CN116082276B - Rectification method for refining ultra-dry cyclohexene oxide - Google Patents
Rectification method for refining ultra-dry cyclohexene oxide Download PDFInfo
- Publication number
- CN116082276B CN116082276B CN202211668076.2A CN202211668076A CN116082276B CN 116082276 B CN116082276 B CN 116082276B CN 202211668076 A CN202211668076 A CN 202211668076A CN 116082276 B CN116082276 B CN 116082276B
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- CN
- China
- Prior art keywords
- entrainer
- epoxy cyclohexane
- water
- crude product
- epoxycyclohexane
- 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.)
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- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 18
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000007670 refining Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003046 tetrablock copolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a rectification method for refining ultra-dry epoxy cyclohexane. The method comprises the following steps: (1) Mixing the crude product of the epoxy cyclohexane with an azeotropic entrainer, rectifying the mixture at the temperature of between 85 and 95 ℃ by the mass fraction of the azeotropic entrainer to enable an upper layer oil layer of distillate to flow back to a tower kettle, and separating a lower layer water layer to achieve the water removal effect; (2) After the crude product of the cyclohexene oxide and the mixture of the azeotropic entrainer are subjected to water diversion, reflux and water removal, continuously heating to 132 ℃, and rectifying the azeotropic entrainer; (3) And (3) carrying out water diversion, reflux and dehydration on the crude product of the epoxy cyclohexane and the mixture of the azeotropic entrainer, rectifying the entrainer, and then heating to 133 ℃ to obtain the rectified epoxy cyclohexane. The purity of the epoxycyclohexane obtained by refining is more than 99.9%, the water content is lower than 150ppm, and the recovery rate of the epoxycyclohexane is more than 98%.
Description
Technical Field
The invention belongs to the field of chemical industry refining and dewatering, and particularly relates to a rectification method for refining ultra-dry epoxy cyclohexane.
Background
Epoxycyclohexane, cyclohexene Oxide, has two molecular structures: first, there is one chemically active epoxy group, and thus can be used as a starting material or intermediate for many organic chemical syntheses; and secondly, a six-membered ring with a rigid structure exists in the molecule, and the six-membered ring is introduced into a high molecular chain structure to obtain a high molecular product with high strength, high hardness and good thermal stability. Due to these two characteristics, epoxycyclohexane is widely used for synthesizing high molecular materials.
CN 111333825a discloses a preparation method of carbon dioxide-based polyester-polycarbonate tetrablock copolymer, which synthesizes the polyester-polycarbonate block copolymer through copolymerization of propylene oxide, epoxycyclohexane, phthalic anhydride and CO2, and can effectively improve the glass transition temperature and tensile strength of PPC. However, the purity requirements for epoxycyclohexane are high for such living polymerizations, especially for the synthesis of high molecular weight products, which require a water content of less than 200ppm.
The purity of the epoxycyclohexane obtained in the industrial production at the present stage is 98-99%, and the epoxycyclohexane has a water content exceeding 1wt% after long-time storage and transportation and cannot be directly used for active polymerization reaction. Meanwhile, in the unconverted epoxycyclohexane recycle product in the industrial synthesis, the impurity with active hydrogen is mainly about 2wt% of water. The chemical method for removing water needs to consume a large amount of high-activity dangerous chemicals, so that the common physical method for rectifying the water is more environment-friendly and energy-saving. However, the epoxycyclohexane has good volatility, and can generate a certain degree of azeotropy with water, so that the direct rectification can not achieve the required separation effect.
Disclosure of Invention
The invention aims to overcome the defect of the prior art about the water removal of the epoxy cyclohexane and provides a rectification method for refining ultra-dry epoxy cyclohexane.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a rectification method for refining ultra-dry cyclohexene oxide comprises the following steps:
(1) Mixing the crude product of the epoxy cyclohexane with an azeotropic entrainer, wherein the mass fraction of the azeotropic entrainer is 20% -30%, rectifying the mixture at the temperature of 85-95 ℃ to enable an upper layer oil layer of distillate to flow back to a tower kettle, and separating a lower layer water layer to achieve the water removal effect;
(2) After the crude product of the cyclohexene oxide and the mixture of the azeotropic entrainer are subjected to water diversion, reflux and water removal, continuously heating to 132 ℃, and rectifying the azeotropic entrainer;
(3) And (3) carrying out water diversion, reflux and dehydration on the crude product of the epoxy cyclohexane and the mixture of the azeotropic entrainer, rectifying the entrainer, and then heating to 133 ℃ to obtain the rectified epoxy cyclohexane.
Preferably, in the above-described rectification method: the crude product of the epoxy cyclohexane is the epoxy cyclohexane with the purity of 98-99 percent which is directly produced in industry.
Preferably, in the above-described rectification method: the crude epoxycyclohexane product refers to unconverted epoxycyclohexane recycle in the semi-aromatic polyester polycarbonate synthesis industry.
Preferably, in the above-described rectification method: the azeotropic entrainer is n-hexane.
Preferably, in the above-described rectification method: the rectification time in the step (1) is 1-3 hours at the temperature of 85-95 ℃.
Compared with the prior art, the invention has the following beneficial effects: the purity of the epoxycyclohexane obtained in the industrial production at the present stage is 98-99%, and the epoxycyclohexane has a water content exceeding 1wt% after long-time storage and transportation and cannot be directly used for active polymerization reaction. Meanwhile, in the unconverted epoxycyclohexane recycle product in the industrial synthesis, the impurity with active hydrogen is mainly about 2wt% of water. The chemical method for removing water needs to consume a large amount of high-activity dangerous chemicals, so that the common physical method for rectifying the water is more environment-friendly and energy-saving. However, the epoxycyclohexane has good volatility, and can generate a certain degree of azeotropy with water, so that the direct rectification can not achieve the required separation effect. According to the invention, a great deal of researches prove that n-hexane can be used as an azeotropic entrainer, so that high-efficiency and high-degree dehydration of the epoxy cyclohexane is realized, ultra-dry epoxy cyclohexane is obtained, the water content of the distilled epoxy cyclohexane is lower than 150ppm, the purity is higher than 99.9%, and the recovery rate is higher than 98%. The epoxycyclohexane refined by the method has the characteristic of ultra-dry high purity, and can be used for industrial production with strict requirements on purity and water content, including but not limited to activity-controllable polymerization of semi-aromatic polyester polycarbonate.
Drawings
FIG. 1 is a schematic diagram of a rectification apparatus.
Detailed Description
The invention is described in further detail below in connection with specific embodiments, while providing corresponding apparatus diagrams. However, the present invention is not limited to the steps and apparatuses of the following examples.
Example 1
As shown in figure 1, the raw materials of the refined ultra-dry cyclohexene oxide mainly originate from cyclohexene oxide 8 directly produced in industry and the recovery 7 of the cyclohexene oxide which is not converted in industrial synthesis, and the purity is 98% -99%.
The raw material was mixed with n-hexane in the column pot 1, and the mass fraction of n-hexane was about 25%.
Heating the tower bottom to about 90 ℃, separating steam in a rectifying tower 2, condensing and liquefying the tower top steam through a condenser 3, adjusting a valve 4 to an n-hexane storage 5, standing, cooling and layering the fraction in the n-hexane storage, discharging a water layer from the lower end, and returning n-hexane to the tower bottom through a valve in the middle. This process lasts about 2 hours.
After the water content in the tower kettle reaches the standard, continuously heating to 132 ℃, closing a valve in the middle of the n-hexane storage device during the period, and stopping reflux, thereby separating n-hexane in the tower kettle.
Then heating to 133 ℃, adjusting the valve 4 into the epoxycyclohexane storage tank 6, and collecting the obtained fraction, namely the ultra-dry epoxycyclohexane, with the purity higher than 99.9%, the water content lower than 150ppm and the recovery rate of 98.6%.
Claims (3)
1. The rectification method for refining the ultra-dry cyclohexene oxide is characterized by comprising the following steps of:
(1) Mixing the crude product of the epoxy cyclohexane with an azeotropic entrainer, rectifying the mixture at the temperature of between 85 and 95 ℃ by the mass fraction of the azeotropic entrainer to enable an upper layer oil layer of distillate to flow back to a tower kettle, and separating a lower layer water layer to achieve the water removal effect;
(2) After the crude product of the cyclohexene oxide and the mixture of the azeotropic entrainer are subjected to water diversion, reflux and water removal, continuously heating to 132 ℃, and rectifying the azeotropic entrainer;
(3) The crude product of the epoxy cyclohexane and the mixture of the entrainer are subjected to water diversion, reflux and dehydration, and after the entrainer is rectified, the temperature is raised to 133 ℃, and the epoxy cyclohexane is rectified;
the azeotropic entrainer is n-hexane;
the rectification time in the step (1) is 1-3 hours at the temperature of 85-95 ℃.
2. The rectification method according to claim 1, wherein: the crude product of the epoxy cyclohexane is the epoxy cyclohexane with the purity of 98-99 percent which is directly produced in industry.
3. The rectification method according to claim 1, wherein: the crude epoxycyclohexane product refers to unconverted epoxycyclohexane recycle in the semi-aromatic polyester polycarbonate synthesis industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211668076.2A CN116082276B (en) | 2022-12-23 | 2022-12-23 | Rectification method for refining ultra-dry cyclohexene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211668076.2A CN116082276B (en) | 2022-12-23 | 2022-12-23 | Rectification method for refining ultra-dry cyclohexene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116082276A CN116082276A (en) | 2023-05-09 |
| CN116082276B true CN116082276B (en) | 2024-01-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211668076.2A Active CN116082276B (en) | 2022-12-23 | 2022-12-23 | Rectification method for refining ultra-dry cyclohexene oxide |
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| CN (1) | CN116082276B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106784A (en) * | 1994-11-25 | 1995-08-16 | 岳阳石油化工总厂研究院 | Process for recovery of n-pentanol and cyclohexene oxide from by-product-light oil from cyclohexanol and cyclohexanone preparation by oxidation of cyclohexane |
| CN1180702A (en) * | 1996-10-22 | 1998-05-06 | 岳阳昌德化工实业有限公司 | Method for recovering epoxy cyclohexane from the by-product clean oil of the oxydation of cyclohexane |
| CN1454893A (en) * | 2003-03-22 | 2003-11-12 | 唐前中 | Method of purifying epoxy cyclohexane |
| WO2012048530A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Refining method for crude propylene oxide product and preparation method for propylene oxide |
| CN102786500A (en) * | 2012-08-20 | 2012-11-21 | 浙江工业大学 | Preparation method of cyclohexene oxide |
-
2022
- 2022-12-23 CN CN202211668076.2A patent/CN116082276B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106784A (en) * | 1994-11-25 | 1995-08-16 | 岳阳石油化工总厂研究院 | Process for recovery of n-pentanol and cyclohexene oxide from by-product-light oil from cyclohexanol and cyclohexanone preparation by oxidation of cyclohexane |
| CN1180702A (en) * | 1996-10-22 | 1998-05-06 | 岳阳昌德化工实业有限公司 | Method for recovering epoxy cyclohexane from the by-product clean oil of the oxydation of cyclohexane |
| CN1454893A (en) * | 2003-03-22 | 2003-11-12 | 唐前中 | Method of purifying epoxy cyclohexane |
| WO2012048530A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Refining method for crude propylene oxide product and preparation method for propylene oxide |
| CN102786500A (en) * | 2012-08-20 | 2012-11-21 | 浙江工业大学 | Preparation method of cyclohexene oxide |
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| CN116082276A (en) | 2023-05-09 |
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