CN105585451B - A kind of method that cyclopentene direct hydration prepares cyclopentanol - Google Patents
A kind of method that cyclopentene direct hydration prepares cyclopentanol Download PDFInfo
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- CN105585451B CN105585451B CN201410566284.0A CN201410566284A CN105585451B CN 105585451 B CN105585451 B CN 105585451B CN 201410566284 A CN201410566284 A CN 201410566284A CN 105585451 B CN105585451 B CN 105585451B
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Abstract
The invention belongs to field of chemical technology, specially a kind of method that cyclopentene direct hydration prepares cyclopentanol.The present invention is by continuing through the fixed bed progress hydration reaction of loading catalyst for the material of cyclopentene, water, mixed solvent composition, wherein the mixed solvent is (0.5~1.5) by weight ratio: 1 o-nitrophenol and alcohol forms, after hydration reaction, reactant is cooling to be layered as oily phase and water phase, rectifying under oil phase material normal pressure, 38~55 DEG C of fraction condenses to obtain unreacted cyclopentene, 105~120 DEG C of fraction condenses to obtain solvent, and 135~165 DEG C of fraction condensation, which is collected, obtains purification cyclopentanol.The conversion ratio of cyclopentene is higher in the present invention, and solvent is more stable, is hydrated cyclopentene and solvent in cyclopentanol preparation process and side reaction does not occur substantially and generate by-product, makes that the purification of cyclopentanol is more easy, energy consumption more saves.
Description
Technical field
The present invention relates to a kind of production methods of cyclopentanol.In particular to it is prepared in a kind of industry by cyclopentene direct hydration
The method of cyclopentanol.
Background technique
Cyclopentanol is colourless viscous liquid, has armaticity smell, is the important medicine of one kind, pesticide fine chemical product
Intermediate, mainly for the preparation of products such as bromocyclopentane, chlorocyclopentane, antimicrobial, antiallergics；Additionally due to it is to each
Kind resin has good solubility property, is used widely in electronics industry as solvent.Traditional cyclopentanol production is main
Obtained after cyclopentanone repeated hydrogenation is made in high temperature decarboxylation using adipic acid as raw material, but due to generate a large amount of pollutant and by
To the restriction of raw material sources, limits the technique and further develop.In recent years, since C5 olefine fraction is from a wealth of sources, price
It is cheap, the great interest of people is caused using the research that C 5 fraction produces cyclopentanol as raw material.Water receiving between wherein cyclopentene can pass through
It closes or directly water to close prepares cyclopentanol, although the advantage that indirect hydration method has high conversion rate, selectivity good, sulfuric acid is to setting
Standby seriously corroded, energy consumption is high for concentration process when retrieval of sulfuric acid is applied；Although and direct hydration method conversion ratio is lower, solves and sets
The problem of energy consumption is high for burn into, has been to be concerned by more and more people.
Since hydration of cyclopentene is reacted by mass transport limitation, mass transfer rate depends primarily on catalyst surface and is formed by hydrone
Thickness of liquid film, and thickness of liquid film is related with the sulfonic group concentration of resin surface, and concentration is higher, and liquid film is thicker, then cyclopentene passes through
Liquid-film resistance is bigger, and reaction rate is slower, on the contrary then rate is faster.In the case where not adding any solvent, cyclopentene is in water
Solubility it is very low, the molecule of the two cannot be contacted sufficiently with catalyst surface so that reaction be not easy to positive direction carry out, conversion
Rate is very low.Therefore, make cyclopentene by adding a certain amount of and affinity solvent of cyclopentanol in existing special technology
Intersolubility between hydrone increases, and improves the conversion ratio of reaction.
Currently available technology generally makees solvent with phenol, pure and mild ethers, such as makees solvent using phenol, yield 17% with
On, hence it is evident that it is higher than other solvents, in addition also it has been reported that making solvent using alcohol, yield is 10% or so, and selectivity is 95%
Left and right.Existing method such as makees solvent using phenol there are apparent defect, due to cyclopentene and phenol occur alkylated reaction and
Cyclopentanol and phenol dehydration can obtain cyclopenta phenolic ether, keep its selectivity slightly lower.In terms of post-processing, alkylated reaction and ether occurs
Changing the by-product that reaction generates is higher-boiling compound, and viscosity is larger, more difficulty is separated after reaction, if not separating
And applied with phenol, then it accumulates in the reaction system, increases system viscosity, bring production problem.And for using alcohol
Make solvent, it is anti-in hydration if alcohol additional amount is excessive since the selectivity of cyclopentanol is reduced with the reduction of solvent butanol additional amount
Ether easily is generated with the intermolecular dehydration of cyclopentanol under the conditions of answering, while after quantity of solvent increase, will increase the energy consumption of post-processing.
Summary of the invention
The present invention provides a kind of method for preparing cyclopentanol by cyclopentene direct hydration, its technical problems to be solved is
Keep the conversion ratio of cyclopentene higher using more preferably dicyandiamide solution, solvent is more stable, is hydrated cyclopentanol preparation process middle ring
Amylene and solvent do not occur side reaction substantially and generate by-product, make that the purification of cyclopentanol is more easy, energy consumption more saves.
It is the technical solution that the present invention solves above-mentioned technical problem below:
A kind of method that cyclopentene direct hydration prepares cyclopentanol, the following steps are included: by cyclopentene, water, mixed solvent
The material of composition continues through filling and carries out hydration reaction by the fixed bed of catalyst, and reaction temperature is 100~160 DEG C, reaction
Pressure is 1.0~3.0MPa, and volume space velocity is 0.5~2hr-1, in which: mixed solvent is (0.5~1.5): 1 neighbour by weight ratio
Nitrophenol and alcohol composition, the weight ratio of mixed solvent and cyclopentene are (0.5~1.5): 1, the molar ratio of water and cyclopentene is
(3.0~10.0): 1, the catalyst is the sulfonic storng-acid cation exchange resin of surface anchoring；After reaction, instead
Object cooling is answered to be layered as oily phase and water phase, rectifying under oil phase material normal pressure, 38~55 DEG C of fraction condenses to obtain unreacted ring
Amylene, 105~120 DEG C of fraction condense to obtain solvent, and 135~165 DEG C of fraction condensation, which is collected, obtains purification cyclopentanol, bottom
Liquid obtains the material rich in o-nitrophenol.
The alcohol of above-mentioned in the mixed solvent is n-butanol.
The weight ratio of above-mentioned in the mixed solvent o-nitrophenol and alcohol is (0.8~1.0): 1.
Above-mentioned reaction temperature is 120~130 DEG C, and reaction pressure is 1.5~2.0MPa, and volume space velocity is 0.8~1.2hr-1。
The beneficial effects of the present invention are:
(1) o-nitrophenol reaction system has as the temperature rises, can be with highly polar water and nonpolar hydro carbons
The characteristics of dissolving each other, being precipitated from water again at normal temperature, can be improved hydrated product conversion ratio；The one way of hydration of cyclopentene reaction
Conversion ratio is up to 15% or more.
(2) it adds o-nitrophenol in right amount in alcoholic solvent, changes the surface nature (polarity is strong and weak) of catalyst, make pair
Significant reaction is reduced, and improves the selectivity of cyclopentanol；Selectivity is 99% or more.
(3) after the additional amount of alcohol is greatly decreased, energy consumption is greatly reduced that (alcohol is directly recycled and followed from recovered overhead, ortho-nitrophenol
Ring use).
Specific embodiment
The present invention is further elaborated below with reference to embodiment.In embodiment, cyclopentene conversion ratio and cyclopentanol choosing
Selecting property is calculated by following two formula respectively:
Embodiment 1-5
The material that cyclopentene, water, mixed solvent form is continued through filling be hydrated instead by the fixed bed of catalyst
Answer, catalyst be the sulfonic storng-acid cation exchange resin of surface anchoring (be purchased from Tianjin Wade International Trading Company Ltd,
Trade name Amberlyst35), reaction temperature be 100~160 DEG C, reaction pressure be 1.0~3.0MPa, volume space velocity be 0.5~
2hr-1, in which: mixed solvent is (0.5~1.5) by weight ratio: 1 o-nitrophenol and n-butanol forms, mixed solvent and ring
The weight ratio of amylene is (0.5~1.5): 1, the molar ratio of water and cyclopentene is (3.0~10.0): 1；After reaction, it reacts
Object cooling is layered as oily phase and water phase, rectifying under oil phase material normal pressure, and 38~55 DEG C of fraction condenses to obtain unreacted cyclopentene,
105~120 DEG C of fraction condenses to obtain solvent, and purification cyclopentanol is collected to obtain in 135~165 DEG C of fraction condensation, and kettle base solution obtains rich
Material containing o-nitrophenol.The wherein selectivity result of the conversion per pass of the condition of hydration reaction and cyclopentene, cyclopentanol
As shown in the table.
Claims (3)
1. a kind of method that cyclopentene direct hydration prepares cyclopentanol, it is characterised in that, the following steps are included: by cyclopentene, water,
The fixed bed that the material of mixed solvent composition continues through loading catalyst carries out hydration reaction, and reaction temperature is 100~160
DEG C, reaction pressure is 1.0~3.0MPa, and volume space velocity is 0.5~2hr-1, in which: mixed solvent by weight ratio be (0.5~
1.5): 1 o-nitrophenol and alcohol composition, the alcohol are n-butanol, the weight ratio of mixed solvent and cyclopentene be (0.5~
1.5): 1, the molar ratio of water and cyclopentene is (3.0~10.0): 1, the catalyst is the sulfonic highly acid sun of surface anchoring
Ion exchange resin；After reaction, reactant, which cools down, is layered as oily phase and water phase, rectifying under oil phase material normal pressure, and 38~55
DEG C fraction condense to obtain unreacted cyclopentene, 105~120 DEG C of fraction condenses to obtain solvent, 135~165 DEG C of fraction
Condensation, which is collected, obtains purification cyclopentanol.
2. according to the method described in claim 1, it is characterized by: the weight ratio of the in the mixed solvent o-nitrophenol and alcohol
For (0.8~1.0): 1.
3. according to the method described in claim 1, reaction pressure is it is characterized by: the reaction temperature is 120~130 DEG C
1.5~2.0MPa, volume space velocity are 0.8~1.2hr-1。
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| CN108299155B (en) * | 2018-01-04 | 2021-03-16 | 中石化上海工程有限公司 | Method for producing cyclopentanol and cyclopentanone from cyclopentene |
| CN112661604A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Preparation method of cyclopentanol based on nickel-based supported catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676504A (en) * | 2004-04-02 | 2005-10-05 | 中国石化上海石油化工股份有限公司 | Cyclopentanol preparing and refining method |
| CN102010296A (en) * | 2010-11-18 | 2011-04-13 | 天津大学 | Method for preparing cyclopentanol from cyclopentene through hydration |
| CN102311317A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol through hydration of cyclopentene |
| CN102911016A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method of producing cyclopentanol via cyclopentene hydration |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676504A (en) * | 2004-04-02 | 2005-10-05 | 中国石化上海石油化工股份有限公司 | Cyclopentanol preparing and refining method |
| CN102311317A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol through hydration of cyclopentene |
| CN102010296A (en) * | 2010-11-18 | 2011-04-13 | 天津大学 | Method for preparing cyclopentanol from cyclopentene through hydration |
| CN102911016A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method of producing cyclopentanol via cyclopentene hydration |
Non-Patent Citations (1)
| Title |
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| 环戊烯水合制备环戊醇;郭世卓等;《华东理工大学学报》;20041231;第30卷(第6期);第621页 |
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