CN102757309B - Alkene hydration method - Google Patents
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Abstract
The invention discloses an alkene hydration method. According to the invention, a fixed bed reactor is adopted, and under the existences of an acidic molecular sieve and resin composite catalyst, alkene and water are subjected to a hydration reaction; an obtained product is separated, and alcohol is obtained. 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 acidic molecular sieve and resin composite catalyst, a problem of poor hydro-thermal stability of a molecular sieve catalyst is solved, and catalyst service life is prolonged. With the method, the alkene conversion per pass is high, and a target product yield is high.
Description
Technical field
The present invention relates to a kind of method of olefin hydration, particularly adopt the low-carbon alkene hydration method of low-carbon alcohol processed continuously.
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, Virahol, 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 catalyzer is generally sulfuric acid and phosphoric acid, because above-mentioned two kinds of catalyzer exist the problems such as burn into loss, is progressively replaced by zeolite catalyst and strong resin catalyzer 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 throughput is low, and make each research institution of the world be devoted to develop low-carbon alkene hydration zeolite catalyst.
Relevant zeolite [molecular sieve 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 Virahol/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 conditions, 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 conditions, catalyst strength is subject to hydrothermal condition to affect decline rapidly, has limited the realization of its industrial application.
CN1245738A discloses the method for a kind of low-carbon alkene hydration low-carbon alcohol processed.The catalyzer 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; Catalyzer consists of (weight percent) modifying element 1 wt% ~ 5wt%, beta-zeolite molecular sieve 40 wt% ~ 80 wt %, binding agent surplus.It is binding agent that the method adopts silicon sol, clay, aluminium hydroxide etc., and the catalyzer hydrothermal stability of preparation is poor, and under olefin hydration reaction conditions, strength degradation is too fast, is difficult to realize industrial application.
CN1872826A discloses a kind of method of continuous production lower alcohol, adopt hydrating process, 80～200 DEG C of temperature of reaction, reaction pressure 4.0～20.0MPa, solid acid catalyst adopts Zeo-karb, low-carbon alkene catalytic hydration is become to low-carbon alcohol, and the alcohol in reaction after product is separated.Catalyzing cation exchange resin olefin hydration per pass conversion 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.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of method of olefin hydration.The method adopts fixed-bed reactor, and the per pass conversion of alkene is high, object product yield is high, catalyzer good hydrothermal stability, long service life.
The method of olefin hydration of the present invention, adopts fixed-bed reactor, under catalyzer exists, and alkene and water generation hydration reaction, products therefrom is isolated to alcohol; Described catalyzer is acidic molecular sieve and resin compounded catalyzer, and taking the weight of catalyzer as benchmark, the content of acidic molecular sieve is 1% ~ 50%, is preferably 10% ~ 30%, and the content of resin is 50% ~ 99%, is preferably 70% ~ 90%.
The character of described acidic molecular sieve and resin compounded catalyzer is as follows: specific surface 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, mordenite, faujusite, 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 cationic 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 polymkeric substance of vinylbenzene 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 the present invention's acidic molecular sieve used and resin compounded catalyzer, comprising:
By acidic molecular sieve powder, prepare polymerization single polymerization monomer and the perforating agent that resin uses and fully mix, under initiator exists, at 20 ~ 150 DEG C, preferably 60 ~ 90 DEG C are carried out polyreaction 1 ~ 10 hour, preferably 3 ~ 6 hours, obtain blocks of solid catalyzer; Then be processed into catalyst solid particle, by above-mentioned catalyst solid particle be added to swelling in halohydrocarbon after, adopt solvent extraction, obtain acidic molecular sieve of the present invention and resin compounded catalyzer.
In the preparation method of used catalyst of the present invention, the add-on of described perforating agent is acidic molecular sieve powder and prepares 30% ~ 60% of polymerization single polymerization monomer gross weight that resin uses.Described perforating agent can be gasoline, C
5~ C
13normal paraffin, C
4~ C
12one or more in fatty alcohol, preferably C
5~ C
13one or more in normal paraffin.
Described preparation in the polymerization single polymerization monomer that resin uses, one is polymerization single polymerization monomer vinylbenzene, 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 initiator can be benzoyl peroxide and/or azo two isopropylcarbinols, and add-on is acidic molecular sieve powder and prepares 0.5% ~ 2.5% of polymerization single polymerization monomer gross weight that resin uses.
When described initiator 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 DEG C.
Described halohydrocarbon can be C
1~ C
4halohydrocarbon, wherein preferably 1,2-ethylene dichloride, 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, butylacetate, ethanol, butanols etc.Described extractive reaction temperature is 30 ~ 60 DEG C, preferably 50 ~ 60 DEG C; The described extracting time is 2 ~ 8 hours, preferably 4 ~ 6 hours.
The described method that blocks of solid catalyzer is processed into catalyst solid particle, can adopt crush method, can also adopt patterning method etc., blocks of solid catalyzer is processed into the catalyst solid particle of suitable size and shape (as stripe shape, spherical, class is spherical etc.).
In the method for olefin hydration of the present invention, alkene generally adopts low-carbon alkene, and carbonatoms is 2 ~ 5, and product obtains corresponding low-carbon alcohol, and alkene is preferably propylene or butylene, and corresponding alcohol is Virahol or sec-butyl alcohol.The operational condition of described olefin hydration is as follows: temperature of reaction is 80～200 DEG C, is preferably 130～180 DEG C; Pressure 2 ~ 20MPa, is preferably 6～8MPa; Water/alkene mol ratio 0.1 ~ 30.0, is preferably 6.0～10.0; Alkene volume space velocity 0.1 ~ 2.0 h
– 1, be preferably 0.2～1.0h
– 1.
The hydration low-carbon alcohol catalytic reaction process processed of low-carbon alkene of the present invention adopts acidic molecular sieve and resin compounded catalyzer, and adopts fixed-bed process, and per pass conversion is high, object product yield is high, long service life.
The inventive method adopts acidic molecular sieve and resin compounded catalyzer, 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 processing condition, catalyzer long service life;
2, after acidic molecular sieve and resin molding compound, do not need high temperature (>500 DEG C) roasting to remove the pore-creating agent adding in moulding process, only need low temperature (150 DEG C of <) extracting pore-creating 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 catalyzer, and object product is had to higher selectivity.
Embodiment
Specific surface 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 determinator to measure.Described particle diameter is to adopt U.S.'s Tyler standard sieve (Tyler standard sieve series) to measure.In the present invention, v% is volume fraction, and wt% is massfraction.
The concrete preparation process of the present invention's acidic molecular sieve used and resin compounded catalyzer is as follows:
(1), polymerization
In polymeric kettle, add acidic molecular sieve powder, polymerization single polymerization monomer vinylbenzene, polymerization single polymerization monomer polyene-based compound, perforating agent, after being uniformly mixed, warming-in-water, while being preferably in 60 ~ 90 DEG C, add initiator, at 60 ~ 150 DEG C, carry out polyreaction 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 catalyzer obtaining after sieve mesh is 4 ~ 16 object Tyler standard sieve screenings, add halohydrocarbon to carry out swelling, the volume of catalyzer and halohydrocarbon is 1:10 ~ 1:1, dissolved swollen 3 ~ 8 hours, pour out after halohydrocarbon, add again extraction solvent to carry out extracting, it is that the volume ratio of extraction solvent and catalyzer is 1:1 ~ 5:1, 30 ~ 60 DEG C 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 catalyzer.This catalyzer can directly pack the catalyzed reaction of carrying out olefin hydration low-carbon alcohol processed in fixed-bed reactor 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 specification sheets 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, vinylbenzene 70g and divinylbenzene 30g, pore-forming material liquid wax (C
9-11normal paraffin) 60g, after being uniformly mixed, while being warmed up to 75 DEG C, add initiator benzoyl peroxide 0.7g, continue to be warmed up to 90 DEG C and maintain 90 DEG C of temperature of reaction 6 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyzer.Catalyzer after polymerization is carried out to broken granulation, and the catalyzer obtaining after sieve mesh is 8 ~ 9 object Tyler standard sieve screenings joins in round-bottom reaction flask, adds 1,2-ethylene dichloride carries out swelling, wherein 1, the volume ratio of 2-ethylene dichloride and catalyzer is 5:1, dissolved swollen 5 hours.Pour out after 1,2-ethylene dichloride, then add ethyl acetate to carry out extracting, wherein the volume ratio of ethyl acetate and catalyzer is 3:1,55 DEG C of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyzer, its physico-chemical property is in table 1.
embodiment 2
Get one liter of polymeric kettle, add beta-molecular sieve 30g, vinylbenzene 70g and divinylbenzene 20g, pore-forming material liquid wax 55g, after being uniformly mixed, while being warmed up to 75 DEG C, add initiator benzoyl peroxide 0.8g, continue to be warmed up to 85 DEG C and maintain 85 DEG C of temperature of reaction 6 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyzer.Catalyzer after polymerization is carried out to broken granulation, and the catalyzer obtaining after sieve mesh is 8 ~ 9 object Tyler standard sieve screenings, joins in round-bottom reaction flask, add 1,2-ethylene dichloride to carry out swelling, wherein 1, the volume ratio of 2-ethylene dichloride and catalyzer is 5:1, dissolved swollen 5 hours.Pour out after 1,2-ethylene dichloride, then add ethyl acetate to carry out extracting, wherein the volume ratio of ethyl acetate and catalyzer is 3:1,55 DEG C of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyzer, its physico-chemical property is in table 1.
embodiment 3
Get one liter of polymeric kettle, add Y zeolite 30g, vinylbenzene 65g and divinylbenzene 40g, pore-forming material liquid wax 60g, after being uniformly mixed, while being warmed up to 70 DEG C, add initiator azo two isopropylcarbinol 1.5g, continue to be warmed up to 80 DEG C and maintain 80 DEG C of temperature of reaction 5 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyzer.Catalyzer after polymerization is carried out to broken granulation, and the catalyzer obtaining after sieve mesh is 8 ~ 9 object Tyler standard sieve screenings, joins in round-bottom reaction flask, add 1,2-ethylene dichloride to carry out swelling, wherein 1, the volume ratio of 2-ethylene dichloride and catalyzer is 5:1, dissolved swollen 5 hours.Pour out after 1,2-ethylene dichloride, then add dimethylbenzene to carry out extracting, wherein the volume ratio of dimethylbenzene and catalyzer is 3:1,55 DEG C of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyzer, its physico-chemical property is in table 1.
embodiment 4
Get one liter of polymeric kettle, add MCM-36 15g, vinylbenzene 65g and divinylbenzene 15g, pore-forming material liquid wax 45g, after being uniformly mixed, while being warmed up to 75 DEG C, add initiator azo two isopropylcarbinol 1.5g, continue to be warmed up to 90 DEG C and maintain 90 DEG C of temperature of reaction 6 hours, polymerization finishes to obtain block acidic molecular sieve and resin compounded catalyzer.Catalyzer after polymerization is carried out to broken granulation, and the catalyzer obtaining after sieve mesh is 8 ~ 9 object Tyler standard sieve screenings, joins in round-bottom reaction flask, add 1,2-ethylene dichloride to carry out swelling, wherein 1, the volume ratio of 2-ethylene dichloride and catalyzer is 5:1, dissolved swollen 5 hours.Pour out after 1,2-ethylene dichloride, then add dimethylbenzene to carry out extracting, wherein the volume ratio of dimethylbenzene and catalyzer is 3:1,55 DEG C of extractive reaction temperature, and 4 hours extracting time, same method carries out three extractings.Obtain activating complete molecular sieve and resin compounded catalyzer, its physico-chemical property is in table 1.
The character of table 1 embodiment gained catalyzer
| ? | 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 ~ 8
Catalyst activity evaluation adopts small fixed reactor, and loaded catalyst is 20ml.Raw material butylene purity 95v%.The catalyzer 20ml that gets respectively embodiment 1 ~ 4 packs diameter 20mm into, in the fixed-bed reactor of long 1200mm, carries out butylene hydration reaction, reaction conditions and the results are shown in Table 2.Above-mentioned catalyzer 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 DEG C, 12h, and 550 DEG C of constant temperature 4h, obtain ZSM-5/Al
2o
3solid catalyst.Recording catalyst strength is 14.8N/mm.Get 20ml and pack diameter 20mm into, in the fixed-bed reactor of long 1200mm, carry out butylene hydration reaction taking butylene, water as raw material, 175 DEG C, pressure 8. 0 MPa, water/alkene mol ratio 8: 1 and volume space velocity 0. 5 h
-1time condition under, butylene per pass conversion 29.6%(mole), sec-butyl alcohol selectivity > 95%(mole).Continuous operation 100 hours, there is white powder in reaction product, detecting catalyst strength is 3.8 N/mm, declines 74.3%.
comparative example 2
Get DNW heatproof cation exchange resin catalyst (butylene hydration catalyzer) 50ml and pack diameter 20mm into, the fixed-bed reactor of long 1200mm, carry out butylene hydration reaction taking butylene, water as raw material, 160 DEG C, pressure 8.0MPa, water/alkene mol ratio 8: 1 and volume space velocity 1.0 h
-1time condition under, butylene per pass conversion 5.2%(mole), sec-butyl alcohol selectivity > 95%(mole).
Table 2 olefin hydration reaction result
| ? | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | Comparative example 2 |
| Catalyzer | A | B | C | D | E | F |
| Raw material | Butylene | Propylene | Propylene | Propylene | Butylene | Butylene |
| Operational condition | ? | ? | ? | ? | ? | ? |
| Temperature of reaction, DEG C | 175 | 160 | 175 | 165 | 175 | 160 |
| Pressure, MPa | 8. 0 | 7.0 | 3.5 | 7. 0 | 8.0 | 8.0 |
| Alkene volume space velocity, h -1 | 0.5 | 0.3 | 0.8 | 0.2 | 0.5 | 1.0 |
| The mol ratio of water and alkene | 8∶1 | 6∶1 | 10∶1 | 10∶1 | 8∶1 | 8∶1 |
| Reaction result | ? | ? | ? | ? | ? | ? |
| Alkene per pass conversion, % (mole) | 30.2 | 65.5 | 58.2 | 28.1 | 29.6 | 5.2 |
| The selectivity of object product *, %(mole) | 96.1 | 95.5 | 95.2 | 98.6 | 97.0 | 98.5 |
* note: the object product of butylene hydration reaction gained is sec-butyl alcohol, the object product of propylene hydration reaction gained is Virahol.
Claims (11)
1. a method for olefin hydration, adopts fixed-bed reactor, under catalyzer exists, and alkene and water generation hydration reaction, products therefrom is isolated to alcohol, and wherein alkene is propylene or butylene, and obtaining corresponding product is Virahol or sec-butyl alcohol; Described catalyzer is acidic molecular sieve and resin compounded catalyzer, and taking the weight of catalyzer as benchmark, the content of acidic molecular sieve is 1%～50%, and the content of resin is 50%～99%; Described resin is the polymkeric substance of vinylbenzene and polyene-based compound, and both weight ratios are 2:1～5:1; Described polyene-based compound is one or more in divinylbenzene, divinyl toluene and biethenyl-xylene;
Described acidic molecular sieve and resin compounded catalyzer are prepared by following method, specific as follows:
By acidic molecular sieve powder, prepare polymerization single polymerization monomer and the perforating agent that resin uses and fully mix, under initiator exists, carry out polyreaction 1～10 hour at 20～150 DEG C, obtain blocks of solid catalyzer; Then be processed into catalyst solid particle, by above-mentioned catalyst solid particle be added to swelling in halohydrocarbon after, adopt solvent extraction, obtain acidic molecular sieve and resin compounded catalyzer; Described perforating agent is gasoline, C
5～C
13normal paraffin, C
4～C
12one or more in fatty alcohol; The add-on of described perforating agent is acidic molecular sieve powder and prepares 30%～60% of polymerization single polymerization monomer gross weight that resin uses; Described initiator is benzoyl peroxide, and the add-on of described initiator is acidic molecular sieve powder and prepares 0.5%～2.5% of polymerization single polymerization monomer gross weight that resin uses; Described halohydrocarbon is 1,2-ethylene dichloride, and described catalyzer and the volume of halohydrocarbon are 1:10～1:1, and swelling time is 3～8 hours; The solvent that described solvent extraction adopts is one or more in benzene,toluene,xylene, ethyl acetate, butylacetate, ethanol, butanols, and the solvent that described solvent extraction adopts and the volume ratio of catalyzer are 1:1～5:1; The temperature of reaction of described solvent extraction is 30～60 DEG C, and the extracting time is 2～8 hours, and extracting number of times is 2～5 times;
The operational condition of described olefin hydration is as follows: temperature of reaction is 80～200 DEG C, pressure 2～20MPa, water/alkene mol ratio 0.1～30.0, alkene volume space velocity 0.1～1.5h
– 1.
2. in accordance with the method for claim 1, it is characterized in that, taking the weight of catalyzer as benchmark, the content of acidic molecular sieve is 10%～30%, and the content of resin is 70%～90%.
3. in accordance with the method for claim 1, it is characterized in that the character of described catalyzer is as follows: specific surface area is 80～200m
2/ g, pore volume is 0.05～0.50cm
3/ g, side pressure strength is 6～16N/mm.
4. in accordance with the method for 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. in accordance with the method for claim 1, it is characterized in that described acidic molecular sieve is one or more in beta-molecular sieve, ZSM Series Molecules sieve, mordenite, faujusite, erionite, A type zeolite, MCM Series Molecules sieve, SAPO Series Molecules sieve.
6. in accordance with the method for 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. in accordance with the method for 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. in accordance with the method for 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. in accordance with the method for claim 1, it is characterized in that described polyene-based compound is divinylbenzene.
10. in accordance with the method for claim 1, it is characterized in that described initiator 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 DEG C.
11. in accordance with the method for claim 1, it is characterized in that the operational condition of described olefin hydration is as follows: temperature of reaction is 120～170 DEG C, pressure 6～8MPa, and water/alkene mol ratio is 6.0～12.0, alkene volume space velocity 0.2～1.2h
– 1.
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2011
- 2011-04-26 CN CN201110105058.9A patent/CN102757309B/en active Active
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|---|---|---|---|---|
| US5012014A (en) * | 1990-04-26 | 1991-04-30 | Mobil Oil Corporation | Catalyst pretreatment for olefin hydration |
| CN1670006A (en) * | 2004-03-15 | 2005-09-21 | 中国科学院大连化学物理研究所 | Process for producing lower alcohol by direct hydration of low carbon olefin |
| CN1872826A (en) * | 2005-05-31 | 2006-12-06 | 中国科学院大连化学物理研究所 | Method for producing lower alcohol continuously |
| CN101961660A (en) * | 2010-10-08 | 2011-02-02 | 同济大学 | Porous hybrid-resin solid acid catalyst and preparation method thereof |
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| Title |
|---|
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