CN101805244A - Cyclohexene hydrating process - Google Patents
Cyclohexene hydrating process Download PDFInfo
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- CN101805244A CN101805244A CN201010141909A CN201010141909A CN101805244A CN 101805244 A CN101805244 A CN 101805244A CN 201010141909 A CN201010141909 A CN 201010141909A CN 201010141909 A CN201010141909 A CN 201010141909A CN 101805244 A CN101805244 A CN 101805244A
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- cyclohexene
- hydration
- solid super
- strong acid
- reaction
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 28
- 230000000887 hydrating effect Effects 0.000 title claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 47
- 238000006703 hydration reaction Methods 0.000 claims abstract description 37
- 230000036571 hydration Effects 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 35
- 239000003930 superacid Substances 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000012546 transfer Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005728 strengthening Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 8
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 230000016507 interphase Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000003351 stiffener Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 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 2
- 241000370738 Chlorion Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001935 cyclohexenes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a cyclohexene hydrating process. A solid superacid with the main activity phase of WO3/ZrO2 is used as a catalyst, and the cyclohexene hydration is carried out in the subcritical zone of the water to obtain cyclohexanol. The catalyst can be a WO3/ZrO2 solid superacid which is prepared by a coprecipitation method and has the BET specific surface of 60-80m<2>/g, or a WO3/ZrO2 solid superacid which is prepared by a sol-gel method and has the BET specific surface of 250-400m<2>/g, or a X-WO3/ZrO2 solid superacid with surface modification, wherein X is Pt, Al or Ga. The reaction temperature of the cyclohexene hydration is 200-300 DEG C, the reaction pressure is 15-35Mpa, the volume ratio of water to cyclohexene is 5/1-1/1, and the cyclohexene hydration is carried out in a fixing bed reactor. The invention has the advantages of skillful design and reasonable process, strengthens the cyclohexene hydration process in a high selection way through eliminating transfer between phases, strengthening reaction dynamics, improving thermaldynamical balance, and the like, greatly accelerates the reaction, enhances the hydration efficiency, and is suitable for industrial scale production and large-scale popularization and application.
Description
Technical field
The present invention relates to the synthetic technical field of compound, particularly the hexalin synthesis technical field specifically is meant a kind of cyclohexene hydrating process, is suitable for the reinforcement of cyclohexene hydration process in the hexanolactam industrial chain.
Background technology
The hydration of tetrahydrobenzene is one of core procedure of hexanolactam greenization production, and it can carry out under the effect of catalyzer such as mineral acid, Phenylsulfonic acid, ion exchange resin and molecular sieve.
Philips Petroleum Co. has just reported the cyclohexene hydrating process of employing sulfuric acid as homogeneous catalyst as far back as the forties in 20th century, but this catalyzer has serious corrosive nature and brings environmental issue equipment.
To 80～nineties, Du Pont and Mitsui petrochemical corporation (complex) attempt adopting the hydration of perfluorinated sulfonic acid polymer and strong-acid ion exchange resin catalysis tetrahydrobenzene respectively, also do not have to solve catalyzer selling at exorbitant prices and catalyzer swollen problem.
The industrialization of company of nineteen eighty-three Japan Asahi Chemical Industry by the catalytic liquid-liquid-solid three-phase of high-silica zeolite ZSM-5 cyclohexene hydrating process.In Asahi Chemical Industry's hydrating process, the tetrahydrobenzene in the organic phase at first is dissolved in water, diffuses to the molecular sieve catalyst that is suspended in aqueous phase by liquid-solid mass transfer then and generates the target product hexalin.Be subjected to that tetrahydrobenzene is extremely low in the solubleness of aqueous phase, the strength of acid of high silica ZSM-5 is weak and the influence of composite factor such as thermodynamics equilibrium limit, reaction mass need stop 2h in two series connection slurry reactors just can reach 12.5% tetrahydrobenzene transformation efficiency.
Once had the scholar to attempt adopting phase reaction rectifying to carry out cyclohexene hydration in recent years, analog calculation shows that the transformation efficiency of tetrahydrobenzene can reach 98%.However, practice confirms because the acid catalysis efficient on the rectifiying plate too lowly makes the coupling of rectifying and heterogeneous catalysis cyclohexene hydration to realize.
For the needs that the hexanolactam industry develops in a healthy way, the urgent hope of industry member can be carried out process intensification and require technology to possess green characteristic the hydration of tetrahydrobenzene.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming of the prior art, a kind of cyclohexene hydrating process is provided, this cyclohexene hydrating process design is ingenious, technology is reasonable, from eliminating interphase mass transfer, strengthening reaction kinetics and improve thermodynamic(al)equilibrium equal angles stiffener rings hexene hydro-combination process, accelerate speed of response greatly, improved combined coefficient, be suitable for commercial scale production and large-scale promotion application.
To achieve these goals, cyclohexene hydrating process of the present invention, its principal feature is to adopt main activity to be WO mutually
3/ ZrO
2Solid super-strong acid be catalyzer, obtain hexalin thereby between the close-to-critical range of water, carry out cyclohexene hydration.
Preferably, described solid super-strong acid is that the BET specific surface that is prepared by coprecipitation method is 60～80m
2The WO of/g
3/ ZrO
2Solid super-strong acid.
Preferably, described solid super-strong acid is that the BET specific surface by Prepared by Sol Gel Method is 250～400m
2The mesoporous WO of/g
3/ ZrO
2Solid super-strong acid.
Preferably, described solid super-strong acid is the X-WO through surface modification
3/ ZrO
2Solid super-strong acid, wherein X is Pt, Al or Ga.
Preferably, the temperature of reaction of described cyclohexene hydration is 200～300 ℃, and reaction pressure is 15～35MPa.
Preferably, the volume ratio of described water and described tetrahydrobenzene is 5/1～1/1.
Preferably, described cyclohexene hydration carries out in fixed-bed reactor.
Beneficial effect of the present invention is specific as follows:
1, the present invention adopts WO
3/ ZrO
2The solid super-strong acid that is main active phase is a catalyzer, thereby between the close-to-critical range of water, carry out cyclohexene hydration and obtain hexalin, design ingenious, technology is reasonable, from eliminating interphase mass transfer, strengthening reaction kinetics and improve thermodynamic(al)equilibrium equal angles stiffener rings hexene hydro-combination process, accelerate speed of response greatly, improved combined coefficient, be suitable for commercial scale production and large-scale promotion application.
2, solid super-strong acid of the present invention is WO
3/ ZrO
2Solid super-strong acid and surface modification solid super-strong acid thereof have good hydrothermal stability, have effectively overcome traditional SO
4 2-/ ZrO
2The defective that the solid super-strong acid active ingredient easily runs off has the highly selective katalysis to the cyclohexene hydration that carries out under the high temperature, designs ingenious, technology is reasonable, accelerate speed of response greatly, improved combined coefficient, be suitable for commercial scale production and large-scale promotion application.
3, cyclohexene hydration reaction temperature of the present invention is 200～300 ℃, reaction pressure is 15～35MPa, reacting fluid is in the homogeneous phase attitude mutually in aforesaid operations spatial certain optimisation zone, thereby avoided the constraint of interphase mass transfer to hydration kinetics, system pressure becomes the effective means of regulation and control hexalin balance yield, further accelerate speed of response, improved combined coefficient, be suitable for commercial scale production and large-scale promotion application.
4, the volume ratio of described water of the present invention and described tetrahydrobenzene is 5/1～1/1, input material volume ratio becomes the effective means of regulation and control hexalin balance yield, further accelerate speed of response, improved combined coefficient, be suitable for commercial scale production and large-scale promotion application.
Embodiment
In order more to be expressly understood technology contents of the present invention, describe in detail especially exemplified by following examples.
Embodiment 1:
With the ammonium metawolframate is the W source, and zirconium oxychloride is the Zr source, by the synthetic WO of co-precipitation
3/ ZrO
2Solid super acid catalyst.A certain amount of zirconium oxychloride is dissolved in the water, is added dropwise to the NH of 30wt.% concentration then
3Water is 10 and at 100 ℃ of backflow 24h until pH value of solution.Gained suspension is through washing centrifugal acquisition Zr (OH) behind no chlorion
4Carrier is immediately 105 ℃ of oven dry.Zr (OH)
4After powder adds certain density ammonium metatungstate solution, the slow evaporation under 80-95 ℃ of condition of this suspension is carried on Zr (OH) until all ammonium metawolframates
4Carrier.Catalyst precursor after the load finally obtains WO behind 700 ℃ of roasting 5h
3/ ZrO
2Solid super-strong acid, the BET specific surface of this catalyzer is 65m
2/ g.WO wherein
3Content in catalyzer is according to ammonium metawolframate and ZrOCl
2Not coexisting of proportioning changes between 8.0～17.5wt.%.Solid super-strong acid through compressing tablet, pulverize, sieving obtains being packed into the fixed bed reaction pipe behind the 40 purpose particles.
Hydration reaction is carried out in fixed-bed reactor.Operational condition is as follows: 250 ℃ of temperature; Pressure 25MPa; Feed water/tetrahydrobenzene volume ratio 4/1; Reaction mass is at the residence time of beds 60s.The once through yield of hexalin reaches 9.8%, fails obviously to detect by products such as methyl cyclopentene in the product.
Embodiment 2:
With the ammonium metawolframate is the W source, and zirconium iso-propoxide is the Zr source, and cetyl trimethylammonium bromide (CTAB) passes through the synthesising mesoporous WO of sol-gel method for template
3/ ZrO
2Solid super acid catalyst.At first, add zirconium iso-propoxide and ammonium metawolframate then simultaneously and continue to stir 5h at 40 ℃ of certain density CTAB transparent micro emulsions of preparation.About the pH value to 10 of regulator solution, the mol ratio of zirconium iso-propoxide and CTAB is controlled at 1.0～1.2 in this process.The gained gel obtains mesoporous WO at 700 ℃ of roasting 5h immediately behind crystallization 24h under 80 ℃ of conditions
3/ ZrO
2Solid super acid catalyst.The BET specific surface of this solid super acid catalyst is 250m
2About/g, mean pore size 6.5nm.WO
3Content in catalyzer changes between 7.0～15.0wt.% according to not coexisting of zirconium iso-propoxide and ammonium metawolframate usage quantity.Catalyzer through compressing tablet, pulverize, sieving obtains being packed into the fixed bed reaction pipe behind the 40 purpose particles.
Hydration reaction is carried out in fixed-bed reactor.Operational condition is as follows: 300 ℃ of temperature; Pressure 15MPa; Feed water/tetrahydrobenzene volume ratio 5/1; Reaction mass is at the residence time of beds 30s.The once through yield of hexalin reaches 10.3%, fails obviously to detect by products such as methyl cyclopentene in the product.
Embodiment 3:
With the ammonium metawolframate is the W source, and zirconium iso-propoxide is the Zr source, and cetyl trimethylammonium bromide (CTAB) passes through the synthesising mesoporous WO of sol-gel method for template
3/ ZrO
2Solid super acid catalyst.At first, add zirconium iso-propoxide and ammonium metawolframate then simultaneously and continue to stir 5h at 40 ℃ of certain density CTAB transparent micro emulsions of preparation.About the pH value to 10 of regulator solution, the mol ratio of zirconium iso-propoxide and CTAB is controlled at 0.8～1.0 in this process.The gained gel obtains mesoporous WO at 750 ℃ of roasting 5h immediately behind crystallization 24h under 80 ℃ of conditions
3/ ZrO
2Solid super acid catalyst.The BET specific surface of this solid super acid catalyst is 395m
2About/g, mean pore size 5.5nm.WO
3Content in catalyzer changes between 7.0～15.0wt.% according to not coexisting of zirconium iso-propoxide and ammonium metawolframate usage quantity.Catalyzer through compressing tablet, pulverize, sieving obtains being packed into the fixed bed reaction pipe behind the 40 purpose particles.
Hydration reaction is carried out in fixed-bed reactor.Operational condition is as follows: 275 ℃ of temperature; Pressure 20MPa; Feed water/tetrahydrobenzene volume ratio 4/1; Reaction mass is at the residence time of beds 35s.The once through yield of hexalin reaches 10.5%, fails obviously to detect by products such as methyl cyclopentene in the product.
Embodiment 4:
With the ammonium metawolframate is the W source, and zirconium oxychloride is the Zr source, and gallium nitrate is as the Ga source, by the synthetic Ga-WO of co-precipitation
3/ ZrO
2Solid super acid catalyst.At first a certain amount of zirconium oxychloride is dissolved in the water, is added dropwise to the NH of 30% concentration then
3Water is 10 and at 100 ℃ of following backflow 24h until pH value of solution.Gained suspension is through washing centrifugal acquisition Zr (OH) behind no chlorion
4Carrier is immediately 105 ℃ of oven dry.Zr (OH)
4After powder adds certain density ammonium metawolframate and gallium nitrate mixing solutions, with this suspension slow evaporate to dryness under 80～95 ℃ of conditions.Catalyst precursor after the load finally obtains Ga-WO behind 700 ℃ of roasting 5h
3/ ZrO
2Solid super acid catalyst, wherein WO
3Content in catalyzer changes between 8.5～17.0wt.%, and the concentration of Ga in catalyzer is controlled at 0.5～1.0wt.%.Solid super-strong acid through compressing tablet, pulverize, sieving obtains being packed into the fixed bed reaction pipe behind the 40 purpose particles.
Hydration reaction is carried out in fixed-bed reactor.Operational condition is as follows: 200 ℃ of temperature; Pressure 35MPa; Feed water/tetrahydrobenzene volume ratio 1/1; Reaction mass is at the residence time of beds 45s.The once through yield of hexalin reaches 9.7%, fails obviously to detect by products such as methyl cyclopentene in the product.
Simultaneously, in the present invention, realize that the key of tetrahydrobenzene efficient green hydration is: eliminate mass transfer between the liquid liquid phase; The strengthening surface reaction; The restriction of breakthrough molecular balance.And the expansion of foregoing is based on following 2 points:
● the multi-element fluid in the cyclohexene hydration system in the Asia (surpassing) of water the ceitical region can be in homogeneous phase or thus the partial miscibility state has been eliminated original liquid liquid mass transfer limit.Be that with the important difference of traditional hydration the raw materials components mole ratio of water/tetrahydrobenzene and system pressure become the effective means of regulating ring hexene equilibrium conversion under the high temperature homogeneous state.Only from eliminating this unitary request of mass transfer between the liquid liquid phase, the operating point of cyclohexene hydration should be to the supercritical water zone migration.Behind further comprehensive this particular case of hydration exothermic nature, hydration operates in the subcritical water zone and then has more advantage.
● WO
3/ ZrO
2And the surface modification solid super-strong acid has good hydrothermal stability, its H
0Value can reach-14.The acid site on these super acids surfaces can show as simple Lewis acid,
Sour and compound acid site.WO
3/ ZrO
2The appearance of super acids has effectively overcome traditional SO
4 2-/ ZrO
2The defective that the solid super-strong acid active ingredient easily runs off is attempted being applied to essential industry catalyst system such as nitrated, alkylation.Active exploration experiment of the present invention shows WO
3/ ZrO
2The series solid super-strong acid has the highly selective katalysis to the cyclohexene hydration that carries out under the high temperature.
Therefore, the present invention utilizes WO
3/ ZrO
2Solid super-strong acid and surface modification solid super-strong acid thereof carry out cyclohexene hydration and obtain hexalin as catalyzer between the close-to-critical range of water.In the method, to load on ZrO
2On WO
3As main catalytic active phase, wherein carrier ZrO
2Has tetragonal crystal structure.WO
3/ ZrO
2The Prepared by Sol Gel Method that catalyzer can adopt coprecipitation method or template to get involved.Adopt by some metallic element WO
3/ ZrO
2Carry out surface modification and can form X-WO
3/ ZrO
2(X=Pt, Ga, Al etc.) solid super acid catalyst.
The hydration reaction of tetrahydrobenzene operates between the close-to-critical range of water, and its temperature of reaction is 200～300 ℃, and pressure is 15～35MPa, and the volume ratio of feed water/tetrahydrobenzene is 5/1～1/1.The cyclohexene hydration of solid superacid as catalyst can be implemented in the isothermal fixed-bed reactor.Raw material tetrahydrobenzene and water are through entering beds and carry out hydration reaction at the solid super strong acid surfaces after the preheating respectively.Usually reaction mass stops 30～60s at beds and can reach tetrahydrobenzene transformation efficiency about 10.0%, and to the selectivity of hexalin greater than 99.0%.
Thereby, between hydration operating point migration the close-to-critical range as for water of the present invention, and introduce for example WO of solid super-strong acid with tetrahydrobenzene
3/ ZrO
2The series solid super-strong acid is as catalyzer.From eliminating interphase mass transfer, strengthening reaction kinetics and improve thermodynamic(al)equilibrium equal angles stiffener rings hexene hydro-combination process.
To sum up, cyclohexene hydrating process design of the present invention is ingenious, technology is reasonable, from eliminating interphase mass transfer, strengthening reaction kinetics and improve thermodynamic(al)equilibrium equal angles stiffener rings hexene hydro-combination process, accelerated speed of response greatly, improve combined coefficient, be suitable for commercial scale production and large-scale promotion application.
In this specification sheets, the present invention is described with reference to its certain embodiments.But, still can make various modifications and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, specification sheets and accompanying drawing are regarded in an illustrative, rather than a restrictive.
Claims (7)
1. a cyclohexene hydrating process is characterized in that, adopts main activity to be WO mutually
3/ ZrO
2Solid super-strong acid be catalyzer, obtain hexalin thereby between the close-to-critical range of water, carry out cyclohexene hydration.
2. cyclohexene hydrating process according to claim 1 is characterized in that, described solid super-strong acid is that the BET specific surface that is prepared by coprecipitation method is 60～80m
2The WO of/g
3/ ZrO
2Solid super-strong acid.
3. cyclohexene hydrating process according to claim 1 is characterized in that, described solid super-strong acid is that the BET specific surface by Prepared by Sol Gel Method is 250～400m
2The mesoporous WO of/g
3/ ZrO
2Solid super-strong acid.
4. cyclohexene hydrating process according to claim 1 is characterized in that, described solid super-strong acid is the X-WO through surface modification
3/ ZrO
2Solid super-strong acid, wherein X is Pt, Al or Ga.
5. cyclohexene hydrating process according to claim 1 is characterized in that, the temperature of reaction of described cyclohexene hydration is 200～300 ℃, and reaction pressure is 15～35MPa.
6. cyclohexene hydrating process according to claim 1 is characterized in that, the volume ratio of described water and described tetrahydrobenzene is 5/1～1/1.
7. cyclohexene hydrating process according to claim 1 is characterized in that described cyclohexene hydration carries out in fixed-bed reactor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010141909 CN101805244B (en) | 2010-04-08 | 2010-04-08 | Cyclohexene hydrating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010141909 CN101805244B (en) | 2010-04-08 | 2010-04-08 | Cyclohexene hydrating process |
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| Publication Number | Publication Date |
|---|---|
| CN101805244A true CN101805244A (en) | 2010-08-18 |
| CN101805244B CN101805244B (en) | 2013-06-26 |
Family
ID=42607217
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|---|---|---|---|
| CN 201010141909 Expired - Fee Related CN101805244B (en) | 2010-04-08 | 2010-04-08 | Cyclohexene hydrating process |
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| Country | Link |
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Cited By (5)
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| CN101979136A (en) * | 2010-11-12 | 2011-02-23 | 中国科学院上海硅酸盐研究所 | Mesoporous composite oxide type solid super acidic catalyst and preparation method thereof |
| CN102259025A (en) * | 2011-06-10 | 2011-11-30 | 河北工业大学 | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof |
| CN103787836A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Cyclopentene hydration method for preparing cyclopentanol |
| WO2016011970A1 (en) * | 2014-07-25 | 2016-01-28 | 苏州汉瀚储能科技有限公司 | Use of tungsten-containing material |
| CN108212205A (en) * | 2018-01-23 | 2018-06-29 | 山东亚科环保科技有限公司 | A kind of cyclohexene prepares the preparation method and applications of cyclohexanol catalyst |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979136A (en) * | 2010-11-12 | 2011-02-23 | 中国科学院上海硅酸盐研究所 | Mesoporous composite oxide type solid super acidic catalyst and preparation method thereof |
| CN101979136B (en) * | 2010-11-12 | 2012-10-31 | 中国科学院上海硅酸盐研究所 | Mesoporous composite oxide type solid super acidic catalyst and preparation method thereof |
| CN102259025A (en) * | 2011-06-10 | 2011-11-30 | 河北工业大学 | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof |
| CN102259025B (en) * | 2011-06-10 | 2013-12-18 | 河北工业大学 | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof |
| CN103787836A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Cyclopentene hydration method for preparing cyclopentanol |
| CN103787836B (en) * | 2012-11-01 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene |
| WO2016011970A1 (en) * | 2014-07-25 | 2016-01-28 | 苏州汉瀚储能科技有限公司 | Use of tungsten-containing material |
| CN108212205A (en) * | 2018-01-23 | 2018-06-29 | 山东亚科环保科技有限公司 | A kind of cyclohexene prepares the preparation method and applications of cyclohexanol catalyst |
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