CN1171839C - Production method of alpha, omega bielement alcohol - Google Patents
Production method of alpha, omega bielement alcohol Download PDFInfo
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- CN1171839C CN1171839C CNB011352663A CN01135266A CN1171839C CN 1171839 C CN1171839 C CN 1171839C CN B011352663 A CNB011352663 A CN B011352663A CN 01135266 A CN01135266 A CN 01135266A CN 1171839 C CN1171839 C CN 1171839C
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Abstract
The present invention relates to a method for producing alpha, omega-dibasic alcohol, which is an industrial production method of long-chain dibasic alcohol. After alpha, omega-binary acid and low-carbon alcohol reach, hydrogenation reaction is carried out, and then, a product is obtained by vacuum distillation and distillation cut\ collection. The alpha, omega-binary acid which is used as a raw material can adopt the long-chain binary acid produced by petroleum fermentation preferably. The production method of the present invention has the advantages of rich raw materials, easy obtaining, greatly reduced production cost, reasonable process, low cost, obtaining of the product with high purity and good quality, high product efficiency, easy control implementation of process procedures and realization of large-scale industrial production; the alpha, omega-binary acid has high purity, and therefore, a basis is paved for preparing the alpha, omega-dibasic alcohol with high purity and quality.
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 continuous improvement 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-long carbon chain dihydric alcohol, 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-long carbon chain diol production method is characterized in that the long carbon chain diol is C12、C13The long carbon chain dihydric alcohol comprises esterification reaction of dibasic acid, catalytic hydrogenation of ester and reduced pressure distillation, and the product is obtained by collecting distillate, wherein the reaction steps and the control conditions are as follows:
(1) corresponding α, omega-long carbon chain dibasic acid and low carbon chain alcohol are subjected to esterification reaction under the catalysis of sulfuric acid as a catalyst to prepare α, omega-long carbon chain dibasic acid ester, the molar ratio of the long carbon chain dibasic acid to the low carbon chain dibasic acid is controlled to be 1: 2-1: 8, the reaction temperature is 60-90 ℃, the final acid value of the reaction is 25, the reaction time is 4-6 hours, the stirring speed is 50-400 r/m, and the adding amount of the catalyst is 1-2%.
When 1, 12-dodecanedioic acid and low-carbon alcohol are used for preparing 1, 12-dodecanedioic acid ester, the preferable molar ratio of the dibasic acid to the low-carbon alcohol is 1: 8, the reaction temperature is 70-90 ℃, the reaction time is 4-6 hours, the addition amount of the catalyst is 1% -2%, and the acid value is less than 25.
When preparing 1, 13-tridecyl dibasic acid ester, the molar ratio of the co-optimized long carbon chain dibasic acid to the low carbon alcohol is 1: 6, the reaction temperature is 65-75 ℃, the reaction time is 5 hours, and the adding amount of the catalyst is 1.5 percent.
(2) Washing with alkaline water.
(3) Sending the alkali-washed long-carbon-chain dibasic acid ester into a fixed bed with a copper system or a nickel system as a catalyst to carry out hydrogenation reaction, and controlling: the hydrogenation pressure is 15-30MPa, the hydrogenation reaction temperature is 220-310 ℃, the preferredreaction temperature is 250-300 ℃, and the material space velocity is 0.1-0.8 ester m3/m3(catalyst)/h, hydrogen circulation volume of 2000-10000 hydrogen m3/m3(catalyst)/h. The reaction product is first passed through a separator to separate the crude long carbon chain diol from the hydrogen.
(4) The crude long carbon chain dihydric alcohol after hydrogen separation is used for vacuum distillation, low carbon alcohol generated in the reaction is separated from the crude long carbon chain dihydric alcohol, the crude long carbon chain dihydric alcohol is returned to the esterification process to be used as a low carbon alcohol raw material, and the fraction at 230 ℃ of 210-230 ℃ is collected under the pressure of 5.333KPa (namely 40mmHg), namely the required α omega-long carbon chain dihydric alcohol.
Taking the production of 1, 12-dodecanediol as an example, the reaction equation is as follows:
the invention is not described in detail, and can be carried out according to the conventional operation requirements.
The invention has the advantages that the raw material α, omega-long carbon chain dibasic acid, which is used in the invention, can be preferably long carbon chain dibasic acid produced by petroleum fermentation, the raw material is rich and is easy to obtain, the production method has reasonable process, the process is easy to implement and control, high-purity products can be obtained, the product purity reaches more than 99 percent, the quality is good, the yield is high, the yield reaches 96 percent, the product cost is low, and large-scale industrial production can be realized.
Drawings
FIG. 1 is a block diagram of a process flow for the production of α, omega-long carbon chain diols according to the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The production process of 1, 12-dodecahydric alcohol includes compounding dodecanedioic acid and methanol in the molar ratio of 1 to 8, adding sulfuric acid catalyst in the amount of 2 wt% of dibasic acid, esterification in a reactor at 70-80 deg.c for 4 hr, stopping the reaction when the acid value is less than 25, and washing with alkali water. Then pumping the reaction product into a hydrogenation kettle by a high-pressure pump, wherein the space velocity is 0.3 ester m3/m3V (catalyst) h, hydrogen is pressed into the reaction tower by a hydrogen circulating compressor, and the space velocity is 5000 hydrogen m3/m3(catalyst) h Using a copper-based fixed bed catalyst at 22MPaCarrying out hydrogenation reaction under the pressure of (1) and the reaction temperature is 250-300 ℃. And then carrying out reduced pressure distillation treatment on the reaction product, and collecting the 215-220 ℃/40mmHg fraction to obtain the 1, 12-dodecanediol product. Purity 99.3%, yield 93%.
Example 2
The production method of 1, 13-tridecane dibasic alcohol is characterized by that it mixes the tridecane dibasic acid and industrial ethyl alcohol according to the mole ratio of 1: 6, adds sulfuric acid catalyst, its addition quantity is 1.5%, and makes them implement esterification reaction in reaction still, its reaction temperature is 65-75 deg.C, reaction time is 5 hr, when the reaction time is 5 hrWhen the acid value is less than 25, the reaction is stopped and washed with alkaline water. Then pumping the reaction product into a hydrogenation kettle by a high-pressure pump, wherein the space velocity is 0.5 ester m3/m3Hydrogen is pressed into the reaction tower by a hydrogen compression circulator, and the space velocity is 8000 hydrogen m3/m3And (catalyst) h, carrying out hydrogenation reaction by using a nickel-based fixed bed catalyst 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 to obtain the 1, 13-tridecanol product. The purity is 99.6 percent, and the yield is 92 percent.
Example 3
The process for producing 1, 12-dodecanediol comprises mixing dodecanedioic acid and methanol at a molar ratio of 1: 2.5, adding sulfuric acid catalyst at a rate of 1%, carrying out esterification reaction in a reaction kettle at 80-90 deg.C for 6 hr, stopping 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/m3V (catalyst) h, hydrogen is pressed into the reaction tower by a hydrogen compression circulator, and the space velocity is 3000 hydrogen m3/m3And (catalyst) h, carrying out hydrogenation reaction by using a nickel-based fixed bed catalyst 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-dodecadienol product. The purity was 99.2% and the yield was 96%.
Claims (4)
1. A production method of α, omega-long carbon chain dihydric alcohol comprises esterification reaction of dibasic acid, catalytic hydrogenation of esterified product and reduced pressure distillation, and the product is obtained by collecting distillate, and is characterized in that the reaction steps and the control conditions are as follows:
(1) carrying out esterification reaction on corresponding α, omega-long carbon chain dibasic acid and low carbon alcohol under the catalytic action of sulfuric acid as a catalyst to prepare α, omega-long carbon chain dibasic acid ester, and controlling:
the molar ratio of the long carbon chain dibasic acid to the low carbon alcohol is 1: 2-1: 8;
the reaction temperature is 60-90 ℃;
the final acid value of the reaction is less than 25;
the reaction time is 4-6 hours, and the stirring speed is 50-400 r/m;
the adding amount of the catalyst is 1-2%;
said α, omega-long carbon chain dibasic acid is selected from C12、C13The long carbon chain dibasic acid of (1);
(2) washing with alkaline water;
(3) carrying out catalytic hydrogenation reaction by using a fixed bed with a copper system or a nickel system as a catalyst, and controlling:
the hydrogenation pressure is 15-30 MPa;
the hydrogenation reaction temperature is 220-310 ℃;
the material space velocity is 0.1-0.8 ester m3/m3Catalyst/h;
the circulation volume of hydrogen is 2000-10000 hydrogen m3/m3Catalyst/h;
(4) the fraction at 210 ℃ and 230 ℃ is collected under the pressure of 5.333KPa, and the product is obtained.
2. The production process as claimed in claim 1, wherein 1, 12-dodecanedioic acid and lower alcohol are used to prepare 1, 12-dodecanedioic ester, the molar ratio of 1, 12-dodecanedioic acid to lower alcohol is 1: 8, the reaction temperature is 70-90 ℃, the reaction time is 4-6 hours, the amount of catalyst added is 1% -2%, and the acid value is less than 25.
3. The production process according to claim 1, wherein 1, 13-tridecyl dibasic acid ester is prepared from 1, 13-tridecyl dibasic acid and lower alcohol, the molar ratio of 1, 13-tridecyl dibasic acid to lower alcohol is 1: 6, the reaction temperature is 65-75 ℃, the reaction time is 5 hours, the amount of catalyst added is 1.5%, and the acid value is less than 25.
4. A process according to claim 1, 2 or 3, characterized in that the hydrogenation is carried out at a reaction temperature of 250-300 ℃.
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 CN1410405A (en) | 2003-04-16 |
| CN1171839C true 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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Families Citing this family (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 |
| NZ743055A (en) * | 2013-03-08 | 2020-03-27 | Xyleco Inc | Equipment protecting enclosures |
| 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 |
| 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 |
| CN110563553B (en) * | 2019-09-03 | 2021-06-01 | 浙江博聚新材料有限公司 | Preparation method of 1, 12-dodecanediol |
| 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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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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