CN111995611A - Synthesis process of caprolactone - Google Patents
Synthesis process of caprolactone Download PDFInfo
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- CN111995611A CN111995611A CN202010832435.8A CN202010832435A CN111995611A CN 111995611 A CN111995611 A CN 111995611A CN 202010832435 A CN202010832435 A CN 202010832435A CN 111995611 A CN111995611 A CN 111995611A
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- CN
- China
- Prior art keywords
- caprolactone
- temperature
- synthesis
- pressure
- mpa
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- -1 Y type Chemical compound 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a synthesis process of caprolactone, which is characterized in that poly-6-hydroxycaproic acid (6-hydroxycaproic acid oligomer) stays in a catalyst bed layer for a plurality of times at a certain temperature and under a certain pressure, and the obtained product is dehydrated in a distillation tower at a certain temperature and under a certain pressure to obtain the caprolactone. The invention has the beneficial effects that: (1) the method has the advantages of simple steps, simplicity and high reaction progress. (2) The poly-6-hydroxycaproic acid is easy to obtain. (3) The yield of caprolactone reaches over 84 percent.
Description
Technical Field
The invention belongs to the chemical industry, relates to the field of synthesis of caprolactone, and particularly relates to a synthesis process of caprolactone.
Background
Caprolactone is a new type polyester monomer, mainly used for producing synthetic rubber, synthetic fiber and synthetic resin, also used for synthesizing polycaprolactone, adipic acid, adipamide and adhesive, and also can be used for improving the gloss, the permeability resistance and the anti-sticking property by being blended with various resins.
The patent CN 106397386B relates to a method for preparing caprolactone by adding cyclohexanone, auxiliary oxidant acrolein and catalyst carbon material into an organic solvent, taking molecular oxygen as an oxidant, and stirring and reacting for 0.1-24 h under the conditions that the pressure is 0.1-2MPa and the temperature is 60-100 ℃, wherein the molecular oxygen oxidation capacity is weak, the auxiliary oxidant needs to be added, and the selectivity of caprolactone reaches more than 54%.
In patent CN 111018823A, cyclohexanone, catalyst and organic solvent are added into a reaction kettle with oxygen pressure of 0.1-1MPa, the temperature is raised to 30-90 ℃ under stirring, methacrolein is slowly added, and the mixture is continuously stirred for 1-12h to obtain a mixed solution of caprolactone, cyclohexanone, methacrylic acid, methacrolein and organic solvent. The mixed solution is subjected to secondary rectification by a rectifying tower to respectively obtain caprolactone and methacrylic acid, the method has a complex process, and the yield of the caprolactone can reach more than 63 percent.
Disclosure of Invention
In order to solve the above problems, the present invention provides a specific experimental scheme: poly 6-hydroxycaproic acid (6-hydroxycaproic acid oligomer) stays in a catalyst bed layer for a certain time at a certain temperature and under a certain pressure, and the obtained product is dehydrated in a distillation tower at a certain temperature and under a certain pressure to obtain caprolactone.
The catalyst bed is selected from: one or more of a slurry bed, a fixed bed, a fluidized bed and a moving bed.
The catalyst is selected from: alpha-Al2O3And molecular sieve such as Y type, beta type, ZSM-5 type, TS-1, or MCM-22 type molecular sieve.
The adding amount of the catalyst is 50-200% of the mass of the poly-6-hydroxycaproic acid.
The temperature is as follows: 200 ℃ and 380 ℃, preferably 250 ℃ and 300 ℃.
The reaction pressure is as follows: -0.1-2 MPa.
The residence time is 0.05-10 h.
The residence time is 0.05-5 h.
The distillation temperature is 100-120 ℃.
The distillation pressure is-0.1 to-0.025 MPa.
The invention has the beneficial effects that:
(1) the method has the advantages of simple steps, simplicity and high reaction progress.
(2) The yield of caprolactone reaches over 84 percent.
Detailed Description
The invention is further described below with reference to examples. The scope of the invention is not limited thereto.
Example 1
500g of poly-6-hydroxycaproic acid was left for 0.05h at 240 ℃ under-0.1 MPa in a fixed bed carrying 250g of a-Al 2O3 catalyst, and then dehydrated at 100 ℃ under-0.1 MPa to give caprolactone in 84.2% yield.
Example 2
500g of poly-6-hydroxycaproic acid was left for 0.05h at a temperature of 260 ℃ under a pressure of-0.1 MPa in a fixed bed carrying 250g of a catalyst of alpha-Al 2O3, and then dehydrated at a temperature of 100 ℃ under a pressure of-0.1 MPa to give caprolactone in a yield of 87.0%.
Example 3
500g of poly-6-hydroxycaproic acid is kept for 0.05h in a fixed bed carrying 500g of alpha-Al 2O3 catalyst at a temperature of 260 ℃ and a pressure of-0.08 MPa, and then dehydrated at a temperature of 100 ℃ and a pressure of-0.08 MPa, so that the yield of caprolactone is 84.9 percent.
Example 4
500g of poly-6-hydroxycaproic acid was left for 0.5h at a temperature of 280 ℃ under a pressure of-0.1 MPa in a fixed bed carrying 250g of a catalyst of alpha-Al 2O3, and then dehydrated at a temperature of 100 ℃ under a pressure of-0.1 MPa to give caprolactone in a yield of 89.5%.
Example 5
500g of poly-6-hydroxycaproic acid is kept for 1 hour in a moving bed carrying 500g of alpha-Al 2O3 catalyst at the temperature of 320 ℃ and the pressure of-0.1 MPa, and then dehydrated at the temperature of 110 ℃ and the pressure of-0.1 MPa, and the yield of caprolactone is 88.9 percent.
Example 6
500g of poly-6-hydroxycaproic acid is kept for 2 hours in a moving bed carrying 750g of alpha-Al 2O3 catalyst at the temperature of 300 ℃ and the pressure of-0.08 MPa, and then dehydrated at the temperature of 100 ℃ and the pressure of-0.08 MPa, and the yield of caprolactone is 92 percent.
Example 7
500g of poly-6-hydroxycaproic acid is kept in a slurry bed carrying 250g of ZSM-5 type molecular sieve catalyst at the temperature of 260 ℃ and the pressure of-0.1 MPa for 2h, and then dehydrated at the temperature of 100 ℃ and the pressure of-0.06 MPa, so that the yield of caprolactone is 86.9 percent.
Example 8
500g of poly-6-hydroxycaproic acid is kept in a slurry bed carrying 250g of ZSM-5 type molecular sieve catalyst at the temperature of 280 ℃ and the pressure of-0.1 MPa for 3h, and then dehydrated at the temperature of 110 ℃ and the pressure of-0.1 MPa, so that the yield of caprolactone is 89.8 percent.
Example 9
500g of poly-6-hydroxycaproic acid is kept for 0.05h at the temperature of 260 ℃ and the pressure of-0.1 MPa in a fixed bed which is loaded with 500g of ZSM-5 type molecular sieve catalyst, and then dehydrated at the temperature of 100 ℃ and the pressure of-0.1 MPa, and the yield of caprolactone is 85.0 percent.
Example 10
500g of poly-6-hydroxycaproic acid is kept for 0.05h in a fixed bed which is loaded with 750g of ZSM-5 type molecular sieve catalyst and has the temperature of 280 ℃ and the pressure of-0.1 MPa, and then dehydrated at the temperature of 110 ℃ and the pressure of-0.1 MPa, and the yield of caprolactone is 92.7 percent.
Example 11
500g of poly-6-hydroxycaproic acid is kept for 0.05h at a temperature of 280 ℃ and a pressure of-0.1 MPa in a fixed bed carrying 250g of beta-type molecular sieve catalyst, and then dehydrated at a temperature of 100 ℃ and a pressure of-0.1 MPa to obtain the caprolactone with the yield of 84.9 percent.
Example 12
500g of poly-6-hydroxycaproic acid is kept for 0.05h in a fixed bed which is loaded with 500g of beta-type molecular sieve catalyst and has the temperature of 280 ℃ and the pressure of-0.1 MPa, and then dehydrated at the temperature of 110 ℃ and the pressure of-0.1 MPa, and the yield of caprolactone is 91.0 percent.
Example 13
500g of poly-6-hydroxycaproic acid is kept for 0.05h in a fixed bed which is loaded with 750g of beta-type molecular sieve catalyst and has the temperature of 280 ℃ and the pressure of-0.1 MPa, and then dehydrated at the temperature of 120 ℃ and the pressure of-0.1 MPa, and the yield of caprolactone is 94.5 percent.
Example 14
500g of poly-6-hydroxycaproic acid is kept for 0.05h in a fixed bed which is loaded with 750g of beta-type molecular sieve catalyst and has the temperature of 300 ℃ and the pressure of-0.08 MPa, and then dehydrated at the temperature of 120 ℃ and the pressure of-0.08 MPa, so that the yield of caprolactone is 95.1 percent.
The experimental data for examples 1-14 are summarized in the following table:
as can be seen from the above table, the yield of caprolactone in the invention is above 84%.
Claims (10)
1. A synthesis process of caprolactone is characterized in that: poly 6-hydroxycaproic acid (6-hydroxycaproic acid oligomer) stays in a catalyst bed layer for a certain time at a certain temperature and under a certain pressure, and the obtained product is dehydrated in a distillation tower at a certain temperature and under a certain pressure to obtain caprolactone.
2. The process according to claim 1, wherein the synthesis of caprolactone comprises: the reaction equation is as follows:
3. the process according to claim 1, wherein the synthesis of caprolactone comprises:
the catalyst bed is selected from: one or more of a slurry bed, a fixed bed, a fluidized bed and a moving bed;
the catalyst is selected from: alpha-Al2O3Molecular sieves such as one or more of Y-type, beta-type, ZSM-5 type, TS-1 and MCM-22 type molecular sieves;
the adding amount of the catalyst is 50-200% of the mass of the poly-6-hydroxycaproic acid.
4. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the temperature is as follows: 200 ℃ and 380 ℃.
5. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the temperature is as follows: 250 ℃ to 300 ℃.
6. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the reaction pressure is as follows: -0.1-2 MPa.
7. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the residence time is 0.05-10 h.
8. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the residence time is 0.05-5 h.
9. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the distillation temperature is as follows: 100-120 ℃.
10. The process according to claim 1, wherein the synthesis of caprolactone comprises:
the distillation pressure is-0.1-0.025 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010832435.8A CN111995611A (en) | 2020-08-18 | 2020-08-18 | Synthesis process of caprolactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010832435.8A CN111995611A (en) | 2020-08-18 | 2020-08-18 | Synthesis process of caprolactone |
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| Publication Number | Publication Date |
|---|---|
| CN111995611A true CN111995611A (en) | 2020-11-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010832435.8A Pending CN111995611A (en) | 2020-08-18 | 2020-08-18 | Synthesis process of caprolactone |
Country Status (1)
| Country | Link |
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| CN (1) | CN111995611A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656442A (en) * | 2022-04-15 | 2022-06-24 | 北京大学 | Method for preparing caprolactone from 5-hydroxymethyl furoic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449394A (en) * | 2000-08-24 | 2003-10-15 | 联合碳化化学及塑料技术公司 | Processes for the manufacture of lactones |
| CN101679342A (en) * | 2007-06-14 | 2010-03-24 | 巴斯夫欧洲公司 | Method for producing e-caprolacton |
| CN101903368A (en) * | 2007-12-21 | 2010-12-01 | 巴斯夫欧洲公司 | Process for preparing e-caprolactone |
| CN104981464A (en) * | 2013-02-08 | 2015-10-14 | 道达尔研究技术弗吕公司 | Process for preparing cyclic esters and cyclic amides |
| CN106632163A (en) * | 2016-12-07 | 2017-05-10 | 合肥利夫生物科技有限公司 | Preparation method of gamma-caprolactone |
-
2020
- 2020-08-18 CN CN202010832435.8A patent/CN111995611A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449394A (en) * | 2000-08-24 | 2003-10-15 | 联合碳化化学及塑料技术公司 | Processes for the manufacture of lactones |
| CN101679342A (en) * | 2007-06-14 | 2010-03-24 | 巴斯夫欧洲公司 | Method for producing e-caprolacton |
| CN101903368A (en) * | 2007-12-21 | 2010-12-01 | 巴斯夫欧洲公司 | Process for preparing e-caprolactone |
| CN104981464A (en) * | 2013-02-08 | 2015-10-14 | 道达尔研究技术弗吕公司 | Process for preparing cyclic esters and cyclic amides |
| CN106632163A (en) * | 2016-12-07 | 2017-05-10 | 合肥利夫生物科技有限公司 | Preparation method of gamma-caprolactone |
Non-Patent Citations (1)
| Title |
|---|
| SANG-HYUN PYO等: "A sustainable synthetic route for biobased", 《GREEN CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656442A (en) * | 2022-04-15 | 2022-06-24 | 北京大学 | Method for preparing caprolactone from 5-hydroxymethyl furoic acid |
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Application publication date: 20201127 |
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