CN105585451A - Method for preparing cyclopentanol by direct hydration of cyclopentene - Google Patents
Method for preparing cyclopentanol by direct hydration of cyclopentene Download PDFInfo
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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
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。
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Cited By (2)
| 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 |
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| 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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Patent Citations (4)
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| 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 |
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Cited By (3)
| 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 |
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