CN102311317B - Method for preparing cyclopentanol through hydration of cyclopentene - Google Patents
Method for preparing cyclopentanol through hydration of cyclopentene Download PDFInfo
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- CN102311317B CN102311317B CN201010221007.8A CN201010221007A CN102311317B CN 102311317 B CN102311317 B CN 102311317B CN 201010221007 A CN201010221007 A CN 201010221007A CN 102311317 B CN102311317 B CN 102311317B
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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 a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, particularly under storng-acid cation exchange resin exists, by the method for Preparation of Cyclopantanol by Hydration of Cyclopentene.
Background technology
Cyclopentanol is a kind of important fine chemical product intermediate, mainly for the preparation of bromocyclopentane, chlorocyclopentane etc., and can be used for manufacturing the medicines such as antibiotic, antianaphylaxis.Cyclopentanol can make cyclopentanone through the high temperature depickling by hexanodioic acid, then by obtaining after hydrogenation reaction, but owing to producing a large amount of pollutents and the restriction that is subject to raw material sources, this preparation method is eliminated gradually.In addition, with the C of petroleum cracking ethylene by-product processed
5in cut, through separating the cyclopentenes obtained, be raw material, through hydration reaction, also can produce cyclopentanol.Hydration process mainly contains two kinds of techniques, the one, indirect hydrating process, the 2nd, direct hydration technique.Although hydrating process has the advantage that transformation efficiency is high, selectivity is good indirectly, owing to using sulfuric acid in technological process, high to the equipment material requirement, waste is difficult to process, and environmental pollution is comparatively serious.And there are not the problems referred to above in indirect hydration in direct hydration technique, be therefore eco-friendly technological line, the documents and materials of report all adopt this operational path in recent years.As proposing to adopt storng-acid cation exchange resin, Japanese Patent JP2003212803 carries out the method for Preparation of Cyclopantanol by Hydration of Cyclopentene, this patent is under the condition of the molar ratio 1.2～3.0 of cyclopentenes and water, the cyclopentenes per pass conversion is 3.50% left and right, selectivity 98% left and right.The weak point of the method is that reaction conversion ratio is relatively low, and raw material cyclopentenes internal circulating load is large.Chinese patent CN1676504A has proposed a kind of method by Preparation of Cyclopantanol by Hydration of Cyclopentene, the method is to take the fixed-bed reactor that material that cyclopentenes, water, solvent phenol and promotor trialkylamine formed is Primary Catalysts by storng-acid cation exchange resin continuously, carry out hydration reaction, volume space velocity is 2～15h
-1, the mol ratio 0.8～5.0 of cyclopentenes and water, in raw material, cocatalyst concentration is 0.01%～0.2%, 130 ℃～180 ℃ of temperature of reaction, reaction pressure 1.0MPa～3.0MPa, under these conditions, the transformation efficiency of cyclopentenes is 27% left and right, selectivity 99% left and right of cyclopentanol.Although the method has improved the transformation efficiency of cyclopentenes, added C in reactive system
2～C
5trialkylamine, due to trialkylamine be alkalescence, neutralized the sulfonic acid group in the storng-acid cation exchange resin, make the activity decreased of storng-acid cation exchange resin.Also added a large amount of phenol (weight ratio of phenol and cyclopentenes is 0.5～1) in system, made non-reaction soln occupy larger proportion in reaction system, it is complicated that technological process becomes, and follow-up separating difficulty strengthens, and energy consumption is relatively high.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene.The inventive method, under the selective conditions of the transformation efficiency that keeps higher cyclopentenes and cyclopentanol, makes subsequent product separate and is more prone to, and energy consumption is lower.
The method of Preparation of Cyclopantanol by Hydration of Cyclopentene of the present invention comprises: cyclopentenes, reaction solvent and water carry out hydration reaction by the reactor that strong acid cation exchange resin catalyst is housed, and during the liquid of cyclopentenes, volume space velocity is 0.5h
-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 cyclopentenes quality.
In above-mentioned reaction process, reaction conditions is preferably: during the liquid of cyclopentenes, volume space velocity is preferably 0.5h
-1～15h
-1; The 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 is: volume space velocity 1.0h during the liquid of cyclopentenes
-1～5.0h
-1; The mol ratio of water and cyclopentenes is 2: 1～5: 1, and the reaction solvent add-on is 1.0%～3.0% of cyclopentenes quality, 120 ℃～150 ℃ of temperature of reaction, reaction pressure 2.0MPa～3.0MPa.And catalyzer is preferably storng-acid cation exchange resin, can use commercial goods, also can be by existing method preparation, the DNW-II type high-temperature cation-exchange resin catalyzer of specifically producing as Dandong Mingzhu Special Type Resin Co., Ltd..Reaction solvent is preferentially selected C
3or C
4one or more of alcohol, add-on is 1%～3% of 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, existence due to 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 formed, thereby having reduced the resistance of cyclopentenes to the catalyst surface diffusion, having increased the formation of carbonium ion, 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
Below by specific embodiment, the present invention will be further described.Cyclopentenes transformation efficiency and cyclopentanol selectivity in embodiment and comparative example are calculated by following formula.
Embodiment 1～32
Hydration reaction is to carry out in the stainless steel reactor of Φ 18mm * 1200mm, the DNW-II type heatproof resin catalyst that 30ml Dandong Mingzhu Special Type Resin Co., Ltd. produces of packing in reactor, reactor head and bottom, be respectively charged into the quartz sand that diameter is Φ 0.5mm～1.2mm, after reactor installs, with nitrogen replacement three times, and tightness test is qualified, by 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 preheating enters hydration reactor and carries out hydration reaction, and controlling temperature of reaction is 100 ℃～200 ℃, and reaction pressure is 1.0MPa～6.0MPa.For 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, add promotor three alkanamines and reaction solvent phenol in charging.
Comparative example 3～4
According to the method for embodiment 1, do not add any promotor and solvent in charging.
Above used DNW-II type heatproof resin catalyst physico-chemical property is in Table 1, and the reaction conditions of each embodiment and comparative example is in Table 2, and reaction result is in Table 3.
Table 1 has been listed test DNW-II type heatproof resin catalyst character used
| Sequence number | Physical property | Index |
| 1 | Rate of small round spheres/% after mill | 94.0 |
| 2 | Exchange capacity/molL -1 | 0.99 |
| 3 | Water content/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 |
From above embodiment and comparative example data, can find out, the inventive method is compared with the hydrating process that does not make used additives, and transformation efficiency obviously improves.The inventive method and a large amount of solvents of existing use 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, do not need to use promotor yet, make the sepn process of reaction product simplify, Energy Intensity Reduction.
Claims (4)
1. the method for a Preparation of Cyclopantanol by Hydration of Cyclopentene, comprising: cyclopentenes, reaction solvent and water carry out hydration reaction by the reactor that strong acid cation exchange resin catalyst is housed, and during the liquid of cyclopentenes, volume space velocity is 0.5h
-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
3～C
4one or more of alcohol, the reaction solvent add-on is 0.05%～5% of cyclopentenes quality.
2. in accordance with the method for claim 1, it is characterized in that reaction conditions is: during the liquid of cyclopentenes, volume space velocity is 0.5h
-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 cyclopentenes quality, and temperature of reaction is 100 ℃～150 ℃, and reaction pressure is 2.0MPa～5.0MPa.
3. in accordance with the method for claim 1, it is characterized in that reaction conditions is: during the liquid of cyclopentenes, volume space velocity is 1.0h
-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 cyclopentenes quality, 120 ℃～150 ℃ of temperature of reaction, reaction pressure 2.0MPa～3.0MPa.
4. it is characterized in that in accordance with the method for claim 1: the reaction solvent add-on is 1%～3% of cyclopentenes quality.
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| CN201010221007.8A CN102311317B (en) | 2010-07-07 | 2010-07-07 | Method for preparing cyclopentanol through hydration of cyclopentene |
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| CN201010221007.8A CN102311317B (en) | 2010-07-07 | 2010-07-07 | Method for preparing cyclopentanol through hydration of cyclopentene |
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| CN102311317B true CN102311317B (en) | 2014-01-01 |
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Families Citing this family (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 |
| 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 |
| 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 |
| CN105523893A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol |
| CN110683935A (en) * | 2019-11-06 | 2020-01-14 | 中国天辰工程有限公司 | Preparation method of cyclododecanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60115542A (en) * | 1983-11-25 | 1985-06-22 | Nippon Zeon Co Ltd | Production of cycloalkanol |
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2010
- 2010-07-07 CN CN201010221007.8A patent/CN102311317B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| JP昭60-115542A 1985.06.22 |
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