CN1410405A - Production method of alpha, omega bielement alcohol - Google Patents
Production method of alpha, omega bielement alcohol Download PDFInfo
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- CN1410405A CN1410405A CN 01135266 CN01135266A CN1410405A CN 1410405 A CN1410405 A CN 1410405A CN 01135266 CN01135266 CN 01135266 CN 01135266 A CN01135266 A CN 01135266A CN 1410405 A CN1410405 A CN 1410405A
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Abstract
A process for preparing alpha, omega-binary alcohol includes such steps as reaction of alpha, omega-dibasic acid on low-carbon alcohol, hydrogenating reaction, pressure-reduction distilling and collecting fractions to obtain the product. It is preferable to choose long-chain dibasic and prepared by fermenting petroleum as the said alpha, omega-dibasic acid. Its advantages are low cost, and high purity, quality and output rate of the product.
Description
Technical Field
The invention relates to a production method of α, omega-dihydric alcohol, which is an industrial production method of long-chain dihydric alcohol.
Background
The long-chain alcohol plays an important role in national economy, the demand of the long-chain alcohol is continuously increased along with the development of economy and the continuousimprovement of the living standard of people, in the fields of medicine synthesis, cosmetics, plasticizers, high polymer and the like, the demand of α omega-diol is larger, the domestic industrially produced diol only contains ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, and can not meet the supply demand in the fields of production, life and the like, the research and development of 1, 8-octanediol, 1, 10-decanediol and the like with longer carbon chains is still in a laboratory stage, and the long-chain alcohol is prepared by a metal sodium reduction method mostly, has low yield and high cost, and is difficult to realize large-scale industrial production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a production method of α omega-diol, which has the advantages of wide raw material source, reasonable production process, low production cost, good product quality and high yield, and can realize large-scale industrial production.
The α omega-dihydric alcohol production method comprises the steps of reacting α omega-dibasic acid with low-carbon alcohol, then carrying out hydrogenation reaction, finally carrying out reduced pressure distillation, and collecting fractions to obtain the product.
Wherein:
α, mixing the reaction materials of omega-dibasic acid and low carbon alcohol according to the molar ratio of 1: 2-8.
α, the catalyst used in the reaction of the omega-dibasic acid and the low carbon alcohol is sulfuric acid, and the addition amount is 0.1-2.0% of the weight of the dibasic acid.
Examples of the lower alcohol include methanol and ethanol.
The control conditions of the reaction are as follows: the temperature is 60-100 ℃, the time is 1-6 hours, and the stirring speed is 50-400 r/min.
The hydrogenation catalyst is copper catalyst, nickel catalyst, fixed bed type catalytic reaction.
The control conditions of the hydrogenation reaction are as follows:
the pressure is 15-30 Mpa, the temperature is 200-350 ℃, and the material airspeed is 0.1-0.8 ester m3/m3(catalyst)/h, the hydrogen circulation volume is 2000-10000 hydrogen m3/m3(catalyst)/h.
And (3) carrying out reduced pressure distillation on the product after the reduced pressure reaction, and collecting a fraction at 210-230 ℃/40mmHg, namely an α omega-diol product.
The equations in the reaction are:
the invention is not described in detail, and can be carried out according to the conventional operation requirements.
The raw material α, omega-diacid can be optimized to long-chain diacid produced by petroleum fermentation, the raw material is rich and easy to obtain, the production cost can be greatly reduced, and α, omega-diacid obtained by petroleum fermentation has high purity, so that a foundation is laid for preparing α, omega-diacid with high purity and high quality.
Drawings
FIG. 1 is a block flow diagram of an embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The production method of 1, 12-dodecanediol comprises the steps of mixing dodecanedioic acid and methanol according to the molar ratio of 1: 8, adding a sulfuric acid catalyst, wherein the addition amount is 2% of the weight of the dibasic acid, carrying out esterification reaction in a reaction kettle at the reaction temperature of 70-80 ℃ for 4 hours, stopping the reaction when the acid value is less than 25, and washing with alkaline water. Then pumping the reaction product into a hydrogenation kettle by a high-pressure pump, wherein the space velocity is 0.3 ester m3/m3(catalyst)/h, hydrogen is pressed into the reaction tower by a hydrogen compression circulator, and the space velocity is 5000 hydrogen m3/m3(catalyst)/h, using copper fixed bed catalyst, carrying out hydrogenation reaction under the pressure of 22Mpa, the reaction temperature is 250-300 ℃. Then will beAnd carrying out reduced pressure distillation treatment on the reaction product, and collecting 215-220 ℃/40mmHg fractions, namely the 1, 12-dodecadienol product. Purity 99.3%, yield 93%.
Example 2
The production process of 1, 13-tridecanediol includes compounding tridecanedioic acid and industrial alcohol in the molar ratio of 1 to 6, adding sulfuric acid catalyst in 1.5% and esterification in a reactor at 65-75 deg.c for 5 hr, and washing with alkali water after the acid value is less than 25. Then pumping the reaction product into a hydrogenation kettle by a high-pressure pump, wherein the space velocity is 0.5 ester m3/m3(catalyst)/h, hydrogen is pressed into the reaction tower by a hydrogen compression circulator,space velocity of 8000 hydrogen m3/m3(catalyst)/h, using nickel fixed bed catalyst, carrying out hydrogenation reaction under the pressure of 25Mpa, wherein the reaction temperature is 230-310 ℃. And then carrying out reduced pressure distillation treatment on the reaction product, and collecting the fraction at 200-230 ℃/40mmHg, namely the 1, 13-tridecyl alcohol product. The purity is 99.6 percent, and the yield is 92 percent.
Example 3
The production method of 1, 12-dodecanediol comprises the steps of mixing dodecanedioic acid and methanol according to the molar ratio of 1: 2.5, adding a sulfuric acid catalyst, wherein the addition amount is 1%, carrying out esterification reaction in a reaction kettle at the reaction temperature of 80-90 ℃ for 6 hours, stopping the reaction when the acid value is less than 25, and washing with alkaline water. Then pumping the reaction product into a hydrogenation kettle by a high-pressure pump, wherein the space velocity is 0.25 ester m3/m3(catalyst)/h, hydrogen is pressed into the reaction tower by a hydrogen compression circulator, and the space velocity is 3000 hydrogen m3/m3(catalyst)/h, using nickel fixed bed catalyst, carrying out hydrogenation reaction under the pressure of 22Mpa, wherein the reaction temperature is 220-260 ℃. And then carrying out reduced pressure distillation treatment on the reaction product, and collecting fractions at 210-220 ℃/40mmHg, namely the 1, 12-dodecanediol product. The purity was 99.2% and the yield was 96%.
Claims (9)
1. A process for preparing α omega-diol includes such steps as reaction between α omega-diacid and low-carbon alcohol, hydrogenation reaction, vacuum distillation and collecting fraction.
2. The production method according to claim 1, wherein α, the molar ratio of the omega-dibasic acid to the low-carbon alcohol reactant material is 1: 2-8.
3. The production method according to claim 1, wherein the catalyst used for the reaction of α omega-dibasic acid and lower alcohol is sulfuric acid.
4. The production process according to claim 3, wherein the catalyst is added in an amount of 0.1 to 2.0%.
5. The production method according to claim 4, characterized in that the reaction conditions are: the temperature is 60-100 ℃, the time is 1-6 hours, and the stirring speed is 50-400 r/min.
6. The production process according to claim 1, wherein the hydrogenation catalyst is a copper-based catalyst or a nickel-based catalyst.
7. The production process according to claim 6, wherein the hydrogenation is catalyzed to a fixed bed type.
8. The production process according to claim 7, wherein the hydrogenation reaction conditions are:
the pressure is 15-30 Mpa, the temperature is 200-350 ℃, and the material airspeed is 0.1-0.8 ester m3/m3(catalyst)/h, the hydrogen circulation volume is 2000-10000 hydrogen m3/m3(catalyst)/h.
9. The production method according to any one of claims 1 to 8, wherein the distillation is carried out under reduced pressure, and a fraction of 210 to 230 ℃/40mmHg is collected as a product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011352663A CN1171839C (en) | 2001-12-21 | 2001-12-21 | Production method of alpha, omega bielement alcohol |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011352663A CN1171839C (en) | 2001-12-21 | 2001-12-21 | Production method of alpha, omega bielement alcohol |
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| CN1410405A true CN1410405A (en) | 2003-04-16 |
| CN1171839C CN1171839C (en) | 2004-10-20 |
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| CNB011352663A Expired - Lifetime CN1171839C (en) | 2001-12-21 | 2001-12-21 | Production method of alpha, omega bielement alcohol |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617280A (en) * | 2012-02-20 | 2012-08-01 | 青岛俪徕精细化工有限公司 | Production method for long carbon chain perfluor alcohol |
| CN103449971A (en) * | 2013-08-07 | 2013-12-18 | 青岛俪徕精细化工有限公司 | Production method of alpha,omega-long carbon chain n-dihydric alcohol |
| CN104529741A (en) * | 2014-12-26 | 2015-04-22 | 淄博广通化工有限责任公司 | Purification method of long-carbon-chain dicarboxylic acid |
| CN105189765A (en) * | 2013-03-08 | 2015-12-23 | 希乐克公司 | Processing and converting biomass |
| CN109678657A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The method that high carbon dicarboxylic acid continuously hydrogen adding prepares high-carbon dihydric alcohol |
| CN110563553A (en) * | 2019-09-03 | 2019-12-13 | 浙江博聚新材料有限公司 | Preparation method of 1, 12-dodecanediol |
| CN115417748A (en) * | 2021-06-01 | 2022-12-02 | 青岛俪徕精细化工有限公司 | Continuous preparation method of environment-friendly multi-carbon normal dihydric alcohol |
-
2001
- 2001-12-21 CN CNB011352663A patent/CN1171839C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617280A (en) * | 2012-02-20 | 2012-08-01 | 青岛俪徕精细化工有限公司 | Production method for long carbon chain perfluor alcohol |
| CN105189765A (en) * | 2013-03-08 | 2015-12-23 | 希乐克公司 | Processing and converting biomass |
| US10543460B2 (en) | 2013-03-08 | 2020-01-28 | Xyleco, Inc. | Upgrading process streams |
| CN103449971A (en) * | 2013-08-07 | 2013-12-18 | 青岛俪徕精细化工有限公司 | Production method of alpha,omega-long carbon chain n-dihydric alcohol |
| CN103449971B (en) * | 2013-08-07 | 2014-12-17 | 青岛俪徕精细化工有限公司 | Production method of alpha,omega-long carbon chain n-dihydric alcohol |
| CN104529741A (en) * | 2014-12-26 | 2015-04-22 | 淄博广通化工有限责任公司 | Purification method of long-carbon-chain dicarboxylic acid |
| CN104529741B (en) * | 2014-12-26 | 2016-03-30 | 淄博广通化工有限责任公司 | The method of purification of Long carbon chain di-carboxylic acid |
| CN109678657A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The method that high carbon dicarboxylic acid continuously hydrogen adding prepares high-carbon dihydric alcohol |
| CN110563553A (en) * | 2019-09-03 | 2019-12-13 | 浙江博聚新材料有限公司 | Preparation method of 1, 12-dodecanediol |
| CN115417748A (en) * | 2021-06-01 | 2022-12-02 | 青岛俪徕精细化工有限公司 | Continuous preparation method of environment-friendly multi-carbon normal dihydric alcohol |
| CN115417748B (en) * | 2021-06-01 | 2024-05-14 | 青岛俪徕精细化工有限公司 | Continuous preparation method of environment-friendly multi-carbon normal dihydric alcohol |
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|---|---|
| CN1171839C (en) | 2004-10-20 |
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Owner name: QINGDAO LILAI FINE CHEMICAL CO., LTD. Free format text: FORMER OWNER: ZIBO GUANGTONG CHEMICAL INDUSTRY ROMPLAST-14 O., LTD Effective date: 20090807 |
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Effective date of registration: 20090807 Address after: No. 27 London Road, Qingdao Free Trade Zone Patentee after: Qingdao Lilai Fine Chemical Co., Ltd. Address before: West head, Longquan Town, Zichuan District, Zibo, Shandong Patentee before: Guangtong Chemical Co., Ltd., Zibo |
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