CN1676506A - Method for preparing cyclopentanol by hydration of cyclopentene - Google Patents
Method for preparing cyclopentanol by hydration of cyclopentene Download PDFInfo
- Publication number
- CN1676506A CN1676506A CN 200410017401 CN200410017401A CN1676506A CN 1676506 A CN1676506 A CN 1676506A CN 200410017401 CN200410017401 CN 200410017401 CN 200410017401 A CN200410017401 A CN 200410017401A CN 1676506 A CN1676506 A CN 1676506A
- Authority
- CN
- China
- Prior art keywords
- cyclopentenes
- promotor
- hydration
- water
- cyclopentanol
- 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
Links
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 29
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000036571 hydration Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 15
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title abstract 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 150000001941 cyclopentenes Chemical class 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 5
- 238000004873 anchoring Methods 0.000 claims description 2
- 239000012190 activator Substances 0.000 abstract 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 carbonium ion Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention is a method that cyclopentene makes cyclopentanol through hydration. It uses cyclopentene and water as raw materials, and cyclopentene, water and activator continuously pass through catalyst fixed bed to carry out hydration reaction, the mole ratio of cyclopentene and water is 0.8-5.0, reaction temperature 130-180deg.C, reaction pressure 1.0-3.0MPa, and the catalyst is strong acid cation exchange resin with sulfo group anchored on the surface, and the activating solvent is trialkylamine. The weigh ration of activators is: cycloamylene: activator=100:(0.2-5). This invention advances the conversion of hydration cyclopentene and maintains the selectivity at high level.
Description
Technical field
The present invention relates to a kind of method by cyclopentenes hydration system cyclopentanol, particularly adopting storng-acid cation exchange resin is the method for catalyzer by cyclopentenes hydration system cyclopentanol.
Background technology
Cyclopentanol is a kind of important fine chemical product intermediate, is mainly used in preparation bromocyclopentane, chlorocyclopentane etc., and can be used for making medicine such as antibiotic, antianaphylaxis.Cyclopentanol can make cyclopentanone through high temperature decarboxylation by hexanodioic acid, and again by obtaining after the hydrogenation reaction, but owing to produce a large amount of pollutents and be subjected to the restriction of raw material sources, this preparation method is restricted day by day.In addition, the cyclopentenes that makes with processing in the C5 fraction of petroleum cracking system ethylene by-product is a raw material, also can produce cyclopentanol by hydration reaction, comprising the indirect hydration of cyclopentenes and two kinds of technologies of direct hydration, though indirectly hydration has transformation efficiency height, advantage that selectivity is good, but owing to need to use sulfuric acid in the preparation process, equipment corrosion-resistant required high, and environmental pollution is still comparatively serious.Then there are not these problems in direct hydration technology, is an eco-friendly technological line therefore, is used in recent years morely.Propose to adopt storng-acid cation exchange resin to carry out the method for cyclopentenes hydration system cyclopentanol as Japanese Patent JP2003212803, it is introduced that molar ratio at cyclopentenes and water is under 1.2～3.0 the condition, the cyclopentenes per pass conversion is about 3.50%, and selectivity is about 98%.Owing under higher cyclopentenes/water mol ratio, react, reduced the consumption of water, make that the removal energy that water consumed is less when the separating ring amylalcohol, thereby improved production efficiency.But it is still relatively low that the deficiency of this method is reaction conversion ratio, and the internal circulating load of raw material cyclopentenes is bigger.
Summary of the invention
The invention provides a kind of method by cyclopentenes hydration system cyclopentanol, the technical problem that it will solve is to attempt further to improve the transformation efficiency of cyclopentenes, wishes that simultaneously the selectivity of cyclopentanol remains on higher level.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of method of cyclopentenes hydration system cyclopentanol, this method is a raw material with cyclopentenes and water, cyclopentenes, water and promotor carry out hydration reaction by the Primary Catalysts fixed bed continuously and make cyclopentanol.The molar ratio of cyclopentenes and water is 0.8～5.0, and volume space velocity is 1～10h
-1, temperature of reaction is 130～180 ℃, reaction pressure is absolute pressure 1.0～3.0MPa.Catalyzer is a storng-acid cation exchange resin, and its surface anchoring sulfonic group, promotor are the trialkylamine with following structural formula:
R wherein
1, R
2And R
3C respectively does for oneself
2～C
5Alkyl, the add-on of promotor is counted with weight ratio:
Cyclopentenes: promotor=100: (0.2～5).
Above-mentioned promotor is preferably triethylamine or tripropyl amine; The add-on of promotor is preferably in weight ratio:
Cyclopentenes: promotor=100: (0.3～1.5).
By the cited documents Japanese Patent JP2003212803 of above-mentioned background technology as can be seen, storng-acid cation exchange resin is a kind of more satisfactory catalyzer of above-mentioned hydration reaction that is used for, and it can make hydration reaction carry out under the molar ratio of higher cyclopentenes/water.But because the wetting ability sulfonic group is contained on above-mentioned catalyzer storng-acid cation exchange resin surface, it forms one deck water molecules liquid film with preferentially adsorbed water and at catalyst surface, the cyclopentenes molecular diffusion is to the liquid film surface, liquid film be must pass and regeneration carbonium ion and water generation electrophilic addition reaction adsorbed with the chemisorption form at catalyst surface.Therefore the liquid film that formed by water molecules of catalyst surface can influence contacting of cyclopentenes and catalyst surface catalytic active center to a certain extent, and this perhaps is exactly the relatively low reason of hydration process transformation efficiency that above-mentioned documents is introduced.
Compared with prior art, distinguishing characteristics of the present invention is to send out to answer in hydration to have added the promotor trialkylamine in the system.The contriver found through experiments, and this alkaline compound of trialkylamine has modification to resin surface, and it can improve the contact environment of cyclopentenes and catalyst surface catalytic active center, helps cyclopentenes to spread to the catalyst surface catalytic active center.After adding trialkylamine in the hydration reaction system, trialkylamine and the reaction of resin surface part sulfonic group, formation is similar to the species of quaternary ammonium salt, make the acidity and the water-absorbent of resin reduce, formed by the common surperficial environment that exists of the species of highly acid sulfonic group and similar quaternary ammonium salt at resin surface like this.Wherein sulfonic group is the hydration reaction active sites, should keep certain concentration at resin surface, and the species of similar quaternary ammonium salt can make the organism cyclopentenes reduce to the diffusional resistance of resin surface.The contriver sees from experimental data, thisly not only can improve the transformation efficiency of hydration reaction cyclopentenes to the improvement of catalyst surface reaction environment, can make the selectivity of target product remain on a higher level simultaneously.
Below will the invention will be further described by specific embodiment.In embodiment and comparative example, cyclopentenes per pass conversion and cyclopentanol optionally are defined as:
Embodiment
[embodiment 1～6]
Hydration reaction is carried out in the stainless steel single tube reactor of φ 25mm * 1000mm, and reactor bottom is settled 300 purpose stainless (steel) wires, and the 100ml Primary Catalysts strongly-acid sun of packing into then is from exchange resin, with nitrogen with the air displacement in the single tube reactor three times.Cyclopentenes, water and promotor trialkylamine are sent into preheater with volume pump in required ratio, and material is heated to 130～180 ℃.Material after the preheating enters single tube reactor and carries out hydration reaction, and control reaction temperature is that 130～180 ℃, reaction pressure are absolute pressure 1.0MPa～3.0MP.Reaction product is chilled to room temperature, standing demix, and fractionation by distillation water material and oil phase material are obtained product cyclopentanol and unreacted cyclopentenes respectively.Water and unreacted cyclopentenes return the charging system reuse.
[comparative example 1～2]
Do not add the promotor trialkylamine in the charging, all the other are with embodiment 1～6.
More than do not give description in each embodiment and the comparative example reaction conditions see Table 1, reaction result sees Table 2.
Table 1.
| Promotor | Cyclopentenes/water (mol ratio) | Cyclopentenes/promotor (weight ratio) | Volume space velocity (hr -1) | |
| Embodiment 1 | Triethylamine | ????3.0 | ????100/4 | ????10.0 |
| Embodiment 2 | Triethylamine | ????2.0 | ????100/5 | ????5.0 |
| Embodiment 3 | Triethylamine | ????5.0 | ????100/1 | ????3.0 |
| Embodiment 4 | Tripropyl amine | ????0.8 | ????100/0.2 | ????1.0 |
| Embodiment 5 | Tripropyl amine | ????2.0 | ????100/0.3 | ????9.0 |
| Embodiment 6 | Tripropyl amine | ????2.0 | ????100/0.5 | ????3.0 |
| Comparative example 1 | ????- | ????1.5 | ????- | ????3.0 |
| Comparative example 2 | ????- | ????2.0 | ????- | ????4.2 |
Table 2.
| Cyclopentenes per pass conversion (%) | Cyclopentanol selectivity (%) | |
| Embodiment 1 | ????7.0 | ????99.8 |
| Embodiment 2 | ????7.2 | ????99.7 |
| Embodiment 3 | ????8.6 | ????99.6 |
| Embodiment 4 | ????8.9 | ????99.5 |
| Embodiment 5 | ????7.1 | ????99.4 |
| Embodiment 6 | ????8.5 | ????99.3 |
| Comparative example 1 | ????2.3 | ????98.3 |
| Comparative example 2 | ????3.5 | ????98.0 |
Claims (3)
1, a kind of method of cyclopentenes hydration system cyclopentanol, this method is a raw material with cyclopentenes and water, cyclopentenes, water and promotor carry out hydration reaction by the Primary Catalysts fixed bed continuously and make cyclopentanol, and the molar ratio of cyclopentenes and water is 0.8～5.0, and volume space velocity is 1～10hr
-1, temperature of reaction is 130～180 ℃, and reaction pressure is absolute pressure 1.0～3.0MPa, and catalyzer is a storng-acid cation exchange resin, and its surface anchoring sulfonic group, promotor are the trialkylamine with following structural formula:
R wherein
1, R
2And R
3C respectively does for oneself
2～C
5Alkyl, the add-on of promotor is counted with weight ratio:
Cyclopentenes: promotor=100: (0.2～5).
2, the method for cyclopentenes hydration system cyclopentanol according to claim 1 is characterized in that described promotor is triethylamine or tripropyl amine.
3, the method for cyclopentenes hydration system cyclopentanol according to claim 1 is characterized in that the add-on of described promotor is counted with weight ratio:
Cyclopentenes: promotor=100: (0.3～1.5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100174014A CN100503537C (en) | 2004-04-02 | 2004-04-02 | Method for preparing cyclopentanol by hydration of cyclopentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100174014A CN100503537C (en) | 2004-04-02 | 2004-04-02 | Method for preparing cyclopentanol by hydration of cyclopentene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1676506A true CN1676506A (en) | 2005-10-05 |
| CN100503537C CN100503537C (en) | 2009-06-24 |
Family
ID=35049269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100174014A Expired - Lifetime CN100503537C (en) | 2004-04-02 | 2004-04-02 | Method for preparing cyclopentanol by hydration of cyclopentene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100503537C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311315A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for producing cyclopentanol through hydrating cyclopentene |
| CN102617290A (en) * | 2012-02-26 | 2012-08-01 | 上海派尔科化工材料有限公司 | Process for preparing cyclopentanol with 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 |
| 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 |
| CN114436855A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine from isobutene |
| CN114436856A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine through isobutene amination |
-
2004
- 2004-04-02 CN CNB2004100174014A patent/CN100503537C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311315A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for producing cyclopentanol through hydrating cyclopentene |
| CN102311315B (en) * | 2010-07-07 | 2014-07-23 | 中国石油化工股份有限公司 | Method for producing cyclopentanol through hydrating cyclopentene |
| CN102617290A (en) * | 2012-02-26 | 2012-08-01 | 上海派尔科化工材料有限公司 | Process for preparing cyclopentanol with 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 |
| 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 |
| CN114436855A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine from isobutene |
| CN114436856A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine through isobutene amination |
| CN114436856B (en) * | 2020-10-31 | 2024-06-04 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine by isobutene amination |
| CN114436855B (en) * | 2020-10-31 | 2024-07-02 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine from isobutene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100503537C (en) | 2009-06-24 |
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Granted publication date: 20090624 |