CN105585451A - Method for preparing cyclopentanol by direct hydration of cyclopentene - Google Patents

Method for preparing cyclopentanol by direct hydration of cyclopentene Download PDF

Info

Publication number
CN105585451A
CN105585451A CN201410566284.0A CN201410566284A CN105585451A CN 105585451 A CN105585451 A CN 105585451A CN 201410566284 A CN201410566284 A CN 201410566284A CN 105585451 A CN105585451 A CN 105585451A
Authority
CN
China
Prior art keywords
cyclopentene
cyclopentanol
reaction
solvent
hydration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410566284.0A
Other languages
Chinese (zh)
Other versions
CN105585451B (en
Inventor
黄勇
周飞
秦技强
黄彩凤
祁正娟
周秀凤
陆徐国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Petrochemical Co Ltd filed Critical China Petroleum and Chemical Corp
Priority to CN201410566284.0A priority Critical patent/CN105585451B/en
Publication of CN105585451A publication Critical patent/CN105585451A/en
Application granted granted Critical
Publication of CN105585451B publication Critical patent/CN105585451B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the field of organic chemical industry and specifically relates to a method for preparing cyclopentanol by direct hydration of cyclopentene. According to the method, materials composed of cyclopentene, water and a mixed solvent continuously pass through a fixed bed filled with a catalyst to undergo a hydration reaction, wherein the mixed solvent is composed of o-nitrophenol and alcohol according to the weight ratio of (0.5-1.5):1; after the hydration reaction, reactants are cooled and layered to obtain an oil phase and a water phase; and the oil phase material undergoes rectification at normal pressure, a fraction of 38-55 DEG C is condensed to obtain unreacted cyclopentene, a fraction of 105-120 DEG C is condensed to obtain a solvent, and a fraction of 135-165 DEG C is condensed and collected to obtain refined cyclopentanol. Conversion rate of cyclopentene is high. The solvent is more stable. During the preparation process of cyclopentanol by hydration, cyclopentene and the solvent basically undergo no side reaction to produce by-products. Thus, refining of cyclopentanol is simpler, and energy consumption is reduced.

Description

A kind of cyclopentene direct hydration is prepared the method for cyclopentanol
Technical field
The present invention relates to a kind of production method of cyclopentanol. Be particularly related in a kind of industry and prepared by cyclopentene direct hydrationThe method of cyclopentanol.
Background technology
Cyclopentanol is colourless viscous liquid, has armaticity smell, is that a kind of important medicine, agricultural chemicals fine chemistry industry are producedProduct intermediate, mainly for the preparation of products such as bromocyclopentane, chlorocyclopentane, antimicrobial, antiallergics; In additionBecause it has good solubility property to various resins, be used widely as solvent in electron trade. TraditionalCyclopentanol is produced mainly with taking adipic acid as raw material, after making cyclopentanone repeated hydrogenation, high temperature decarboxylation obtains, but due to productRaw a large amount of pollutants and the restriction that is subject to raw material sources, limited this technique and further developed. In recent years, due toC5 olefine fraction wide material sources, cheap, the research of producing cyclopentanol taking C 5 fraction as raw material causes that people are very bigInterest. Wherein cyclopentene can be closed and be prepared cyclopentanol by indirect hydration or direct water, although hydration method has indirectlyHigh, the selective good advantage of conversion ratio, but sulfuric acid is serious to equipment corrosion, retrieval of sulfuric acid cover used time concentration process energy consumptionGreatly; Although and direct hydration method conversion ratio is lower, solved equipment corrosion, problem that energy consumption is large, be more and more subject toPeople's concern.
Because hydration of cyclopentene reaction is subject to mass transport limitation, mass transfer rate depends primarily on catalyst surface and is formed by hydroneThickness of liquid film, and thickness of liquid film is relevant with the sulfonic group concentration of resin surface, the higher liquid film of concentration is thicker, encircles pentaAlkene is larger by liquid-film resistance, and reaction rate is slower, otherwise speed is faster. In the situation that not adding any solvent,The solubility of cyclopentene in water is very low, and both molecules can not fully contact with catalyst surface, and reaction is difficult forCarry out to positive direction, conversion ratio is very low. Therefore, in existing special technology, pass through to add a certain amount of and cyclopentanol toolThere is the solvent of compatibility, the intersolubility between cyclopentene and hydrone is increased, improve the conversion ratio of reaction.
Currently available technology is generally made solvent with phenol, alcohol and ethers, and as adopted phenol to make solvent, yield is 17%Above, apparently higher than other solvent, also have in addition bibliographical information, adopt alcohol to make solvent, yield is 10% left and right, choosingSelecting property is 95% left and right. There is obvious defect in existing method, as used phenol to make solvent, due to cyclopentene and phenolGeneration alkylated reaction and cyclopentanol and phenol dehydration all can obtain cyclopenta phenolic ether, make it selectively lower slightly. From post processingSee, the accessory substance that alkylated reaction and etherification reaction generation occur is higher-boiling compound, and viscosity is larger, reactionAfter finishing, separate comparatively difficulty, apply mechanically with phenol if do not separate, in reaction system, accumulate, increased bodyBe viscosity, bring production problem. And for using alcohol to make solvent, due to selectively adding with solvent butanols of cyclopentanolThe minimizing of amount and reducing, as excessive in alcohol addition, under hydration reaction condition easily with the intermolecular dehydration generation of cyclopentanol ether,After quantity of solvent increases simultaneously, can increase the energy consumption of post processing.
Summary of the invention
The invention provides a kind of method of being prepared cyclopentanol by cyclopentene direct hydration, the technical problem that it will solve isAdopt more preferably dicyandiamide solution to make the conversion ratio of cyclopentene higher, solvent is more stable, hydration cyclopentanol preparation processSubstantially not there is not side reaction and generate accessory substance in middle cyclopentene and solvent, makes refining more easy, the energy consumption of cyclopentanol moreEconomize.
Below the technical scheme that the present invention solves the problems of the technologies described above:
Cyclopentene direct hydration is prepared a method for cyclopentanol, comprises the following steps: by molten to cyclopentene, water, mixingThe material of agent composition carries out hydration reaction by filling by the fixed bed of catalyst continuously, and reaction temperature is 100~160DEG C, reaction pressure is 1.0~3.0MPa, volume space velocity is 0.5~2hr-1, wherein: mixed solvent by weight ratio be (0.5~1.5): 1 o-nitrophenol and alcohol composition, the weight ratio of mixed solvent and cyclopentene is (0.5~1.5): 1, waterWith the mol ratio of cyclopentene be (3.0~10.0): 1, described catalyst is the sulfonic highly acidic cation of surface anchoringExchanger resin; After reaction finishes, cooling oil phase and the water of being layered as of reactant, rectifying under oil phase material normal pressure, 38~The cut condensation of 55 DEG C obtains unreacted cyclopentene, and the cut condensation of 105~120 DEG C obtains solvent, 135~165DEG C cut condensation collect and obtain refining cyclopentanol, kettle base solution obtains being rich in the material of o-nitrophenol.
Alcohol in above-mentioned mixed solvent is n-butanol.
In above-mentioned mixed solvent, the weight ratio of 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
Beneficial effect of the present invention is:
(1) o-nitrophenol reaction system has the rising along with temperature, can with the water of strong polarity and nonpolar hydrocarbonClass is dissolved each other, and the feature that can separate out from water again at normal temperatures can improve hydrated product conversion ratio; Hydration of cyclopentene is anti-The conversion per pass of answering can reach more than 15%.
(2) in alcoholic solvent, add in right amount o-nitrophenol, changed the surface nature (polarity power) of catalyst,Side reaction is obviously reduced, improved the selective of cyclopentanol; Selectively more than 99%.
(3), after the addition of alcohol significantly reduces, energy consumption significantly reduces that (alcohol is from recovered overhead, and ortho-nitrophenol directly returnsReceipts recycle).
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated. In embodiment, cyclopentene conversion ratio and cyclopentanol choosingSelecting property is respectively by two formulas calculating below:
Embodiment 1-5
The material of cyclopentene, water, mixed solvent composition is carried out to hydration by filling by the fixed bed of catalyst continuously anti-Should, catalyst is that the sulfonic storng-acid cation exchange resin of surface anchoring is (limited purchased from the international trade of Vad, TianjinCompany, trade name Amberlyst35), reaction temperature is 100~160 DEG C, reaction pressure is 1.0~3.0MPa, bodyLong-pending air speed is 0.5~2hr-1, wherein: mixed solvent is (0.5~1.5) by weight ratio: 1 o-nitrophenol and justButanols composition, the weight ratio of mixed solvent and cyclopentene is (0.5~1.5): 1, the mol ratio of water and cyclopentene is(3.0~10.0): 1; After reaction finishes, cooling oil phase and the water of being layered as of reactant, rectifying under oil phase material normal pressure,The cut condensation of 38~55 DEG C obtains unreacted cyclopentene, and the cut condensation of 105~120 DEG C obtains solvent, 135~165DEG C cut condensation collect to obtain refining cyclopentanol, kettle base solution must be rich in the material of o-nitrophenol. Wherein hydration reactionThe conversion per pass of condition and cyclopentene, the selective result of cyclopentanol are as shown in the table.

Claims (4)

1. cyclopentene direct hydration is prepared a method for cyclopentanol, it is characterized in that, comprises the following steps: by cyclopentene,The material of water, mixed solvent composition carries out hydration reaction by the fixed bed of loading catalyst continuously, and reaction temperature is100~160 DEG C, reaction pressure is 1.0~3.0MPa, and volume space velocity is 0.5~2hr-1, wherein: mixed solvent byWeight ratio is (0.5~1.5): 1 o-nitrophenol and alcohol composition, the weight ratio of mixed solvent and cyclopentene is(0.5~1.5): 1, the mol ratio of water and cyclopentene is (3.0~10.0): 1, described catalyst is surface anchoringSulfonic storng-acid cation exchange resin; After reaction finishes, cooling oil phase and water, the oil phase of being layered as of reactantRectifying under material normal pressure, the cut condensation of 38~55 DEG C obtains unreacted cyclopentene, and the cut of 105~120 DEG C is coldThe solidifying solvent that obtains, the cut condensation of 135~165 DEG C is collected and is obtained refining cyclopentanol.
2. method according to claim 1, is characterized in that: the alcohol in described mixed solvent is n-butanol.
3. method according to claim 1, is characterized in that: the weight of o-nitrophenol and alcohol in described mixed solventAmount is than being (0.8~1.0): 1.
4. method according to claim 1, is characterized in that: described reaction temperature is 120~130 DEG C, reaction pressurePower is 1.5~2.0MPa, and volume space velocity is 0.8~1.2hr-1
CN201410566284.0A 2014-10-22 2014-10-22 A kind of method that cyclopentene direct hydration prepares cyclopentanol Active CN105585451B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410566284.0A CN105585451B (en) 2014-10-22 2014-10-22 A kind of method that cyclopentene direct hydration prepares cyclopentanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410566284.0A CN105585451B (en) 2014-10-22 2014-10-22 A kind of method that cyclopentene direct hydration prepares cyclopentanol

Publications (2)

Publication Number Publication Date
CN105585451A true CN105585451A (en) 2016-05-18
CN105585451B CN105585451B (en) 2019-07-16

Family

ID=55925393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410566284.0A Active CN105585451B (en) 2014-10-22 2014-10-22 A kind of method that cyclopentene direct hydration prepares cyclopentanol

Country Status (1)

Country Link
CN (1) CN105585451B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299155A (en) * 2018-01-04 2018-07-20 中石化上海工程有限公司 The method that cyclopentene produces cyclopentanol and cyclopentanone
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
郭世卓等: "环戊烯水合制备环戊醇", 《华东理工大学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299155A (en) * 2018-01-04 2018-07-20 中石化上海工程有限公司 The method that cyclopentene produces cyclopentanol and cyclopentanone
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

Also Published As

Publication number Publication date
CN105585451B (en) 2019-07-16

Similar Documents

Publication Publication Date Title
CN109517141A (en) Cardanol modified waterborne epoxy curing agent and preparation method thereof
WO2011143976A1 (en) Method for preparing polymethoxy dimethyl ethers by acetalization reaction of formaldehyde and methanol
CN104211885A (en) Low-temperature expandable phenolic resin and method of employing same to prepare phenolic foam
CN105503550A (en) Green preparation method for compounding pinacolone
CN105315164A (en) Environment-friendly choline ionic liquid and preparation method therefor
CN103865036A (en) Self-emulsifying water-borne epoxy resin curing agent and preparation method thereof
CN108715574A (en) A method of synthesis '-biphenyl diphenol
CN105585451A (en) Method for preparing cyclopentanol by direct hydration of cyclopentene
CN101168493A (en) Preparation method for fluorochlorobenzene
CN104672431B (en) A kind of tetra functional epoxy resin and preparation method and application
CN104672059A (en) Production method of neopentyl glycol
CN100415791C (en) Calixarene [4] modified thermosetting phenolic resin and preparation method thereof
CN106117063A (en) cardanol polyoxyethylene ether fatty acid ester and its preparation method and application
CN104926605A (en) Benzene-propanol azeotrope rectification separation method based on choline chloride further-co-melting solvent
CN104592166B (en) A kind of Supported on Zeolite process for catalytic synthesis of glycidyl allyl ether
CN104193598A (en) Multi-reflux environment-friendly dimethoxymethane preparation process
CN103965016A (en) Method for preparing fatty alcohol through hydrogenation of fatty acid methyl ester in presence of temperature control catalytic system
CN103130630B (en) Cyclopentanol green synthetic method
CN105523893A (en) Method for preparing cyclopentanol
CN106380383A (en) Synthesis method of 2-hexenal
CN102399134A (en) Method for preparing cyclohexanol by cyclohexene hydration
CN102030665A (en) Method for preparing tetrabutylammonium hydroxide
CN105585468B (en) A method of cyclopentanone is prepared by raw material of cyclopentene
CN104230636A (en) Preparation method of ethylbenzene from hydrogenation of low content acetophenone
CN102731250A (en) Method for synthesizing sec-butyl alcohol

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant