CN102311317A - Method for preparing cyclopentanol through hydration of cyclopentene - Google Patents
Method for preparing cyclopentanol through hydration of cyclopentene Download PDFInfo
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- CN102311317A CN102311317A CN2010102210078A CN201010221007A CN102311317A CN 102311317 A CN102311317 A CN 102311317A CN 2010102210078 A CN2010102210078 A CN 2010102210078A CN 201010221007 A CN201010221007 A CN 201010221007A CN 102311317 A CN102311317 A CN 102311317A
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Abstract
The invention discloses a method for preparing cyclopentanol through hydration of cyclopentene. The method comprises a step of continuously performing hydration reaction on the cyclopentene and water through a fixed-bed reactor which holds a strongly acidic cation exchange resin catalyst, wherein the liquid hourly space velocity of the cyclopentene is 0.5h <-1> to 20h <-1>; the molar ratio of the cyclopentene to the water is 0.5-10:1; a reaction solvent is C1-C4 low-carbon alcohol; the amount of the added reaction solvent is 0.05-10 percent of the amount of the cyclopentene; the reaction temperature is 100-200 DEG C; and the reaction pressure is 1.0-6.0MPa. Compared with the prior art, the method has the advantages of single material in a reaction system, high conversion efficiency, high selectivity, fewer byproducts, high convenience in product separation, low energy consumption and the like.
Description
Technical field
The invention discloses the method that a kind of cyclopentenes hydration prepares cyclopentanol, particularly in the presence of strongly acidic cationic exchange resin, prepare the method for cyclopentanol by the cyclopentenes hydration.
Background technology
Cyclopentanol is a kind of important fine chemical product midbody, is mainly used in preparation bromocyclopentane, chlorocyclopentane etc., and can be used for making medicine such as antibiotic, antianaphylaxis.Cyclopentanol can make ketopentamethylene through the high temperature depickling by hexanodioic acid, and again through obtaining after the hydrogenation reaction, but owing to produce a large amount of pollutents and the restriction that receives raw material sources, this preparation method is eliminated gradually.In addition, with the C of petroleum cracking system ethylene by-product
5In the cut, be raw material, also can produce cyclopentanol through hydration reaction through separating the cyclopentenes that obtains.Hydration process mainly contains two kinds of technologies, the one, indirect hydrating process, the 2nd, direct hydration technology.Though indirectly hydrating process has transformation efficiency height, advantage that selectivity is good, owing to use sulfuric acid in the technological process, equipment material is required high, waste is difficult to processing, and environmental pollution is comparatively serious.And there are not the problems referred to above in the indirect hydration in direct hydration technology, is eco-friendly technological line therefore, and the documents and materials of report all adopt this operational path in recent years.Propose to adopt strongly acidic cationic exchange resin to carry out the method that the cyclopentenes hydration prepares cyclopentanol like Japanese Patent JP2003212803; This patent is under the condition of the molar ratio 1.2～3.0 of cyclopentenes and water; The cyclopentenes per pass conversion is about 3.50%, selectivity about 98%.The weak point of this method is that reaction conversion ratio is relatively low, and raw material cyclopentenes internal circulating load is big.Chinese patent CN1676504A has proposed a kind of method that is prepared cyclopentanol by the cyclopentenes hydration; This method is to be the fixed-bed reactor of Primary Catalysts continuously through strongly acidic cationic exchange resin with the material that cyclopentenes, water, solvent phenol and promotor trialkylamine are formed; Carry out hydration reaction, volume space velocity is 2～15h
-1, the mol ratio 0.8～5.0 of cyclopentenes and water, cocatalyst concentration is 0.01%～0.2% in the raw material; 130 ℃～180 ℃ of temperature of reaction, reaction pressure 1.0MPa～3.0MPa, under these conditions; The transformation efficiency of cyclopentenes is about 27%, the selectivity about 99% of cyclopentanol.Though this method has improved the transformation efficiency of cyclopentenes, in reactive system, added C
2～C
5Trialkylamine because trialkylamine be an alkalescence, the sulfonic acid group in the strongly acidic cationic exchange resin that neutralized makes the activity reduction of strongly acidic cationic exchange resin.Also added a large amount of phenol (weight ratio of phenol and cyclopentenes is 0.5～1) in the system, made non-reaction soln in reaction system, occupy larger proportion, it is complicated that technological process becomes, and follow-up separating difficulty strengthens, and energy consumption is higher relatively.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of cyclopentenes hydration to prepare the method for cyclopentanol.The inventive method makes subsequent product separate and is more prone to that energy consumption is lower under the selective conditions of transformation efficiency that keeps higher cyclopentenes and cyclopentanol.
The method that cyclopentenes hydration of the present invention prepares cyclopentanol comprises: cyclopentenes, reaction solvent and water carry out hydration reaction through the reactor drum that strong acid cation exchange resin catalyst is housed, and volume space velocity is 0.5h during the liquid of cyclopentenes
-1～20h
-1, the mol ratio of water and cyclopentenes is 0.5: 1～10: 1,100 ℃～200 ℃ of temperature of reaction, and reaction pressure is 1.0MPa～6.0MPa, reaction solvent is C
1～C
4One or more of alcohol, the reaction solvent add-on is 0.05%～10% of a cyclopentenes quality.
In above-mentioned reaction process, reaction conditions is preferably: volume space velocity is preferably 0.5h during the liquid of cyclopentenes
-1～15h
-1The mol ratio of water and cyclopentenes is preferably 1: 1～and 8: 1, the reaction solvent add-on is preferably 0.5%～5% of cyclopentenes quality, and temperature of reaction is preferably 100 ℃～150 ℃, and reaction pressure is preferably 2.0MPa～5.0MPa.And the reaction conditions that override is selected for use is: volume space velocity 1.0h during the liquid of cyclopentenes
-1～5.0h
-1The mol ratio of water and cyclopentenes is 2: 1～5: 1, and the reaction solvent add-on is 1.0%～3.0% of a cyclopentenes quality, 120 ℃～150 ℃ of temperature of reaction, reaction pressure 2.0MPa～3.0MPa.And catalyzer is preferably strongly acidic cationic exchange resin, can use the commercial goods, also can be by existing method preparation, the DNW-II type high-temperature cation-exchange resin catalyzer of specifically producing like Dandong Mingzhu Special Type Resin Co., Ltd..Reaction solvent is preferentially selected C for use
3Or C
4One or more of alcohol, add-on is 1%～3% of a cyclopentenes quality.
Compared with prior art, the present invention has added C in reactive system
1～C
4Low-carbon alcohol, under the hydration reaction condition, because the existence of a small amount of low-carbon alcohol; Improved the mutual solubility of cyclopentenes and water; Make catalyst surface seldom form the water molecules liquid film or make the moisture thinning of liquid film of formation, thereby reduced the resistance of cyclopentenes, increased the formation of carbonium ion to the catalyst surface diffusion; Improve the speed of hydration reaction, thereby improved the speed of response of cyclopentenes.The substance classes that the inventive method is used is few, and low-carbon alcohol consumption in reaction system seldom and is easy to separate, and the sepn process energy consumption is low.
Embodiment
Through specific embodiment the present invention is done further description below.Cyclopentenes transformation efficiency and cyclopentanol selectivity in embodiment and comparative example are calculated through following formula.
Embodiment 1～32
Hydration reaction is in the stainless steel reactor of Φ 18mm * 1200mm, to carry out; The DNW-II type heatproof resin catalyst that 30ml Dandong Mingzhu Special Type Resin Co., Ltd. produces of in reactor drum, packing into, reactor head and bottom are respectively charged into the silica sand that diameter is Φ 0.5mm～1.2mm; After reactor drum installs; With nitrogen replacement three times, and tightness test is qualified, with cyclopentenes, water and C
1～C
4Low-carbon alcohol send into preheater with volume pump according to the ratio of defined, material is preheating to 100 ℃～200 ℃.Material after the preheating gets into hydration reactor and carries out hydration reaction, and control reaction temperature is 100 ℃～200 ℃, and reaction pressure is 1.0MPa～6.0MPa.Be the contrast reaction effect, each embodiment and comparative example all carry out under 130 ℃ and 2MPa.Unreacted cyclopentenes recycles.
Comparative example 1～2
According to the method for embodiment 1, in charging, add promotor three alkanamines and reaction solvent phenol.
Comparative example 3～4
According to the method for embodiment 1, in charging, do not add any promotor and solvent.
More than employed DNW-II type heatproof resin catalyst physico-chemical property see table 1, the reaction conditions of each embodiment and comparative example is seen table 2, reaction result is seen table 3.
Table 1 has been listed the used DNW-II type heatproof resin catalyst character of test
| Sequence number | Rerum natura | Index |
| 1 | Mill back rate of small round spheres/% | 94.0 |
| 2 | Exchange capacity/molL -1 | 0.99 |
| 3 | Water cut/quality % | 59.94 |
| 4 | Wet volume density/gmL -1 | 0.81 |
| 5 | Wet true density/gmL -1 | 1.182 |
The reaction conditions of each embodiment of table 2 and comparative example
The reaction result of each embodiment of table 3 and comparative example
| Project | The cyclopentenes per pass conversion, % | The cyclopentanol selectivity, % |
| Embodiment 1 | 12.5 | 98.6 |
| Embodiment 2 | 14.0 | 98.2 |
| Embodiment 3 | 11.4 | 99.1 |
| Embodiment 4 | 15.6 | 98.2 |
| Embodiment 5 | 14.8 | 98.4 |
| Embodiment 6 | 14.5 | 99.3 |
| Embodiment 7 | 12.6 | 98.1 |
| Embodiment 8 | 27.5 | 99.6 |
| Embodiment 9 | 25.6 | 96.8 |
| Embodiment 10 | 29.7 | 95.2 |
| Embodiment 11 | 24.7 | 99.2 |
| Embodiment 12 | 28.9 | 98.5 |
| Embodiment 13 | 24.5 | 97.6 |
| Embodiment 14 | 18.6 | 95.6 |
| Embodiment 15 | 20.1 | 96.4 |
| Embodiment 16 | 18.6 | 98.6 |
| Embodiment 17 | 17.5 | 97.5 |
| Embodiment 18 | 18.6 | 98.4 |
| Embodiment 18 | 16.7 | 99.3 |
| Embodiment 20 | 27.2 | 98.2 |
| Embodiment 21 | 14.3 | 98.6 |
| Embodiment 22 | 15.7 | 97.5 |
| Embodiment 23 | 13.2 | 98.2 |
| Comparative example 1 | 27.2 | 99.1 |
| Comparative example 2 | 27.5 | 98.9 |
| Comparative example 3 | 2.3 | 98.3 |
| Comparative example 4 | 3.5 | 98.0 |
Can find out that from above embodiment and comparative example data the inventive method is compared with the hydrating process that does not make used additives, transformation efficiency obviously improves.The inventive method and the existing high amounts of solvents of using make the hydrating process of used additives compare simultaneously, and transformation efficiency and selectivity under the typical process condition are suitable; But the quantity of solvent of using obviously reduces; Also need not use promotor, make the sepn process of reaction product simplify, energy consumption reduces.
Claims (5)
1. a cyclopentenes hydration prepares the method for cyclopentanol, and comprising: cyclopentenes, reaction solvent and water carry out hydration reaction through the reactor drum that strong acid cation exchange resin catalyst is housed, and volume space velocity is 0.5h during the liquid of cyclopentenes
-1～20h
-1, the mol ratio of water and cyclopentenes is 0.5: 1～10: 1,100 ℃～200 ℃ of temperature of reaction, and reaction pressure is 1.0MPa～6.0MPa, it is characterized in that: reaction solvent is C
1～C
4One or more of alcohol, the reaction solvent add-on is 0.05%～10% of a cyclopentenes quality.
2. according to the described method of claim 1, it is characterized in that reaction conditions is: volume space velocity is 0.5h during the liquid of cyclopentenes
-1～15h
-1, the mol ratio of water and cyclopentenes is 1: 1～8: 1, and the reaction solvent add-on is 0.5%～5% of a cyclopentenes quality, and temperature of reaction is 100 ℃～150 ℃, and reaction pressure is preferably 2.0MPa～5.0MPa.
3. according to the described method of claim 1, it is characterized in that reaction conditions is: volume space velocity is 1.0h during the liquid of cyclopentenes
-1～5.0h
-1, the mol ratio of water and cyclopentenes is 2: 1～5: 1, the reaction solvent add-on is 1.0%～3.0% of a cyclopentenes quality, 120 ℃～150 ℃ of temperature of reaction, reaction pressure 2.0MPa～3.0MPa.
4. according to the described method of claim 1, it is characterized in that: reaction solvent is one or more of C3 or C4 alcohol.
5. according to claim 1 or 4 described methods, it is characterized in that: the reaction solvent add-on is 1%～3% of a cyclopentenes quality.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603486A (en) * | 2012-02-26 | 2012-07-25 | 上海派尔科化工材料有限公司 | Method for preparing cyclopentanol from cyclopentene |
| CN103785330A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Alkene hydration reactor and application thereof |
| CN105523893A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol |
| CN105585468A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing cyclopentanone by using cyclopentene as raw material |
| CN105585451A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol by direct hydration of cyclopentene |
| CN110683935A (en) * | 2019-11-06 | 2020-01-14 | 中国天辰工程有限公司 | Preparation method of cyclododecanol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60115542A (en) * | 1983-11-25 | 1985-06-22 | Nippon Zeon Co Ltd | Production of cycloalkanol |
| CN1233609A (en) * | 1998-04-24 | 1999-11-03 | 中国石油化工总公司 | Method for preparing tertiary amyl alcohol |
| CN1676505A (en) * | 2004-04-02 | 2005-10-05 | 中国石化上海石油化工股份有限公司 | Method for preparing cyclopentanol by hydration of cyclopentene |
-
2010
- 2010-07-07 CN CN201010221007.8A patent/CN102311317B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60115542A (en) * | 1983-11-25 | 1985-06-22 | Nippon Zeon Co Ltd | Production of cycloalkanol |
| CN1233609A (en) * | 1998-04-24 | 1999-11-03 | 中国石油化工总公司 | Method for preparing tertiary amyl alcohol |
| CN1676505A (en) * | 2004-04-02 | 2005-10-05 | 中国石化上海石油化工股份有限公司 | Method for preparing cyclopentanol by hydration of cyclopentene |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603486A (en) * | 2012-02-26 | 2012-07-25 | 上海派尔科化工材料有限公司 | Method for preparing cyclopentanol from cyclopentene |
| CN103785330A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Alkene hydration reactor and application thereof |
| CN103785330B (en) * | 2012-11-01 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of application of olefin hydration reactor |
| CN105523893A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol |
| CN105585468A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing cyclopentanone by using cyclopentene as raw material |
| CN105585451A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol by direct hydration of cyclopentene |
| CN105585468B (en) * | 2014-10-22 | 2019-02-15 | 中国石油化工股份有限公司 | A method of cyclopentanone is prepared by raw material of cyclopentene |
| CN105585451B (en) * | 2014-10-22 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of method that cyclopentene direct hydration prepares cyclopentanol |
| CN110683935A (en) * | 2019-11-06 | 2020-01-14 | 中国天辰工程有限公司 | Preparation method of cyclododecanol |
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