CN102755910B - 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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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.Catalyst of the present invention is suitable for the epoxidation of styrene of fixed-bed process and prepares in the catalytic reaction process of Styryl oxide, preparing epichlorohydrin by chloropropene epoxidation.
Background technology
From Italian Enichem company's nineteen eighty-three first since synthesis of titanium silicon molecular sieve catalyst TS-1, because the selective and gentle reaction condition of the oxidation of its excellence becomes 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 very important effect aspect organic compound selective oxidation, as preparing epoxypropane by epoxidation of propene, preparing epichlorohydrin by chloropropene epoxidation, epoxidation of styrene is prepared Styryl oxide, phenol is prepared benzenediol with hydrogen peroxide oxidation under HTS effect, and cyclohexanone carries out prepared by ammoxidation for cyclohexanone oxime etc. with hydrogen peroxide under titanium-silicon molecular sieve catalyst effect.In commercial Application, titanium-silicon molecular sieve catalyst shows good shape selective catalysis performance, general particle diameter is less, catalyst activity is higher, selectively better, in practical application, the particle diameter of titanium-silicon molecular sieve catalyst is about 0.1-15.0 μ m, but, so little particle diameter brings great difficulty with separating of product can to catalyst, although the 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 producing when its filtration the size that does not lie in the duct of filtering material, but come from superfine little catalyst particle and occupy and stop up the duct of formed filter cake, especially the catalyst particle that particle diameter is less than 2 μ m is the most unfavorable to filtering, cause like this production efficiency low, also have influence on the process of HTS industrial applications.The catalyst of small particle diameter in the time filtering except stopping up filter cake duct, part 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 and in product material, cause further side reaction, cause the increase of separation costs, affect product quality.
Epoxychloropropane is a kind of important industrial chemicals and synthetic intermediate, and in epoxide, the output of epoxychloropropane is only second to oxirane and expoxy propane.Its purposes is very extensive, is mainly used to synthetic epoxy resin chlorohydrin rubber; Also be the primary raw material of epoxy resin, nitroglycerine, fiberglass, electric insulation goods; Also can be used as producing the raw material of 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%.Having relatively high expectations of the decay resistance of propylene high-temperature chloridising to reactor, and energy consumption is larger, consumption chlorine is more, and accessory substance is more, needs purified treatment, and environmental pollution is serious; Propylene acetate method, has adopted acetoxylation technology, reaction condition gentleness, and chlorine consumption reduces half, and accessory substance is less, but the method step is many, and technological process is long, and three wastes discharge amount is large.Due to oil price rise, cause industrial chemicals price to increase considerably, seek more economical route production epoxychloropropane and receive much concern.Take HTS as catalyst, H
2o
2as the oxygen source of epoxidation reaction, its active o content is higher than ROOH, in addition H
2o
2after epoxidation reaction, self changes H into
2o, the byproduct that is not difficult to processing, so the method is environment amenable, more clean process route.
CN1534030A has proposed a kind of epoxychloropropane preparation method, comprise: chloropropene, hydrogen peroxide, solvent and titanium-silicon molecular sieve catalyst particle are put into reactor and reacted, solvent and unreacted chloropropene directly turn back to reactor through fractionator, slurries in reactor after filtering, gained clear liquid is isolated to epoxychloropropane product, gained returns to reactor containing the concentrated slurry of catalyst, and from clear liquid, isolated solvent and chloropropene also return to reactor continuation use.Although this process provides a kind of flow process is simple, energy consumption is low chloropropene Direct Epoxidation to prepare the method for epoxychloropropane, but owing to adopting batch process operation, catalyst is slurry state, after reaction, need to from product, separate, reuse, this makes technological process loaded down with trivial details, and is unfavorable for large-scale industrial production, in this process, catalyst also can produce inevitable loss in addition.
In order to solve in epoxychloropropane production process, owing to there being the strong polar compound such as water or alcohol in reaction system, to there is catalysis ring-opening reaction in the epoxide moiety generating, reduce the problem of the yield of epoxides, CN1319099A discloses a kind of ancillary method that improves epoxides yield, add alkaline organic to improve selective, but owing to having introduced the third component, to make product purify and increase difficulty, and this process remains and adopts batch process operation, does not solve above-mentioned catalyst and is difficult to the problem separating.
USP 4833260 discloses a kind of take HTS as catalyst, directly alkene is carried out to epoxidation produce epoxides method with hydrogen peroxide.But because HTS need to could show high catalytic activity in the reaction system that be solvent at strong polar compounds such as alcohols, and the surface acidity of catalyst can cause product epoxides generation catalysis ring-opening reaction to generate accessory substance ethers, what make epoxides selectively only has 85% left and right, and the yield of epoxides is lower.
Styryl oxide can be used as diluent, UV-absorbent, fumet of epoxy resin etc., it is also the important intermediate of organic synthesis, pharmacy and perfume industry simultaneously, as Styryl oxide hydrogenation can obtain bata-phenethyl alcohol, this route has high and easy refining, the advantage such as environmental pollution is little of product yield, and Styryl oxide is also the main intermediate of synthetic levamisol.
Industrial Styryl oxide synthetic method is halogenohydrin method and peroxy acid direct oxidation method.The former environmental pollution is serious, is a kind of anxious improved production technology for the treatment of; The latter's organic peroxide acid price comparison used costliness, serious to equipment corrosion, and be difficult to separate from reactant, production specifications require high.
The method that hydrogen peroxide catalyzed epoxidation vinyl benzene is prepared Styryl oxide has safety, economy, non-environmental-pollution, the advantage such as environmentally friendly, but needs corresponding catalyst.That research is more at present is Fe-silicalite/H
2o
2epoxidation process.As S.B. Kumar etc. (J. Catal. 1995,156: 163-166) report use TS-1/H
2o
2system epoxidation vinyl benzene, (the Journal of Dalian University of Technology Total 2002,42 (5): 535-538) make catalyst with the synthetic TS-1 of cheap raw material styrene is carried out to epoxidation etc. such as Li Gang.But Fe-silicalite/H
2o
2when system epoxidation vinyl benzene, product is mainly phenylacetaldehyde, and Styryl oxide is selectively lower, and this is because catalyst is acid, has promoted Styryl oxide open loop isomerization to generate phenylacetaldehyde, makes the elective reduction of product.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of for good, selective high HTS fixed bed reactors, active and resin compounded modified catalyst and preparation method thereof.
HTS of the present invention and resin compounded modified catalyst, take the weight of catalyst as benchmark, the content of HTS is 1% ~ 50%, is preferably 5% ~ 40%, the content of resin is 50% ~ 99%, is preferably 60% ~ 95%; Described catalyst acid intensity H
0the acidity of≤+ 3.85 o'clock is 0.005 ~ 0.015mmol/g.
The character of described HTS and resin compounded modified catalyst is as follows: specific area is 70 ~ 260m
2/ g, pore volume is 0.15 ~ 0.50 cm
3/ g, side pressure strength is 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, biethenyl-xylene, is preferably divinylbenzene.
The preparation method of HTS of the present invention and resin compounded modified catalyst, comprising:
HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, under initator exists, at 60 ~ 150 ℃, preferably 80 ~ 100 ℃ are carried out polymerisation 3 ~ 10 hours, preferably 4 ~ 6 hours, obtain blocks of solid catalyst; Then be processed into catalyst solid particle, by above-mentioned catalyst solid particle be added to swelling in halogenated hydrocarbons after, adopt solvent extraction, obtain HTS and resin compounded modified catalyst precursor; Above-mentioned catalyst precarsor, under the atmosphere of ammonia and nitrogen mixture, at 120 ~ 200 ℃, is preferably at 150 ~ 180 ℃ of temperature, and gaseous mixture volume air speed is 500 ~ 2500h
-1, keep 36 ~ 48 hours, 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, 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 isobutanols, and addition is HTS powder and prepares 0.5% ~ 2.5% of polymerization single polymerization monomer weight that resin uses.
When described initator adds and comprise HTS, prepares the reaction system of polymerization single polymerization monomer that resin uses and perforating agent, the temperature of this reaction system is 60 ~ 90 ℃.
Described halogenated hydrocarbons can be C
1~ C
4halogenated hydrocarbons, wherein preferably 1,2-dichloroethanes, described swelling time is 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 ℃, preferably 50 ~ 60 ℃; The described extracting time is 2 ~ 8 hours, preferably 4 ~ 6 hours.
In described ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 0.1 ~ 5:100, is preferably 0.5 ~ 1:100.
When described catalyst precarsor is processed with ammonia and nitrogen mixture, heating rate is not more than 60 ℃/h, is preferably and is not more than 30 ℃/h.
The described method that blocks of solid catalyst is processed into catalyst solid particle, can adopt crush method, can also adopt patterning method etc., blocks of solid catalyst is processed into the catalyst solid particle of suitable size and shape (as stripe shape, spherical, class is spherical etc.).
The catalyst that the inventive method obtains is applied to the epoxidation of styrene of fixed-bed process to be prepared in the catalytic reaction process of Styryl oxide, preparing epichlorohydrin by chloropropene epoxidation, catalytic effect excellence.
Compared with prior art, catalyst of the present invention has following feature:
1, after shaping of catalyst, can adopt fixed bed reaction mode, solve the problem that the catalyst of Ti-Si catalyst powder is difficult to separate with reactant liquor, improve reaction efficiency;
2, in catalytic reaction process due to the diluting effect of a large amount of dispersants, HTS is existed with the form of isolation, so oxidation reaction fuel factor relaxes, can reduce side reaction and occur, improved reaction selectivity;
3, after HTS polymerization forming, do not need high temperature (>500 ℃) roasting to remove the perforating agent adding in 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 activity;
4, catalyst of the present invention, by ammonia atmosphere modification at a certain temperature, improves the acidity of catalyst, is beneficial to raising selectivity of product;
5, catalyst backbone of the present invention is water-fast, is conducive at H
2o
2in reaction atmosphere, react.
The specific embodiment
Specific area described in the present invention adopts low temperature liquid nitrogen determination of adsorption method according to ASTM D3663-2003 standard.Described pore volume adopts 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 Hammett indicator, and n-butylamine titration method records.In the present invention, v% is volume fraction, and wt% is mass fraction.
The concrete preparation process of the inventive method is as follows:
(1), polymerization
In polymeric kettle, add HTS powder, polymerization single polymerization monomer polyene-based compound, perforating agent, after being uniformly mixed, warming-in-water, while being preferably in 60 ~ 90 ℃, add initator, at 60 ~ 150 ℃, carry 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 catalyst solid particle, such as through broken granulation, the catalyst obtaining after sieve mesh is 4 ~ 16 object Taylor standard sieve screenings, add halogenated hydrocarbons to carry out swelling, the volume of catalyst and halogenated hydrocarbons is 1:10 ~ 1:1, dissolved swollen 3 ~ 8 hours, pour out after halogenated hydrocarbons, add again extraction solvent to 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, obtain 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 pipe type calciner, airtight qualified after, pass into ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 0.5 ~ 1:100, 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, obtains HTS of the present invention and resin compounded modified catalyst.This catalyst can directly pack into and in fixed bed reactors, carries out the catalytic reaction that epoxidation of styrene is prepared Styryl oxide, preparing epichlorohydrin by chloropropene epoxidation.
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.
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 being uniformly mixed, when warming-in-water to 60 ℃, add initator benzoyl peroxide 1.5g, at 90 ℃, polymeric reaction temperature 6 hours, obtains block titanium-silicon molecular sieve catalyst.Then carry out broken granulation, the catalyst obtaining after sieve mesh is 8 ~ 9 object Taylor standard sieves screenings, adds 1,2-dichloroethanes to carry out swelling, and wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved swollen 5 hours.Pour out 1, after 2-dichloroethanes, then add ethyl acetate to 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, same method carries out three extractings, obtains HTS and resin compounded modified catalyst precursor, above-mentioned HTS and resin compounded modified catalyst precursor are packed in pipe type calciner, airtight qualified after, pass into 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, in the time that temperature reaches 180 ℃, keeps 36 hours, obtains HTS and resin compounded modified catalyst A, and its physico-chemical property is in 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 being uniformly mixed, when warming-in-water to 80 ℃, adds initator azo two isobutanol 2.0g, and at 100 ℃, polymeric reaction temperature 6 hours, obtains block titanium-silicon molecular sieve catalyst.Then carry out broken granulation, the catalyst obtaining after sieve mesh is 8 ~ 9 object Taylor standard sieves screenings, adds 1,2-dichloroethanes to carry out swelling, and wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved swollen 5 hours.Pour out 1, after 2-dichloroethanes, then add dimethylbenzene to carry out solvent extraction, wherein the volume ratio of dimethylbenzene and catalyst is 3:1,55 ℃ of extractive reaction temperature, 4 hours extracting time, same method carries out three extractings, obtains HTS and resin compounded modified catalyst precursor, above-mentioned HTS and resin compounded modified catalyst precursor are packed in pipe type calciner, airtight qualified after, pass into 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, in the time that temperature reaches 150 ℃, keeps 48 hours, obtains HTS and resin compounded modified catalyst B, and its physico-chemical property is in table 1.
Embodiment 3
The weight of HTS powder in embodiment 1 is become to 30g, and the pipe type calciner 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 in table 1.
Embodiment 4
The weight of HTS powder in embodiment 1 is become to 45g, and pipe type calciner heating rate is ≯ 30 ℃/h, and all the other obtain HTS and resin compounded modified catalyst D with embodiment 1, and its physico-chemical property is in table 1.
Embodiment 5
The weight of HTS powder in embodiment 1 is become to 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 in table 1.
Embodiment 6
The weight of HTS powder in embodiment 1 is become to 75g, pass into ammonia gas volume concentrations and be 1.5% ammonia/nitrogen gaseous mixture, all the other obtain HTS and resin compounded modified catalyst F with embodiment 1, and its physico-chemical property is in 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 table 1 refers to acid strength H
0the acidity of≤+ 3.85 o'clock.
Embodiment 7
The catalyst C 50ml that gets embodiment 2 packs diameter 20mm into, in the fixed bed reactors of long 1200mm, carries out 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 selective > 98%(mole of epoxychloropropane).
Embodiment 8
The catalyst D 50ml that gets embodiment 3 packs diameter 20mm into, in the fixed bed reactors of long 1200mm, carries out 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 selective > 67%(mole of Styryl oxide).
Claims (23)
1. a preparation method for HTS and resin compounded modified catalyst, this catalyst, take the weight of catalyst as benchmark, the content of HTS is 1%～50%, and the content of resin is 50%～99%, and its preparation process comprises:
HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, under initator exists, carry out polymerisation 3～10 hours at 60～150 ℃, obtain blocks of solid catalyst; Then be processed into catalyst solid particle, by above-mentioned catalyst solid particle be added to swelling in halogenated hydrocarbons after, 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 at 120～200 ℃ of temperature, gaseous mixture volume air speed is 500～2500h
-1, keep 36～48 hours, obtain HTS and resin compounded modified catalyst.
2. in accordance with the method for claim 1, it is characterized in that described polymeric reaction temperature is 80～100 ℃, the reaction time is 4～6 hours.
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 1, 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 isobutanols, addition is HTS powder and prepares 0.5%～2.5% of polymerization single polymerization monomer weight that resin uses.
6. in accordance with the method for claim 1, it is characterized in that described halogenated hydrocarbons is C
1～C
4halogenated hydrocarbons, described catalyst and the volume of halogenated hydrocarbons are 1:10～1:1, described swelling time is 3～8 hours.
7. in accordance with the method for claim 1, it is characterized in that described halogenated hydrocarbons is 1,2-dichloroethanes, described catalyst and the volume of halogenated hydrocarbons are 1:10～1:1, and described swelling time is 5～6 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 extraction solvent and the volume ratio of catalyst are 1:1～5:1.
9. in accordance with the method for claim 1, it is characterized in that described extractive reaction temperature is 30～60 ℃; The described extracting time is 2～8 hours, and extracting number of times is 2～5 times.
10. in accordance with the method for claim 1, it is characterized in that described extractive reaction temperature is 50～60 ℃; The described extracting time is 4～6 hours, and extracting number of times is 2～5 times.
11. in accordance with the method for claim 1, it is characterized in that described initator add comprise HTS, while preparing the reaction system of polymerization single polymerization monomer that resin uses and perforating agent, the temperature of this reaction system is 60～90 ℃.
12. in accordance with the method for claim 1, it is characterized in that in described ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 0.1～5:100.
13. in accordance with the method for claim 1, it is characterized in that in described ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 0.5～1:100.
14. in accordance with the method for claim 1, and the temperature that it is characterized in that described catalyst precarsor ammonia and nitrogen mixture processing is 150～180 ℃.
15. in accordance with the method for claim 1, it is characterized in that heating rate when described catalyst precarsor ammonia and nitrogen mixture are processed is not more than 60 ℃/h.
16. in accordance with the method for claim 1, it is characterized in that heating rate when described catalyst precarsor ammonia and nitrogen mixture are processed is not more than 30 ℃/h.
17. in accordance with the method for claim 1, it is characterized in that weight take catalyst is as benchmark, and the content of HTS is 5%～40%, and the content of resin is 60%～95%.
18. in accordance with the method for claim 1, it is characterized in that described resin is the polymer of styrene and polyene-based compound, polyene-based compound is one or more in divinylbenzene, divinyl toluene and biethenyl-xylene.
19. in accordance with the method for claim 18, it is characterized in that described polyene-based compound is divinylbenzene.
20. in accordance with the method for claim 18, it is characterized in that in described resin, the weight ratio of styrene and polyene-based compound is 2:1～5:1.
21. 1 kinds of HTSs and resin compounded modified catalyst, is characterized in that adopting the arbitrary described method of claim 1～20 to prepare.
22. according to the catalyst described in claim 21, it is characterized in that the acid strength H of described catalyst
0the acidity of≤+ 3.85 o'clock is 0.005～0.015mmol/g.
23. according to the catalyst described in claim 21, it is characterized in that the character of described catalyst is as follows: specific area is 70～260m
2/ g, pore volume is 0.15～0.50cm
3/ g, side pressure strength is 8～20N.mm
-1.
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| CN113181961B (en) * | 2020-01-14 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method and application of propylene epoxidation catalyst |
| SG11202109384VA (en) * | 2020-01-14 | 2021-09-29 | Wanhua Chemical Group Co Ltd | Preparation method for propylene epoxidation catalyst and use thereof |
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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 |
-
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 |
Non-Patent Citations (2)
| Title |
|---|
| D. Trong On等.Epoxidation of alkenes over new amorphous materials containing different acidic functions.《Chem. Commun.》.1996, |
| Epoxidation of alkenes over new amorphous materials containing different acidic functions;D. Trong On等;《Chem. Commun.》;19961231;第1161-1162页 * |
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