agitated reactor after filtering, the gained clear liquid obtains the epoxychloropropane product through separation; The concentrated slurry that gained contains catalyst returns agitated reactor, and isolated solvent and chloropropene also return agitated reactor continuation use from clear liquid.Though this process provides the direct epoxidation of chloropropene that a kind of flow process is simple, energy consumption is low to prepare the method for epoxychloropropane, owing to adopt the batch process operation, catalyst is slurry state; Need from product, separate after the reaction; Reuse, this makes technological process loaded down with trivial details, and is unfavorable for large-scale commercial production; In this process, catalyst also can produce inevitable loss in addition.
In order to solve in the epoxychloropropane production process; Because have strong polar compound such as water or alcohol in the reaction system, the catalysis ring-opening reaction will take place in the epoxide moiety of generation, reduce the problem of the yield of epoxides; CN1319099A discloses a kind of ancillary method that improves the epoxides yield; Add alkaline organic and improve selectivity, but owing to introduced the third component, will make product purify has increased difficulty; And this process remains and adopts the batch process operation, does not solve the problem that above-mentioned catalyst is difficult to separate.
It is catalyst with the HTS that USP 4833260 discloses a kind of, directly alkene is carried out epoxidation with hydrogen peroxide and produces the epoxides method.But because HTS need could show high catalytic activity in the reaction system that strong polar compounds such as alcohols are solvent; And the surface acidity of catalyst can cause product epoxides generation catalysis ring-opening reaction to generate the accessory substance ethers; Make the selectivity of epoxides have only about 85%, the yield of epoxides is lower.
Styryl oxide can be used as diluent, UV-absorbent, fumet of epoxy resin etc.; It also is the important intermediate of organic synthesis, pharmacy and perfume industry simultaneously; Can obtain bata-phenethyl alcohol like the Styryl oxide hydrogenation; This route has the product yield height and is prone to advantages such as refining, that environmental pollution is little, and Styryl oxide also is the main intermediate of synthetic levamisol.
The Styryl oxide synthetic method is halogenohydrin method and peroxy acid direct oxidation method in the industry.The former environmental pollution is serious, is that a kind of urgency is treated improved production technology; The used organic peroxide acid price comparison of the latter is expensive, and is serious to equipment corrosion, and is difficult to from reactant, separate, and production specifications require high.
The method that hydrogen peroxide catalyzed epoxidation vinyl benzene prepares Styryl oxide has safety, economy, non-environmental-pollution, advantage such as environmentally friendly, but needs corresponding catalyst.That research is more at present is iron si molecular sieves/H
2O
2Epoxidation process.As S.B. Kumar etc. (J. Catal. 1995,156: 163-166) report uses TS-1/H
2O
2The system epoxidation vinyl benzene, (Dalian University of Technology's journal 2002,42 (5): 535-538) make catalyst styrene is carried out epoxidation etc. such as Li Gang with the synthetic TS-1 of cheap raw material.But iron si molecular sieves/H
2O
2During the system epoxidation vinyl benzene, product is mainly phenylacetaldehyde, and the selectivity of Styryl oxide is lower, and this is because catalyst is acid, has promoted Styryl oxide open loop isomerization to generate phenylacetaldehyde, makes product selectivity reduce.
Summary of the invention
For overcoming the deficiency that exists in the prior art, the invention provides a kind of HTS bed bioreactor, that activity is good, selectivity is high and resin compounded modified catalyst and preparation method thereof of being used for fixing.
HTS of the present invention and resin compounded modified catalyst are benchmark with the weight of catalyst, and the content of HTS is 1% ~ 50%, is preferably 5% ~ 40%, and the content of resin is 50% ~ 99%, is preferably 60% ~ 95%; Said catalyst acid intensity H
0≤+3.85 o'clock acidity is 0.005 ~ 0.015mmol/g.
The character of described HTS and resin compounded modified catalyst is following: specific area is 70 ~ 260m
2/ g, pore volume are 0.15 ~ 0.50 cm
3/ g, side pressure strength are 8 ~ 20 N.mm
-1
Described resin is the polymer of styrene and polyene-based compound, and both weight ratios are 2:1 ~ 5:1.Described polyene-based compound can be one or more in divinylbenzene, divinyl toluene, the biethenyl-xylene, is preferably divinylbenzene.
The preparation method of HTS of the present invention and resin compounded modified catalyst comprises:
HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed; In the presence of initator, at 60 ~ 150 ℃, preferably 80 ~ 100 ℃ were carried out polymerisation 3 ~ 10 hours; Preferably 4 ~ 6 hours, obtain the blocks of solid catalyst; Be processed into the catalyst solid particle then, above-mentioned catalyst solid particle is added in the halogenated hydrocarbons after the swelling, adopt solvent extraction, obtain HTS and resin compounded modified catalyst precursor; Above-mentioned catalyst precarsor at 120 ~ 200 ℃, is preferably under 150 ~ 180 ℃ of temperature under the atmosphere of ammonia and nitrogen mixture, and gaseous mixture volume air speed is 500 ~ 2500h
-1, kept 36 ~ 48 hours, promptly obtain HTS of the present invention and resin compounded modified catalyst.
Described polymerization single polymerization monomer polyene-based compound can be one or more in divinylbenzene, divinyl toluene, the biethenyl-xylene.
Described perforating agent can be gasoline, C
5~ C
13N-alkane, C
4~ C
12In the fatty alcohol one or more, preferably C
5~ C
13In the n-alkane one or more.
Described initator can be benzoyl peroxide and/or azo two isobutanols, 0.5% ~ 2.5% of the addition polymerization single polymerization monomer weight that to be the HTS powder use with the preparation resin.
When described initator added the reaction system that comprises HTS, polymerization single polymerization monomer that the preparation resin is used and perforating agent, the temperature of this reaction system was 60 ~ 90 ℃.
Described halogenated hydrocarbons can be C
1~ C
4Halogenated hydrocarbons, wherein preferably 1,2-dichloroethanes, described swelling time are 3 ~ 8 hours, preferably 5 ~ 6 hours.
Described extraction solvent can be one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, the butanols etc.Described extractive reaction temperature is 30 ~ 60 ℃, preferably 50 ~ 60 ℃; The described extracting time is 2 ~ 8 hours, preferably 4 ~ 6 hours.
In described ammonia and the nitrogen mixture, the volume ratio of ammonia and nitrogen is 0.1 ~ 5:100, is preferably 0.5 ~ 1:100.
When described catalyst precarsor was handled with ammonia and nitrogen mixture, heating rate was not more than 60 ℃/h, is preferably to be not more than 30 ℃/h.
The described method that the blocks of solid catalyst is processed into the catalyst solid particle; Can adopt crush method; Can also adopt patterning method etc., the blocks of solid catalyst is processed into the catalyst solid particle of suitable size and shape (like stripe shape, sphere, type sphere etc.).
The catalyst applications that the inventive method obtains prepares in the catalytic reaction process of Styryl oxide, preparing epichlorohydrin by chloropropene epoxidation in the epoxidation of styrene of fixed-bed process, and catalytic effect is excellent.
Compared with prior art, catalyst of the present invention has following characteristics:
1, can adopt the fixed bed reaction mode behind the shaping of catalyst, solve the catalyst and the problem that reactant liquor is difficult to separate of Ti-Si catalyst powder, improve reaction efficiency;
2, in catalytic reaction process because the diluting effect of a large amount of dispersants makes HTS exist with the form of isolating, so the oxidation reaction fuel factor relaxes, can reduce side reaction and take place, improved reaction selectivity;
3, behind the HTS polymerization forming; Not needing 500 ℃ of high temperature (>) roasting removes the perforating agent that adds in the forming process; Only need low temperature extracting activation and ammonia/nitrogen gaseous mixture K cryogenic treatment; Can avoid causing framework of molecular sieve to cave in or titanium detaches skeleton, fully keep HTS active;
4, catalyst of the present invention passes through ammonia atmosphere modification at a certain temperature, improves the acidity of catalyst, is beneficial to the raising selectivity of product;
5, catalyst backbone of the present invention is water-fast, helps at H
2O
2React in the reaction atmosphere.
The specific embodiment
Specific area described in the present invention adopts the low temperature liquid nitrogen determination of adsorption method according to ASTM D3663-2003 standard.Described pore volume adopts the low temperature liquid nitrogen determination of adsorption method according to ASTM D4222-2003 standard.Described side pressure strength is according to HG/T 2782-1996 standard, adopts QCY-602 type catalyst strength analyzer to measure.Described particle diameter is to adopt U.S.'s Taylor standard sieve (Tyler standard sieve series) to measure.The acid strength of described catalyst and acidity are to adopt the Hammett indicator, and the n-butylamine titration method records.Among the present invention, v% is a volume fraction, and wt% is a mass fraction.
The concrete preparation process of the inventive method is following:
(1), polymerization
In polymeric kettle, add HTS powder, polymerization single polymerization monomer polyene-based compound, perforating agent, after mixing; Warming-in-water; Add initator when being preferably in 60 ~ 90 ℃, under 60 ~ 150 ℃, carried out polymerisation 3 ~ 10 hours, obtain block titanium-silicon molecular sieve catalyst;
(2), solvent extraction activation
Above-mentioned block titanium-silicon molecular sieve catalyst is processed into the catalyst solid particle, such as through broken granulation, is the catalyst that obtains after 4 ~ 16 purpose Taylor standard sieves sieve through sieve mesh; Add halogenated hydrocarbons and carry out swelling, the volume of catalyst and halogenated hydrocarbons is 1:10 ~ 1:1, dissolved expanding 3 ~ 8 hours; After pouring out halogenated hydrocarbons, add extraction solvent again and carry out extracting, it is that the volume ratio of extraction solvent and catalyst is 1:1 ~ 5:1; 30 ~ 60 ℃ of extractive reaction temperature; 2 ~ 6 hours extracting time, extracting number of times 2 ~ 5 times obtains HTS of the present invention and resin compounded modified catalyst precursor;
(3), catalyst modification
Above-mentioned HTS and resin compounded modified catalyst precursor are packed in the tubular type roaster, airtight qualified after, feed ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 0.5 ~ 1:100, the mist air speed is 500 ~ 1500h
-1(volume) heats up simultaneously, and heating rate is not more than 30 ℃/h for being not more than 60 ℃/h, being preferably, and when temperature reaches, in the time of 120 ~ 200 ℃, keeps 36 ~ 48 hours, promptly obtains HTS of the present invention and resin compounded modified catalyst.This catalyst can directly be packed into and carried out the catalytic reaction that epoxidation of styrene prepares Styryl oxide, preparing epichlorohydrin by chloropropene epoxidation in the fixed bed reactors.
Below in conjunction with embodiment the present invention is done further detailed description; Following examples are not the restriction to protection domain of the present invention; Those skilled in the art combines specification of the present invention and can do suitable expansion in full, and these expansions all should be protection scope of the present invention.
Embodiment 1
In polymeric kettle, add HTS powder 7.5g, polymerization single polymerization monomer styrene 90g and divinylbenzene 30g, perforating agent liquid wax (C
9-11N-alkane) 60g after mixing, during warming-in-water to 60 ℃, adds initator benzoyl peroxide 1.5g, 90 ℃ of following polymeric reaction temperatures 6 hours, obtains block titanium-silicon molecular sieve catalyst.Carry out broken granulation then, the catalyst that after sieve mesh is 8 ~ 9 purpose Taylor standard sieves screenings, obtains adds 1, and the 2-dichloroethanes carries out swelling, and wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved bloated 5 hours.Pour out 1, behind the 2-dichloroethanes, add ethyl acetate again and carry out solvent extraction; Wherein the volume ratio of ethyl acetate and catalyst is 3:1,55 ℃ of extractive reaction temperature, 4 hours extracting time; Carry out three extractings with quadrat method, obtain HTS and resin compounded modified catalyst precursor, above-mentioned HTS and resin compounded modified catalyst precursor are packed in the tubular type roaster; Airtight qualified after, feed the ammonia gas volume concentrations and be 0.5% ammonia/nitrogen gaseous mixture, gas space velocity is 1000h
-1(volume) heats up simultaneously, and heating rate is ≯ 25 ℃/h, when temperature reaches 180 ℃, keeps 36 hours, promptly obtains HTS and resin compounded modified catalyst A, and its physico-chemical property is seen table 1.
Embodiment 2
In polymeric kettle, add HTS powder 15g, polymerization single polymerization monomer styrene 90g, divinyl toluene 15 g, biethenyl-xylene 25g, perforating agent C
5Fatty alcohol 60g after mixing, during warming-in-water to 80 ℃, adds initator azo two isobutanol 2.0g, 100 ℃ of following polymeric reaction temperatures 6 hours, obtains block titanium-silicon molecular sieve catalyst.Carry out broken granulation then, the catalyst that after sieve mesh is 8 ~ 9 purpose Taylor standard sieves screenings, obtains adds 1, and the 2-dichloroethanes carries out swelling, and wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved bloated 5 hours.Pour out 1, behind the 2-dichloroethanes, add xylenes again and carry out solvent extraction; Wherein the volume ratio of xylenes and catalyst is 3:1,55 ℃ of extractive reaction temperature, 4 hours extracting time; Carry out three extractings with quadrat method, obtain HTS and resin compounded modified catalyst precursor, above-mentioned HTS and resin compounded modified catalyst precursor are packed in the tubular type roaster; Airtight qualified after, feed the ammonia gas volume concentrations and be 1% ammonia/nitrogen gaseous mixture, gas space velocity is 500h
-1(volume) heats up simultaneously, and heating rate is ≯ 25 ℃/h, when temperature reaches 150 ℃, keeps 48 hours, promptly obtains HTS and resin compounded modified catalyst B, and its physico-chemical property is seen table 1.
Embodiment 3
The weight of HTS powder among the embodiment 1 is become 30g, and the tubular type roaster processing time is 48 hours, and all the other obtain HTS and resin compounded modified catalyst C with embodiment 1, and its physico-chemical property is seen table 1.
Embodiment 4
The weight of HTS powder among the embodiment 1 is become 45g, and tubular type roasting furnace temperature elevation speed is ≯ 30 ℃/h, and all the other obtain HTS and resin compounded modified catalyst D with embodiment 1, and its physico-chemical property is seen table 1.
Embodiment 5
The weight of HTS powder among the embodiment 1 is become 60g, and ammonia and nitrogen mixture air speed are 1500h
-1(volume), all the other obtain HTS and resin compounded modified catalyst E with embodiment 1, and its physico-chemical property is seen table 1.
Embodiment 6
The weight of HTS powder among the embodiment 1 is become 75g, and feeding ammonia gas volume concentrations is 1.5% ammonia/nitrogen gaseous mixture, and all the other obtain HTS and resin compounded modified catalyst F with embodiment 1, and its physico-chemical property is seen table 1.
The physico-chemical property of table 1 catalyst
| Catalyst | Specific area, m 2/g | Pore volume, cm 3/g | Side pressure strength, N/mm | Acidity *, mmol/g |
| A | 83.2 | 0.21 | 16.5 | 0.013 |
| B | 95.4 | 0.17 | 15.6 | 0.006 |
| C | 112.2 | 0.22 | 10.2 | 0.009 |
| D | 138.6 | 0.30 | 11.5 | 0.009 |
| E | 170.3 | 0.39 | 9.9 | 0.010 |
| F | 210.9 | 0.23 | 8.1 | 0.008 |
* the acidity in the table 1 is meant acid strength H
0≤+3.85 o'clock acidity.
Embodiment 7
The catalyst C 50ml that the gets embodiment 2 diameter 20mm that packs in the fixed bed reactors of long 1200mm, carries out the vinyl chloride epoxidation reaction, at 60 ℃ of reaction temperatures, pressure 0.5MPa, chloropropene and H
2O
2Mol ratio be 5: 1, methyl alcohol and H
2O
2Mol ratio be that 15: 1, reactant liquor phase volume air speed are 10h
-1Condition under, H
2O
2Conversion ratio 97% (mole), the selectivity of epoxychloropropane＞98% (mole).
Embodiment 8
The catalyst D 50ml that the gets embodiment 3 diameter 20mm that packs in the fixed bed reactors of long 1200mm, carries out the epoxidation of styrene reaction, at 70 ℃ of reaction temperatures, pressure 0.5MPa, styrene and H
2O
2Mol ratio be 2: 1, acetone and cinnamic volume ratio are that 2: 1, volume of styrene air speed are 0.2h
-1Condition under, H
2O
2Conversion ratio 70 % (mole), the selectivity of Styryl oxide＞67% (mole).
Claims (22)
1. HTS and resin compounded modified catalyst are benchmark with the weight of catalyst, and the content of HTS is 1% ~ 50%, and the content of resin is 50% ~ 99%, said catalyst acid intensity H
0≤+3.85 o'clock acidity is 0.005 ~ 0.015mmol/g.
2. according to the described catalyst of claim 1, it is characterized in that the character of said catalyst is following: specific area is 70 ~ 260m
2/ g, pore volume are 0.15 ~ 0.50 cm
3/ g, side pressure strength are 8 ~ 20 N.mm
-1
3. according to the described catalyst of claim 1, it is characterized in that the weight with catalyst is benchmark, the content of HTS is 5% ~ 40%, and the content of resin is 60% ~ 95%.
4. according to the described catalyst of claim 1, it is characterized in that described resin is the polymer of styrene and polyene-based compound, the polyene-based compound is one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene.
5. according to the described catalyst of claim 4, it is characterized in that described polyene-based compound is a divinylbenzene.
6. according to the described catalyst of claim 4, it is characterized in that in the described resin that the weight ratio of styrene and polyene-based compound is 2:1 ~ 5:1.
7. the preparation method of arbitrary said HTS of claim 1 ~ 6 and resin compounded modified catalyst comprises:
HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, in the presence of initator, carried out polymerisation 3 ~ 10 hours, obtain the blocks of solid catalyst at 60 ~ 150 ℃; Be processed into the catalyst solid particle then, above-mentioned catalyst solid particle is added in the halogenated hydrocarbons after the swelling, adopt solvent extraction, obtain HTS and resin compounded modified catalyst precursor; Above-mentioned catalyst precarsor is under the atmosphere of ammonia and nitrogen mixture, and under 120 ~ 200 ℃ of temperature, gaseous mixture volume air speed is 500 ~ 2500h
-1, kept 36 ~ 48 hours, promptly obtain HTS and resin compounded modified catalyst.
8. according to the described method of claim 7, it is characterized in that described polymeric reaction temperature is 80 ~ 100 ℃, the reaction time is 4 ~ 6 hours.
9. according to the described method of claim 7, it is characterized in that described perforating agent is gasoline, C
5~ C
13N-alkane, C
4~ C
12In the fatty alcohol one or more.
10. according to the described method of claim 7, it is characterized in that described perforating agent is C
5~ C
13In the n-alkane one or more.
11. according to the described method of claim 7, it is characterized in that described initator is benzoyl peroxide and/or azo two isobutanols, 0.5% ~ 2.5% of the addition polymerization single polymerization monomer weight that to be the HTS powder use with the preparation resin.
12., it is characterized in that described halogenated hydrocarbons is C according to the described method of claim 7
1~ C
4Halogenated hydrocarbons, the volume of described catalyst and halogenated hydrocarbons is 1:10 ~ 1:1, described swelling time is 3 ~ 8 hours.
13. according to the described method of claim 7, it is characterized in that described halogenated hydrocarbons is 1,2-dichloroethanes, the volume of described catalyst and halogenated hydrocarbons are 1:10 ~ 1:1, described swelling time is 5 ~ 6 hours.
14. according to the described method of claim 7, it is characterized in that described extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, the butanols, the volume ratio of described extraction solvent and catalyst is 1:1 ~ 5:1.
15., it is characterized in that described extractive reaction temperature is 30 ~ 60 ℃ according to the described method of claim 7; The described extracting time is 2 ~ 8 hours, and the extracting number of times is 2 ~ 5 times.
16., it is characterized in that described extractive reaction temperature is 50 ~ 60 ℃ according to the described method of claim 7; The described extracting time is 4 ~ 6 hours, and the extracting number of times is 2 ~ 5 times.
17. according to the described method of claim 7, when it is characterized in that described initator adds the reaction system that comprises HTS, polymerization single polymerization monomer that the preparation resin is used and perforating agent, the temperature of this reaction system is 60 ~ 90 ℃.
18., it is characterized in that in described ammonia and the nitrogen mixture that the volume ratio of ammonia and nitrogen is 0.1 ~ 5:100 according to the described method of claim 7.
19., it is characterized in that in described ammonia and the nitrogen mixture that the volume ratio of ammonia and nitrogen is 0.5 ~ 1:100 according to the described method of claim 7.
20., it is characterized in that it is 150 ~ 180 ℃ that said catalyst precarsor uses ammonia and nitrogen mixture treatment temperature according to the described method of claim 7.
21., it is characterized in that the heating rate when said catalyst precarsor is handled with ammonia and nitrogen mixture is not more than 60 ℃ according to the described method of claim 7.
22., it is characterized in that the heating rate when said catalyst precarsor is handled with ammonia and nitrogen mixture is not more than 30 ℃ according to the described method of claim 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801404A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of titanium silicon molecular sieve and resin composite catalyst |
| WO2021142635A1 (en) * | 2020-01-14 | 2021-07-22 | 万华化学集团股份有限公司 | Method for preparing catalyst for epoxidation of propylene and use thereof |
| CN113181961A (en) * | 2020-01-14 | 2021-07-30 | 万华化学集团股份有限公司 | Preparation method and application of propylene epoxidation catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399794B1 (en) * | 2001-11-15 | 2002-06-04 | Arco Chemical Technology, L.P. | Direct epoxidation process using carbonate modifiers |
| CN101124044A (en) * | 2004-03-09 | 2008-02-13 | 利安德化学技术有限公司 | Polymer-encapsulated titanium zeolites for oxidation reactions |
| CN101596463A (en) * | 2009-07-09 | 2009-12-09 | 天津大学 | Granular titanium-silicon molecular sieve catalyst and preparation method thereof |
-
2011
- 2011-04-26 CN CN201110105053.6A patent/CN102755910B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399794B1 (en) * | 2001-11-15 | 2002-06-04 | Arco Chemical Technology, L.P. | Direct epoxidation process using carbonate modifiers |
| CN101124044A (en) * | 2004-03-09 | 2008-02-13 | 利安德化学技术有限公司 | Polymer-encapsulated titanium zeolites for oxidation reactions |
| CN101596463A (en) * | 2009-07-09 | 2009-12-09 | 天津大学 | Granular titanium-silicon molecular sieve catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| D. TRONG ON等: "Epoxidation of alkenes over new amorphous materials containing different acidic functions", 《CHEM. COMMUN.》, 31 December 1996 (1996-12-31) * |
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