CN110563553A - Preparation method of 1, 12-dodecanediol - Google Patents
Preparation method of 1, 12-dodecanediol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The application relates to the technical field of pharmaceutical chemicals, in particular to a preparation method of 1, 12-dodecanediol. The method adopts esterification reaction of dodecanedioic acid and n-hexanol to obtain dihexyl dodecanedioic acid, and then prepares the target product 1, 12-dodecanediol through hydrogenation reduction. The method does not need catalyst, reduces the catalyst separation steps, realizes esterification, reduces the production steps and reduces the production cost.
Description
Technical Field
The application relates to the technical field of pharmaceutical chemicals, in particular to a preparation method of 1, 12-dodecanediol.
Background
the 1, 12-dodecanediol is used for synthesizing medicines, high-grade coatings, high-grade printing ink, high-grade resin, synthetic fiber rubber, a surfactant and the like, is white solid at normal temperature, is environment-friendly and has good chemical stability. The high carbon dibasic acid is esterified with methanol to generate high carbon dibasic ester, then hydrogenated to prepare high carbon dibasic alcohol, and finally rectified and purified to obtain pure high carbon dibasic alcohol, so that the purity of the product can be effectively improved, the generation of byproducts is reduced, the three wastes are less, and the raw materials are easy to obtain.
The Chinese patent application (publication No. CN 109678657A) discloses a method for preparing high-carbon dihydric alcohol by continuously hydrogenating high-carbon dibasic acid, which comprises the following steps:
(1) And esterification reaction: uniformly mixing high-carbon dibasic acid, a solvent and a cosolvent according to a proportion, and adding the solution into a preheater filled with a solid acid catalyst to perform an esterification reaction;
(2) And catalytic hydrogenation: mixing the material passing through the preheater with hydrogen, carrying out hydrogenation reaction in the presence of a hydrogenation catalyst, and carrying out gas-liquid separation on the reaction material after passing through a cooler to obtain a high-carbon dihydric alcohol crude product;
(3) And high-carbon polyhydric alcohol rectification: and (3) purifying the high-carbon-content dihydric alcohol crude product obtained in the step (2) by adopting a continuous rectification method to finally obtain the high-carbon-content dihydric alcohol crude product.
The Chinese patent application (publication number CN 104961627A) discloses a preparation method of 1, 10-decanediol, which comprises the following steps: adding sebacic acid, decanediol and a titanate catalyst into a dry wax esterification reaction kettle, slowly heating to 130-180 ℃ under stirring, and finishing vacuum dehydration reaction for 5-30 hours to obtain decanediol sebacate wax ester; the decanediol sebacate wax ester is subjected to reduction reaction with hydrogen under the action of a hydrogenation catalyst, the hydrogen pressure is maintained at 10.0MPa to 20.0MPa, and the hydrogen flow rate is 300m3/h～1000m3And h, generating a crude decanediol product, and distilling under high vacuum to obtain the 1, 10-decanediol.
In the method, the esterification of the high-carbon dihydric alcohol needs to be carried out by adding a catalyst, after the esterification is finished, the post-treatment is carried out, the catalyst is separated, and if the esterification is not carried out, the influence on the catalytic hydrogenation catalyst applied in the subsequent application (the poisoning of the catalyst is caused) and the product quality are influenced.
in addition, mixed C6 monohydric alcohol is co-produced in the production process of 1, 6-hexanediol, and the mixed C6 monohydric alcohol mainly comprises n-hexanol and 20-30% of methylcyclopentanol and the like.
Disclosure of Invention
in order to solve the technical problem that the catalyst needs to be separated after the esterification is finished, the first object of the application is to provide a preparation method of 1, 12-dodecanediol, which can realize the esterification without using the catalyst, reduce the catalyst separation steps, reduce the production steps and reduce the production cost. The second object of the present application is to provide a method for separating high purity n-hexanol from a by-product containing n-hexanol, which realizes separation of high purity n-hexanol from a by-product of n-hexanol, providing added value to the by-product.
In order to achieve the first object, the following technical solutions are adopted in the present application:
The method adopts esterification reaction of dodecanedioic acid and n-hexanol to obtain dihexyl dodecanedioic acid, and then prepares the target product 1, 12-dodecanediol through hydrogenation reduction of the dihexyl dodecanedioic acid.
Preferably, the n-hexanol is a by-product containing more than 20% by weight of n-hexanol and C6 monohydric alcohol except n-hexanol.
preferably, the n ~ hexanol is a by ~ product generated in the production of 1, 6 ~ hexanediol, and the by ~ product contains 30 ~ 40% of n ~ hexanol and 20 ~ 30% of methylcyclopentanol by weight percentage.
preferably, the mass ratio of the dodecanedioic acid to the n ~ hexanol is 1 (2 ~ 5), the reaction time is 8 ~ 12 hours, the esterification reaction temperature is 150 ~ 220 ℃, the medium acid value is less than 40mgKOH/g, and after the reaction is finished, the excessive n ~ hexanol is removed through reduced pressure distillation to obtain the dihexyl dodecanedioic acid.
preferably, the dihexyl dodecanedioate is subjected to catalytic hydrogenation reduction by passing through a hydrogenation reaction tower filled with a catalyst under the pressure of 1 ~ 20MPa, preferably 5 ~ 20MPa, at the temperature of 100 ~ 220 ℃ and preferably 130 ~ 220 ℃ to obtain a crude product of 1,12 ~ dodecanediol.
Preferably, the catalyst is a supported copper catalyst. The catalyst can realize lower hydrogenation pressure, lower hydrogenation temperature and lower hydrogen-ester ratio for the catalytic hydrogenation of the dihexyl dodecanedioate.
In order to achieve the second object, the following technical solutions are adopted in the present application:
The process of separating high purity n-hexanol from n-hexanol containing side product includes esterification of dodecanedioic acid with n-hexanol containing side product to obtain dihexyl dodecanedioate, hydrogenation to reduce 1, 12-dodecanediol and hydrogenation to reduce n-hexanol to obtain high purity n-hexanol.
preferably, the dihexyl dodecanedioate passes through a hydrogenation reaction tower filled with a catalyst, hydrogen is introduced, the pressure is controlled to be 1 ~ 20MPa, the temperature is controlled to be 100 ~ 220 ℃, and the catalytic hydrogenation reduction is carried out to obtain a 1,12 ~ dodecanediol crude product.
Preferably, the catalyst is a supported copper catalyst.
preferably, the esterification reaction is carried out to remove excessive byproducts of n ~ hexanol and methylcyclopentanol by reduced pressure distillation, so as to obtain methylcyclopentanol with the mass percentage content of 60 ~ 70%.
Due to the adoption of the technical scheme, the dodecanedioic acid and the n-hexanol belong to the catalyst-free esterification reaction. In the process, the n-hexanol is a reaction raw material and a good esterification water-carrying solvent, and water generated by the esterification reaction can be separated out of a reaction system, so that the esterification reaction is smoothly carried out. No catalyst is used in the esterification process, and no complex post-treatment process is needed after the esterification is finished.
The catalyst-free in this application means that the reaction can be carried out without adding an additional catalyst in general, but if a part of the catalyst is added to further increase the rate or conversion of the reaction and to facilitate separation, it should be included in this application, for example, the addition of a resin acid catalyst during esterification to further increase the rate or conversion of the reaction.
In addition, cyclopentyl alcohols in the mixed alcohol as a byproduct of n-hexanol are difficult to form esters due to steric hindrance, while n-hexanol is a straight chain and is easy to form dibasic esters. In the subsequent application, n-hexanol with the content of more than 99.0% can be separated and purified in the hydrogenation process, and methylcyclopentanol with high purity (60-70%) can be separated in the esterification process and used as perfume; can also be used as surfactant, plasticizer, etc. Thereby improving the market application added value of the byproduct n-hexanol.
the catalytic hydrogenation catalyst for the dihexyl dodecanedioate is a supported copper ~ zinc catalyst, and is a copper ~ zinc catalyst prepared by an impregnation method through improvement of a carrier, and the catalytic hydrogenation of the dihexyl dodecanedioate by the catalyst can realize lower hydrogenation pressure (1 ~ 20 MPa), lower hydrogenation temperature (100 ~ 220 ℃) and lower hydrogen ~ ester ratio.
The conversion rate of the raw material dihexyl dodecanedioate is more than or equal to 99.5%, and the selectivity of 1, 12-dodecanediol is more than or equal to 98.0%. And rectifying and purifying the crude product to obtain the target product 1, 12-dodecanediol. The purity of the product is detected to be more than or equal to 99.5 percent.
Drawings
FIG. 1 is a reaction equation of the present application.
Fig. 2 is a process flow diagram of the present application.
FIGS. 3 and 4 are the spectra of 1, 12-dodecanediol and n-hexanol prepared in example 6 of the present application.
FIGS. 5 and 6 are the spectra of 1, 12-dodecanediol and n-hexanol prepared in example 7 of the present application.
FIGS. 7 and 8 are the spectra of 1, 12-dodecanediol and n-hexanol prepared in example 8 of the present application.
FIGS. 9 and 10 are the spectra of 1, 12-dodecanediol and n-hexanol prepared in example 9 of the present application.
FIGS. 11 and 12 show the spectra of 1, 12-dodecanediol and n-hexanol prepared in example 10 of the present application.
Detailed Description
The original source of the application:
1. Dodecanedioic acid is prepared from biomass raw materials by Zhejiang Bomo New Material Co., Ltd through a fermentation method to obtain a crude product, and the crude product is refined and purified to obtain the dodecanedioic acid.
2. the byproduct n ~ hexanol is a byproduct generated in the production of 1, 6 ~ hexanediol of Zhejiang Bopolymer new materials Co., Ltd, and the n ~ hexanol content is 30 ~ 40%, and 20 ~ 30% of mixed C6 monohydric alcohol such as methylcyclopentanol.
As shown in fig. 1, the target product 1, 12-dodecanediol (shown in fig. 2) is prepared by esterification and hydrogenation reduction of dodecanedioic acid derived from biomass and byproduct n-hexanol serving as raw materials.
Example 1: 575 g dodecanedioic acid and 2875 g of the n-hexanol mixture are put into a reaction bottle, stirred and heated. And (4) refluxing the reaction, and separating water generated in the reaction. And finally heating to 150 ℃ for reflux reaction, carrying out reflux water diversion reaction for 8 hours, sampling and detecting, measuring the acid value of the sample to be 36.1mgKOH/g, stopping heat preservation and reflux after the reaction is finished, and cooling the material for later use.
Example 2: 575 g of dodecanedioic acid and 2300 g of the n-hexanol mixture are put into a reaction bottle, stirred and heated. And (4) refluxing the reaction, and separating water generated in the reaction. And finally heating to 170 ℃ for reflux reaction, carrying out reflux water diversion reaction for 9 hours, sampling and detecting, measuring the acid value of the sample to be 32.1mgKOH/g, stopping heat preservation and reflux after the reaction is finished, and cooling the material for later use.
Example 3: 575 g dodecanedioic acid and 2012.5 g of n-hexanol mixture are put into a reaction bottle, stirred and heated. And (4) refluxing the reaction, and separating water generated in the reaction. And finally, heating to 185 ℃, carrying out reflux water diversion reaction for 10 hours, sampling and detecting, measuring the acid value of a sample to be 30.3mgKOH/g, stopping heat preservation and reflux after the reaction is finished, and cooling the material for later use.
Example 4: 575 g dodecanedioic acid and 1725 g of n-hexanol mixture are added into a reaction bottle, stirred and heated. And (4) refluxing the reaction, and separating water generated in the reaction. And finally, heating to 200 ℃, carrying out reflux water diversion reaction for 11 hours, sampling and detecting, measuring the acid value of the sample to be 27.6mgKOH/g, stopping heat preservation and refluxing after the reaction is finished, and cooling the material for later use.
Example 5: 575 g dodecanedioic acid and 1150 g of n-hexanol mixture are put into a reaction bottle, stirred and heated. And (4) refluxing the reaction, and separating water generated in the reaction. And finally, heating to 220 ℃, carrying out reflux water diversion reaction for 12 hours, sampling and detecting, measuring the acid value of the sample to be 24.5mgKOH/g, stopping heat preservation and reflux after the reaction is finished, and cooling the material for later use.
Example 6: 200g of hydrogenation catalyst and a proper amount of catalyst auxiliary materials are filled in a hydrogenation reactor with the diameter of 40mm and the length of 1800mm, the temperature in the reactor is maintained at 130 ℃, the hydrogen pressure is maintained at 20MPa, hydrogen enters the hydrogenation reactor from the lower end, dodecanedioic acid ester prepared in the first embodiment enters the hydrogenation reactor from the lower end, the feeding flow rate of the dodecanedioic acid ester is controlled at 120 g per hour, a product of the hydrogenation reaction flows out from the upper end of the hydrogenation reactor, the effluent is cooled to 50 ℃ by a condenser and then transferred to a distillation device, and a crude product is sampled, detected and analyzed. The conversion of the starting ester was 99.61% and the selectivity to 1, 12-dodecanediol was 98.23%. Rectifying the crude product, distilling out front and rear fractions, and collecting fraction I: n-hexanol. Collecting a second fraction: 1, 12-dodecanediol. The n-hexanol prepared above was measured by gas chromatography, and as shown in fig. 4, the n-hexanol content was 99.12%, and as shown in fig. 3, the 1, 12-dodecanediol total content was 99.56% by gas chromatography.
Example 7: 200g of hydrogenation catalyst and a proper amount of catalyst auxiliary materials are filled in a hydrogenation reactor with the diameter of 40mm and the length of 1800mm, the temperature in the reactor is maintained at 150 ℃, the hydrogen pressure is maintained at 16MPa, hydrogen enters the hydrogenation reactor from the lower end, dodecanedioic acid ester prepared in the second embodiment enters the hydrogenation reactor from the lower end, the feeding flow rate of the dodecanedioic acid ester is controlled at 120 g per hour, a product of the hydrogenation reaction flows out from the upper end of the hydrogenation reactor, the effluent is cooled to 50 ℃ by a condenser and then transferred to a distillation device, and a crude product is sampled, detected and analyzed. The conversion of the starting ester was 99.57% and the selectivity to 1, 12-dodecanediol was 98.18%. Rectifying the crude product, distilling out front and rear fractions, and collecting fraction I: n-hexanol. Collecting a second fraction: 1, 12-dodecanediol. The n-hexanol prepared above was measured by gas chromatography, and as shown in fig. 6, the n-hexanol content was 99.25%, and as shown in fig. 5, the 1, 12-dodecanediol content was 99.62% in total by gas chromatography.
Example 8: 200g of hydrogenation catalyst and a proper amount of catalyst auxiliary materials are filled in a hydrogenation reactor with the diameter of 40mm and the length of 1800mm, the temperature in the reactor is maintained at 170 ℃, the hydrogen pressure is maintained at 12MPa, hydrogen enters the hydrogenation reactor from the lower end, dodecanedioic acid ester prepared in the third embodiment enters the hydrogenation reactor from the lower end, the feeding flow rate of the dodecanedioic acid ester is controlled at 120 g per hour, a product of the hydrogenation reaction flows out from the upper end of the hydrogenation reactor, the effluent is cooled to 50 ℃ by a condenser and then transferred to a distillation device, and a crude product is sampled, detected and analyzed. The conversion of the starting ester was 99.66% and the selectivity to 1, 12-dodecanediol was 98.35%. Rectifying the crude product, distilling out front and rear fractions, and collecting fraction I: n-hexanol. Collecting a second fraction: 1, 12-dodecanediol. The n-hexanol prepared above was measured by gas chromatography, and as shown in fig. 8, the n-hexanol content was 99.09%, and as shown in fig. 7, the 1, 12-dodecanediol was measured by gas chromatography, and the total 1, 12-dodecanediol content was 99.81%.
Example 9: 200g of hydrogenation catalyst and a proper amount of catalyst auxiliary materials are filled in a hydrogenation reactor with the diameter of 40mm and the length of 1800mm, the temperature in the reactor is maintained at 195 ℃, the hydrogen pressure is maintained at 9MPa, hydrogen enters the hydrogenation reactor from the lower end, dodecanedioic acid ester prepared in the fourth embodiment enters the hydrogenation reactor from the lower end, the feeding flow rate of the dodecanedioic acid ester is controlled at 120 g per hour, a product of the hydrogenation reaction flows out from the upper end of the hydrogenation reactor, the effluent is cooled to 50 ℃ by a condenser and then transferred to a distillation device, and a crude product is sampled, detected and analyzed. The conversion of the starting ester was 99.70% and the selectivity to 1, 12-dodecanediol was 98.45%. Rectifying the crude product, distilling out front and rear fractions, and collecting fraction I: n-hexanol. Collecting a second fraction: 1, 12-dodecanediol. The n-hexanol prepared above was measured by gas chromatography, and as shown in fig. 10, the n-hexanol content was 99.21%, and as shown in fig. 9, the 1, 12-dodecanediol content was 99.72% in total by gas chromatography.
Example 10: 200g of hydrogenation catalyst and a proper amount of catalyst auxiliary materials are filled in a hydrogenation reactor with the diameter of 40mm and the length of 1800mm, the temperature in the reactor is maintained at 220 ℃, the hydrogen pressure is maintained at 5MPa, hydrogen enters the hydrogenation reactor from the lower end, dodecanedioic acid ester prepared in the fifth embodiment enters the hydrogenation reactor from the lower end, the feeding flow rate of the dodecanedioic acid ester is controlled at 120 g per hour, a product of the hydrogenation reaction flows out from the upper end of the hydrogenation reactor, the effluent is cooled to 50 ℃ by a condenser and then transferred to a distillation device, and a crude product is sampled, detected and analyzed. The conversion of the starting ester was 99.68% and the selectivity to 1, 12-dodecanediol was 98.31%. Rectifying the crude product, distilling out front and rear fractions, and collecting fraction I: n-hexanol. Collecting a second fraction: 1, 12-dodecanediol. The n-hexanol prepared above was measured by gas chromatography, and as shown in fig. 12, the n-hexanol content was 99.16%, and as shown in fig. 11, the 1, 12-dodecanediol total content was 99.68% by gas chromatography.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present disclosure, including any person skilled in the art, having the benefit of the present disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of 1, 12-dodecanediol is characterized in that dodecanedioic acid and n-hexanol are subjected to esterification reaction to obtain dihexyl dodecanedioic acid, and the dihexyl dodecanedioic acid is subjected to hydrogenation reduction to prepare the target product 1, 12-dodecanediol.
2. The process according to claim 1, wherein n-hexanol is a by-product containing n-hexanol, wherein the by-product contains more than 20 wt% of n-hexanol and C6 monoalcohols other than n-hexanol.
3. the method of claim 1,12 ~ dodecanediol, wherein n ~ hexanol is a by ~ product of 1, 6 ~ hexanediol production, and the by ~ product comprises 30 ~ 40 wt% of n ~ hexanol and 20 ~ 30 wt% of methylcyclopentanol.
4. the method for preparing 1,12 ~ dodecanediol according to claim 1, wherein the mass ratio of dodecanedioic acid to n ~ hexanol is 1 (2 ~ 5), the reaction time is 8 ~ 12 hours, the esterification reaction temperature is 150 ~ 220 ℃, the medium ~ controlled acid value is less than 40mgKOH/g, and after the reaction is finished, the excess n ~ hexanol is removed by reduced pressure distillation to obtain dihexyl dodecanedioate.
5. the method for preparing 1,12 ~ dodecanediol according to claim 1, wherein the dihexyl dodecanedioate is subjected to catalytic hydrogenation reduction by passing through a hydrogenation reaction tower filled with a catalyst under a pressure of 1 ~ 20MPa and at a temperature of 100 ~ 220 ℃ to obtain a crude product of 1,12 ~ dodecanediol.
6. The process according to claim 6, wherein the catalyst is a supported copper catalyst.
7. The method is characterized in that dodecanedioic acid and the byproduct containing the n-hexanol are subjected to esterification reaction to obtain dihexyl dodecanedioate, 1, 12-dodecanediol is prepared by hydrogenation reduction, and the high-purity n-hexanol is obtained by hydrogenation reduction.
8. the method for separating high ~ purity n ~ hexanol from a by ~ product containing n ~ hexanol according to claim 7, wherein the dihexyl dodecanedioate is subjected to catalytic hydrogenation reduction by passing through a hydrogenation reaction tower filled with a catalyst and introducing hydrogen at a pressure of 1 ~ 20MPa and a temperature of 100 ~ 220 ℃ to obtain a crude product of 1,12 ~ dodecanediol.
9. The process of claim 8, wherein the catalyst is a supported copper based catalyst.
10. the method for separating high ~ purity n ~ hexanol from a by ~ product containing n ~ hexanol according to claim 7, wherein the esterification reaction is performed to remove excess n ~ hexanol and methylcyclopentanol by reduced pressure distillation to obtain methylcyclopentanol with a mass percentage content of 60 ~ 80%.
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| CN113683483A (en) * | 2021-06-07 | 2021-11-23 | 浙江博聚新材料有限公司 | Production method and device of high-purity 1, 6-hexanediol |
| US11492316B1 (en) | 2021-06-07 | 2022-11-08 | Zhejiang Boju New Materials Co., Ltd. | Production method and production device of high-purity 1,6-hexanediol |
| CN114230438A (en) * | 2021-12-30 | 2022-03-25 | 南京中设石化工程有限公司 | Process for producing fatty alcohols |
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