CN102755904B - Preparation method of acidic molecular sieve and resin composite catalyst - Google Patents
Preparation method of acidic molecular sieve and resin composite catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of an acidic molecular sieve and resin composite catalyst. According to the invention, acidic 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 the acidic molecular sieve and resin composite catalyst is obtained. With the catalyst, a problem of poor hydro-thermal stability of a molecular sieve catalyst used in an alkene hydration reaction is solved, and catalyst service life is prolonged. When the catalyst is used in a fixed bed alkene hydration reaction process, a one-path conversion rate is high, and a target product yield is high.
Description
Technical field
The present invention relates to a kind of acidic molecular sieve and resin compounded Catalysts and its preparation method, this catalyst can be used in olefin hydration low-carbon alcohols processed, ether process.
Background technology
Olefin hydration is one of important organic catalytic reaction.In olefin hydration reaction tool represent meaning and with practical value be the reaction that olefin hydration is prepared corresponding alcohols, as ethanol, isopropyl alcohol, sec-butyl alcohol have purposes widely as important Organic Chemicals and solvent in industries such as coating, dyestuff, medicine, synthetic rubber, spices, agricultural chemicals.In recent years, along with the level of crude oil processing increases, produced a large amount of C
2～C
7alkene, and olefin hydration is the important means that consumes alkene, is also the important method of industrial production alcoholic product.Olefin hydration reaction is typical acid catalyzed reaction, and its catalyst is generally sulfuric acid and phosphoric acid, because above-mentioned two kinds of catalyst exist the problems such as burn into loss, is progressively replaced by zeolite catalyst and strong resin catalyst in recent years.Although strong resin has certain catalytic activity, due to its exist preparation complicated, easily inactivation, can not regenerate, the shortcoming such as production capacity is low, and make each research institution of the world be devoted to develop low-carbon alkene hydration zeolite catalyst.
Relevant zeolite molecular sieve catalyst is more for the research report of olefin hydration, as EP210793, EP323268, EP323268, EP458048, US4857664, US4727977, US5012014.Above-mentioned document shows that propylene hydration prepared in the zeolite that isopropyl alcohol/isopropyl ether adopts, and β zeolite effect is best.ZSM-5 has good catalytic effect to ethylene hydration, and butylene hydration sec-butyl alcohol processed adopts ZSM series effect good.Under olefin hydration reaction condition, zeolite-type molecular sieve has good catalytic performance, but is subject to the restriction of preparation condition, also exists hydrothermal stability of molecular sieve poor, under reaction condition, catalyst strength is subject to hydrothermal condition to affect decline rapidly, has limited the realization of its commercial Application.
CN1245738A discloses the method for a kind of low-carbon alkene hydration low-carbon alcohols processed.The catalyst that the method adopts is made up of beta-molecular sieve and the binding agent of modification, and modifying element is selected from least one in La, B, Fe, Ge, Ni, Cr, Co, Cu, Mg, Ca, Sr, Ge; Catalyst consists of (percentage by weight) modifying element 1 wt% ~ 5wt%, beta-zeolite molecular sieve 40 wt% ~ 80 wt%, binding agent surplus.It is binding agent that the method adopts Ludox, clay, aluminium hydroxide etc., and the catalyst hydrothermal stability of preparation is poor, under olefin hydration reaction condition intensity decline too fast, be difficult to realize commercial Application.
CN1872826A discloses a kind of method of continuous production lower alcohol, adopt hydrating process, 80～200 ℃ of reaction temperatures, reaction pressure 4.0～20.0MPa, solid acid catalyst adopts cationic ion-exchange resin, low-carbon alkene catalysis hydration is become to low-carbon alcohols, and the alcohol in reaction afterproduct is separated.Catalyzing cation exchange resin olefin hydration conversion per pass lower (<10%), along with reaction is carried out, sulfonate radical runs off and causes equipment corrosion, and needs supporting deionized water system to remove the ion in recirculated water, complex technical process.
Acidic molecular sieve is also for alkene direct hydration etherificate coproduction correspondent alcohol and ether technology, especially propylene hydration etherificate diisopropyl ether processed.Diisopropyl ether blending octane number is high, and Reynolds steam forces down, and exhaust emissions amount is few, is a kind of desirable gasoline additive, and the research that propylene one step hydration and etherification is prepared isopropyl alcohol and diisopropyl ether in recent years comes into one's own day by day.
US 5231233 discloses the propylene hydration etherification method take layer column type MCM-36 as catalyst, at 7.0MPa, 160 ℃, water alkene weight ratio 0.92, LHSV 0.69h
-1the different ether of propylene conversion 17.2%, two selective 10.9% under condition.The method propylene conversion and diisopropyl ether are selectively all lower, have limited its commercial Application.
CN 101757942A discloses the method for a kind of Y zeolite through Cr, Mo modification for propylene etherificate diisopropyl ether processed.The method reaches 90%, diisopropyl ether selective 95% take propylene, water, isopropyl alcohol as raw material at 160 ℃, 2.5MPa, alcohol/alkene mol ratio propylene conversion under 1.0 condition.The method, owing to having introduced isopropyl alcohol, has increased separation of products difficulty, and technical process is more complicated.
CN 1298761A discloses a kind of method of beta-zeolite molecular sieve modification, prepares the method for diisopropyl ether for propylene one-step method hydration and etherification, and the method is take propylene, water as raw material is at 160 ℃, 7.0MPa, propylene air speed 0.5h
-1under condition, propylene conversion 60%, diisopropyl ether selective 71%.
Acidic molecular sieve is applied in olefin hydration, etherification reaction process, has good catalytic activity, but rarely realizes at present commercial Application, and main cause is because molecular sieve all uses SiO in preparation process
2, Al
2o
3, SiO
2-Al
2o
3, clay, aluminium hydroxide etc. are binding agent, such binding agent has under the reaction condition that water exists in hydration, etherificate etc., hydrothermal stability extreme difference, intensity reduces rapidly, is difficult to reach commercial Application requirement.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of acidic molecular sieve and resin compounded Catalysts and its preparation method.This catalyst good hydrothermal stability, catalyst strength is good, is applicable in olefin hydration low-carbon alcohols processed, ether process, and conversion per pass is high, object product yield is high, long service life.
Acidic molecular sieve of the present invention and resin compounded catalyst, take the weight of catalyst as benchmark, the content of acidic molecular sieve is 1% ~ 50%, is preferably 10% ~ 30%, the content of resin is 50% ~ 99%, is preferably 70% ~ 90%.
The character of described catalyst is as follows: specific area is 80 ~ 200 m
2/ g, pore volume is 0.05 ~ 0.50 cm
3/ g, side pressure strength is 6 ~ 16N/mm.
Described acidic molecular sieve refers to the molecular sieve with acid catalysis function, be selected from but be not limited to following molecular sieve: Si-Al molecular sieve, one or more in silicoaluminophosphamolecular molecular sieves, be preferably beta-molecular sieve, ZSM Series Molecules sieve, modenite, faujasite, erionite, A type zeolite, MCM Series Molecules sieve, one or more in SAPO Series Molecules sieve, ZSM Series Molecules sieve can be ZSM-5, ZSM-8, ZSM-11, one or more in ZSM-35, SAPO Series Molecules sieve can be SAPO-5, one or more in SAPO-11, MCM Series Molecules sieve can be MCM-22, MCM-36, one or more in MCM-41 molecular sieve, more preferably beta-molecular sieve, ZSM-5 molecular sieve, MCM-36, one or more in Y zeolite.Described acidic molecular sieve is one or more in hydrogen type molecular sieve and modified molecular screen, polyvalent cation exchange molecular sieve and modified molecular screen thereof, is preferably one or more in hydrogen type molecular sieve and modified molecular screen thereof.Described hydrogen type molecular sieve can obtain after ammonium exchange in decomposition or the hydrogen ion exchange of ammonium ion, described polyvalent cation exchange molecular sieve is that exchange obtains through polyvalent cation, such as alkaline earth metal cation-exchanged molecular sieve, rare earth metal cation exchange molecular sieve etc.Described modified molecular screen includes but not limited to adopt the molecular sieve obtaining after Molecular regulator sieve acidity, pore structure, silica alumina ratio, the isoparametric method modification of non-framework aluminum.
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 and biethenyl-xylene, is preferably divinylbenzene.
The preparation method of acidic molecular sieve of the present invention and resin compounded catalyst, comprising:
By acidic molecular sieve powder, prepare polymerization single polymerization monomer and the perforating agent that resin uses and fully mix, under initator exists, at 20 ~ 150 ℃, preferably 60 ~ 90 ℃ are carried out polymerisation 1 ~ 10 hour, preferably 3 ~ 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 acidic molecular sieve of the present invention and resin compounded catalyst.
In the inventive method, the addition of described perforating agent is acidic molecular sieve powder and prepares 30% ~ 60% of polymerization single polymerization monomer gross weight that resin uses.
Described preparation in the polymerization single polymerization monomer that resin uses, one is polymerization single polymerization monomer styrene, another kind of polymerization single polymerization monomer polyene-based compound, and both weight ratios are 2:1 ~ 5:1.
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 acidic molecular sieve powder and prepares 0.5% ~ 2.5% of polymerization single polymerization monomer gross weight that resin uses.When described initator adds and comprise acidic molecular sieve, 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.
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.).
Catalyst of the present invention is applied in the hydration low-carbon alcohols processed, ether catalytic reaction process of the low-carbon alkene of fixed-bed process, and conversion per pass is high, object product yield is high, long service life.
Catalyst of the present invention has following feature:
1, after acidic molecular sieve and resin compounded, hydrothermal stability is greatly improved, and can adapt to low-carbon alkene hydration reaction process conditions, catalyst long service life;
2, after acidic molecular sieve resin molding compound, do not need high temperature (>500 ℃) roasting to remove the pore-foaming agent adding in forming process, only need low temperature (150 ℃ of <) extracting pore-foaming agent, can avoid causing framework of molecular sieve to cave in, fully keep molecular sieve catalytic active;
3, hydration has higher catalytic activity to low-carbon alkene for acidic molecular sieve and resin compounded catalyst, object product is had higher selective.
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.In the present invention, v% is volume fraction, and wt% is mass fraction.
The concrete preparation process of catalyst of the present invention is as follows:
(1), polymerization
In polymeric kettle, add acidic molecular sieve powder, polymerization single polymerization monomer styrene, 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 acidic molecular sieve and resin compounded catalyst intermediate;
(2), solvent extraction activation
Above-mentioned acidic molecular sieve and resin compounded catalyst intermediate are 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 ratio 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 acidic molecular sieve of the present invention and resin compounded catalyst.This catalyst can directly pack the catalytic reaction of carrying out olefin hydration low-carbon alcohols processed, ether in fixed bed reactors into.
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
Get one liter of polymeric kettle, add ZSM-5 molecular sieve 15g, styrene 70g and divinylbenzene 30g, pore creating material liquid wax (C
9-11n-alkane) 60g, after being uniformly mixed, while being warmed up to 75 ℃, add initator benzoyl peroxide 0.7g, continue to be warmed up to 90 ℃ and maintain 90 ℃ of reaction temperatures 6 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyst.Catalyst after polymerization is carried out to broken granulation, and the catalyst obtaining after sieve mesh is 8 ~ 9 object Taylor standard sieve screenings joins in round-bottom reaction flask, adds 1,2-dichloroethanes carries out swelling, wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved swollen 5 hours.Pour out after 1,2-dichloroethanes, then add ethyl acetate to carry out extracting, wherein the volume ratio of ethyl acetate and catalyst is 3:1,55 ℃ of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyst, its physico-chemical property is in table 1.
Embodiment 2
Get one liter of polymeric kettle, add beta-molecular sieve 30g, styrene 70g and divinylbenzene 20g, pore creating material liquid wax 55g, after being uniformly mixed, while being warmed up to 75 ℃, add initator benzoyl peroxide 0.8g, continue to be warmed up to 85 ℃ and maintain 85 ℃ of reaction temperatures 6 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyst.Catalyst after polymerization is carried out to broken granulation, and the catalyst obtaining after sieve mesh is 8 ~ 9 object Taylor standard sieve screenings, joins in round-bottom reaction flask, add 1,2-dichloroethanes to carry out swelling, wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved swollen 5 hours.Pour out after 1,2-dichloroethanes, then add ethyl acetate to carry out extracting, wherein the volume ratio of ethyl acetate and catalyst is 3:1,55 ℃ of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyst, its physico-chemical property is in table 1.
Embodiment 3
Get one liter of polymeric kettle, add Y zeolite 30g, styrene 65g and divinylbenzene 40g, pore creating material liquid wax 60g, after being uniformly mixed, while being warmed up to 70 ℃, add initator azo two isobutanol 1.5g, continue to be warmed up to 80 ℃ and maintain 80 ℃ of reaction temperatures 5 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyst.Catalyst after polymerization is carried out to broken granulation, and the catalyst obtaining after sieve mesh is 8 ~ 9 object Taylor standard sieve screenings, joins in round-bottom reaction flask, add 1,2-dichloroethanes to carry out swelling, wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved swollen 5 hours.Pour out after 1,2-dichloroethanes, then add dimethylbenzene to carry out extracting, wherein the volume ratio of dimethylbenzene and catalyst is 3:1,55 ℃ of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyst, its physico-chemical property is in table 1.
Embodiment 4
Get one liter of polymeric kettle, add MCM-36 15g, styrene 65g and divinylbenzene 15g, pore creating material liquid wax 45g, after being uniformly mixed, while being warmed up to 75 ℃, add initator azo two isobutanol 1.5g, continue to be warmed up to 90 ℃ and maintain 90 ℃ of reaction temperatures 6 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyst.Catalyst after polymerization is carried out to broken granulation, and the catalyst obtaining after sieve mesh is 8 ~ 9 object Taylor standard sieve screenings, joins in round-bottom reaction flask, add 1,2-dichloroethanes to carry out swelling, wherein 1, the volume ratio of 2-dichloroethanes and catalyst is 5:1, dissolved swollen 5 hours.Pour out after 1,2-dichloroethanes, then add dimethylbenzene to carry out extracting, wherein the volume ratio of dimethylbenzene and catalyst is 3:1,55 ℃ of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyst, its physico-chemical property is in table 1.
The character of table 1 embodiment gained catalyst
| ? | Specific surface, m 2/g | Pore volume, cm 3/g | Aperture, dust | Side pressure strength, N/mm |
| Embodiment 1 | 163 | 0.32 | 79 | 12.5 |
| Embodiment 2 | 178 | 0.38 | 70 | 10.8 |
| Embodiment 3 | 152 | 0.29 | 79 | 13.2 |
| Embodiment 4 | 111 | 0.23 | 86 | 12.7 |
Embodiment 5
Catalyst activity evaluation adopts small fixed reactor, and loaded catalyst is 20ml.Raw material butylene purity 95%.The catalyst 20ml that gets embodiment 1 packs diameter 20mm into, in the fixed bed reactors of long 1200mm, carries out butylene hydration reaction, 175 ℃, pressure 8. 0MPa, water/alkene mol ratio 8: 1 and volume space velocity 0.5h
-1time condition under, butylene conversion per pass 30.2%(mole), the selective > 95%(mole of sec-butyl alcohol).This test continuous operation 500 hours, catalyst strength, activity have no decline.
Embodiment 6
The catalyst 20ml that gets embodiment 2 packs diameter 20mm into, in the fixed bed reactors of long 1200mm, carries out propylene hydration reaction, 160 ℃, pressure 7. 0 MPa, water/alkene mol ratio 8: 1 and volume space velocity 0.4h
-1time condition under, propylene conversion per pass 45.5%(mole), the selective > 95%(mole of isopropyl alcohol).This test continuous operation 500 hours, catalyst strength, activity have no decline.
Embodiment 7
The catalyst 20ml that gets embodiment 3 packs diameter 20mm into, in the fixed bed reactors of long 1200mm, carries out propylene etherification reaction take propylene, isopropyl alcohol, water as raw material, at 170 ℃, pressure 7.0MPa, alcohol/alkene mol ratio 1: 1 and LHSV=0.5h
-1condition under, propylene conversion per pass 75.3%(mole), the selective 81.2%(mole of diisopropyl ether).This test continuous operation 500 hours, catalyst strength, activity have no decline.
Embodiment 8
The catalyst 20ml that gets embodiment 4 packs diameter 20mm into, in the fixed bed reactors of long 1200mm, carries out propylene direct hydration etherification reaction take propylene, water as raw material, 165 ℃, pressure 8.0MPa, water/alkene mol ratio 10: 1 and volume space velocity 0.2h
-1time, condition under, propylene conversion per pass 28.1%(mole), the selective 75%(mole of isopropyl alcohol), the selective 23.6%(mole of diisopropyl ether).This test continuous operation 500 hours, catalyst strength, activity have no decline.
Comparative example 1
Get ZSM-5 molecular sieve powder 100g, by ZSM-5:Al (OH)
3: the ratio of sesbania powder=39:15:1 mixes, then uses rare nitric acid furnishing pasty state, is shaped to 2mm strip with banded extruder, dries through 120 ℃, 12h, and 550 ℃ of constant temperature 4h, obtain ZSM-5/Al
2o
3solid catalyst.Recording catalyst side Compressive Strength is 14.8N/mm.Get 20ml and pack diameter 20mm into, in the fixed bed reactors of long 1200mm, carry out butylene hydration reaction take butylene, water as raw material, 175 ℃, pressure 8.0MPa, water/alkene mol ratio 8: 1 and volume space velocity 0.5h
-1time condition under, butylene conversion per pass 29.6%(mole), the selective > 95%(mole of sec-butyl alcohol).Continuous operation 100 hours, there is white powder in product, detecting catalyst side Compressive Strength is 3.8 N/mm, declines 74.3%.
Comparative example 2
Get DNW heatproof cation exchange resin catalyst (butylene hydration catalyst) 50ml and pack diameter 20mm into, the fixed bed reactors of long 1200mm, carry out butylene hydration reaction take butylene, water as raw material, 160 ℃, pressure 8.0MPa, water/alkene mol ratio 8: 1 and volume space velocity 1.0h
-1time condition under, butylene conversion per pass 5.2%(mole), the selective > 95%(mole of sec-butyl alcohol).
Claims (12)
1. acidic molecular sieve and a resin compounded catalyst, take the weight of catalyst as benchmark, the content of acidic molecular sieve is 1%～50%, the content of resin is 50%～99%; Described resin is the polymer of styrene and polyene-based compound, and both weight ratios are 2:1～5:1, and described polyene-based compound is one or more in divinylbenzene, divinyl toluene and biethenyl-xylene;
This catalyst is prepared by following method: by acidic molecular sieve powder, prepare polymerization single polymerization monomer and the perforating agent that resin uses and fully mix, under initator exists, carry out polymerisation 1～10 hour at 20～150 ℃, 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 acidic molecular sieve and resin compounded catalyst; Described perforating agent is gasoline, C
5～C
13n-alkane, C
4～C
12one or more in fatty alcohol; The addition of described perforating agent is acidic molecular sieve powder and prepares 30%～60% of polymerization single polymerization monomer gross weight that resin uses; Described initator is benzoyl peroxide and/or azo two isobutanols; The addition of described initator is acidic molecular sieve powder and prepares 0.5%～2.5% of polymerization single polymerization monomer gross weight that resin uses; Described halogenated hydrocarbons is C
1～C
4halogenated hydrocarbons; Described catalyst and the volume ratio of halogenated hydrocarbons are 1:10～1:1, and swelling time is 3～8 hours; Described extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, butanols, and described extraction solvent and the volume ratio of catalyst are 1:1～5:1; Described extractive reaction temperature is 30～60 ℃; The described extracting time is 2～8 hours, and extracting number of times is 2～5 times.
2. according to catalyst claimed in claim 1, it is characterized in that, take the weight of catalyst as benchmark, the content of acidic molecular sieve is 10%～30%, and the content of resin is 70%～90%.
3. according to catalyst claimed in claim 1, it is characterized in that the character of described catalyst is as follows: specific area is 80～200m
2/ g, pore volume is 0.05～0.50cm
3/ g, side pressure strength is 6～16N/mm.
4. according to catalyst claimed in claim 1, it is characterized in that described acidic molecular sieve is selected from one or more in Si-Al molecular sieve, silicoaluminophosphamolecular molecular sieves.
5. according to catalyst claimed in claim 1, it is characterized in that described acidic molecular sieve is one or more in beta-molecular sieve, ZSM Series Molecules sieve, modenite, faujasite, erionite, A type zeolite, MCM Series Molecules sieve, SAPO Series Molecules sieve.
6. according to catalyst claimed in claim 5, it is characterized in that described ZSM Series Molecules sieve is one or more in ZSM-5, ZSM-8, ZSM-11, ZSM-35, SAPO Series Molecules sieve is one or more in SAPO-5, SAPO-11, and MCM Series Molecules sieve is one or more in MCM-22, MCM-36, MCM-41 molecular sieve.
7. according to catalyst claimed in claim 1, it is characterized in that described acidic molecular sieve is one or more in beta-molecular sieve, ZSM-5 molecular sieve, MCM-36, Y zeolite.
8. according to catalyst claimed in claim 1, it is characterized in that described acidic molecular sieve is one or more in hydrogen type molecular sieve and modified molecular screen, polyvalent cation exchange molecular sieve and modified molecular screen thereof.
9. according to catalyst claimed in claim 1, it is characterized in that described polyene-based compound is divinylbenzene.
10. according to catalyst claimed in claim 1, it is characterized in that described polymeric reaction temperature is 60～90 ℃, the reaction time is 3～6 hours.
11. according to catalyst claimed in claim 1, it is characterized in that described halogenated hydrocarbons is 1,2-dichloroethanes.
12. according to catalyst claimed in claim 1, it is characterized in that described initator add comprise acidic molecular sieve, 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 ℃.
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| CN1555924A (en) * | 2003-12-31 | 2004-12-22 | 沧州市冀中化工厂 | High exchange capacity resin catalyst and its preparation method |
| CN101062958A (en) * | 2006-04-24 | 2007-10-31 | 东丽纤维研究所（中国）有限公司 | Composite material formed of organic polymer and mesoporous molecular sieve and its interface structure and preparation method thereof |
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| CN1555924A (en) * | 2003-12-31 | 2004-12-22 | 沧州市冀中化工厂 | High exchange capacity resin catalyst and its preparation method |
| CN101062958A (en) * | 2006-04-24 | 2007-10-31 | 东丽纤维研究所（中国）有限公司 | Composite material formed of organic polymer and mesoporous molecular sieve and its interface structure and preparation method thereof |
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