CN110092719B - Synthetic method of gulonic acid methyl ester - Google Patents
Synthetic method of gulonic acid methyl ester Download PDFInfo
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- CN110092719B CN110092719B CN201810096475.3A CN201810096475A CN110092719B CN 110092719 B CN110092719 B CN 110092719B CN 201810096475 A CN201810096475 A CN 201810096475A CN 110092719 B CN110092719 B CN 110092719B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a synthetic method of gulonic acid methyl ester. According to the method, a material formed by mixing acidic ion exchange resin and polytetrafluoroethylene particles is used as a catalyst and is filled in a fixed bed reactor in a specific proportion, the method can be used for efficiently catalyzing gulonic acid and methanol to react and dehydrate at a lower temperature to prepare gulonic acid methyl ester, and the conversion rate of the gulonic acid can reach more than 98%. Compared with the traditional method, the method has the advantages that the acid value of the obtained gulonic acid methyl ester is low, the catalyst is not easy to collapse and run off, and the service life of the catalyst is long.
Description
Technical Field
The invention relates to the field of chemical engineering, in particular to a synthetic method of gulonic acid methyl ester.
Background
Methyl gulonate is an important fine chemical product, and is mainly used for producing vitamin C. Methyl gulonate is currently produced primarily by the condensation of gulonic acid and methanol. The catalyst is mainly an acidic catalyst and comprises ionic resin, inorganic acid, organic acid and the like. Although the prior acidic catalyst has better effect in the synthesis of gulonic acid methyl ester, the conversion rate is always maintained at about 90 percent, which causes the problems of large consumption of alkali, difficult separation, more three wastes and the like in the subsequent process of vitamin C production. The key problem for restricting the further improvement of the conversion rate is that the water generated by the reaction cannot be separated in time, so that how to further improve the conversion rate of the gulonic acid and reduce the difficulty of subsequent treatment becomes a new challenge.
Disclosure of Invention
In order to solve the problem that the reaction conversion rate is further improved in the synthesis of the gulonic acid methyl ester, the invention provides a synthesis method of the gulonic acid methyl ester, which uses a material formed by mixing acidic ion exchange resin and polytetrafluoroethylene particles as a catalyst, and the material is filled in a fixed bed reactor (figure 1) in a specific proportion, and the proportion of the polytetrafluoroethylene is gradually reduced from bottom to top. Because of the hydrophobic property of the polytetrafluoroethylene, after the gulonic acid is converted to a certain degree, the proportion of the polytetrafluoroethylene in the catalyst bed is increased, the water and the gulonic acid are separated in the reaction process, and the concentration of the gulonic acid is locally improved, so that the conversion rate of the gulonic acid is further improved. Under the action of the catalyst, the conversion rate of gulonic acid can reach more than 98%.
According to the invention, acidic ion exchange resin and polytetrafluoroethylene particles are physically and uniformly mixed, the mass ratio of the acidic ion exchange resin to the polytetrafluoroethylene particles is 1:9-1: 0.2, and the mixture is marked as Cat-A-X: Y, wherein A is the type of the acidic ion resin, X: y is the mass ratio of the acidic ion exchange resin to the polytetrafluoroethylene particles.
According to the invention, the ion exchange resin can be one or more of A15, A16, D001, D002 and D006.
The catalyst filling mode is that the catalyst is filled in four sections in the fixed bed, and the catalyst is sequentially 1 section, 2 section, 3 section and 4 section from the bottom of the fixed bed;
the ranges of X and Y of the four different catalysts are different;
wherein X: Y of the 1-stage catalyst is 1:9-1:7, X: Y of the 2-stage catalyst is 1: <7-1:5(X: Y is 1: 5-less than 7), X: Y of the 3-stage catalyst is 1: <5-1:3(X: Y is 1: 3-less than 5), X: Y of the 4-stage catalyst is 1: <3-1:0.2(X: Y is 1: 0.2-less than 3)
According to the invention, the synthesis reaction of methyl gulonate is carried out in a fixed bed reactor.
According to the invention, the reaction temperature is 40-120 ℃, preferably 50-60 ℃, and the mass space velocity is 0.5-3h-1Preferably 1h-1. The molar ratio of the gulonic acid to the methanol is 1:1 to 1:10, preferably 1: 3;
the height of each section of bed layer from top to bottom is 1/4 of the filling height of the reactor;
the acidic ion exchange resin and the polytetrafluoroethylene particles have the same particle size, and are 4 meshes to 20 meshes, preferably 8 meshes, and the invention has the beneficial effects that: the method can efficiently catalyze the reaction and dehydration of gulonic acid and methanol at a lower temperature to prepare the gulonic acid methyl ester, and the conversion rate of the gulonic acid can reach more than 98 percent.
Compared with the traditional acid catalyst, the method has the advantages of high conversion rate of gulonic acid, low acid value of the obtained gulonic acid methyl ester, reduction of three wastes in Vc production by subsequent treatment, and reduction of total material consumption and energy consumption. The filled catalyst is not easy to collapse and run off, and the service life of the catalyst is long.
Drawings
The catalyst filling diagram in fig. 1 shows that 1 is raw material, 2 is liquid distributor, 3 is product, 4 is 4-stage catalyst, 5 is 3-stage catalyst, 6 is 2-stage catalyst, and 7 is 1-stage catalyst.
Detailed Description
The process provided by the present invention is described in detail below with reference to examples, but the present invention is not limited thereto in any way.
Example 1
Filling 1 section, 2 section, 3 section and 4 section of catalysts in a fixed bed reactor (an equal diameter cylindrical reactor, the diameter of the bottom is 5cm, the filling height can be 20cm), wherein the used 1 section of catalyst is Cat-A15-1:9, the 2 section of catalyst is Cat-A15-1:6, the 3 section of catalyst is Cat-A15-1:3, the 4 section of catalyst is Cat-A15-1:1, and the height of each section is the same and is 5 cm. The catalyst particles used were 4 mesh. Heating the reactor to 60 ℃, and adding gulonic acid and methanol liquid from the top end of the reactor, wherein the molar ratio of the gulonic acid to the methanol liquid is 1:4, and the space velocity is 1h-1The acid value of the gulonic acid methyl ester solution obtained after the reaction was 0.015mg/KOH/g, and the conversion of the reaction gulonic acid was 99.1%.
Example 2
Filling 1-section, 2-section, 3-section and 4-section catalysts in a fixed bed reactor (an equal-diameter cylindrical reactor, the diameter of the bottom is 5cm, and the filling height is 20cm), wherein the used 1-section catalyst is Cat-A16-1:7, the 2-section catalyst is Cat-A16-1:5, the 3-section catalyst is Cat-A16-1:3, and the 4-section catalyst is Cat-A16-1:1, and the heights of all the sections are the same and are 5 cm. The catalyst particles used were 8 mesh. Heating the reactor to 60 deg.C, adding gulonic acid and methanol liquid from the top of the reactorThe molar ratio of (1: 3) and the space velocity of 0.5h-1The acid value of the methyl gulonic acid solution obtained after the reaction was 0.025mg/KOH/g, and the conversion of the reaction gulonic acid was 98.5%.
Example 3
Filling 1 section, 2 sections, 3 sections and 4 sections of catalysts in a fixed bed reactor (an equal-diameter cylindrical reactor, the diameter of the bottom is 5cm, and the filling height can be 20cm) from bottom to top, wherein the used 1 section of catalyst is Cat-D001-1:9, the 2 section of catalyst is Cat-D001-1:5, the 3 section of catalyst is Cat-D001-1:4, and the 4 section of catalyst is Cat-D001-1:0.8, and the heights of all the sections are the same and are 5 cm. The catalyst particles used were 8 mesh. Heating the reactor to 50 ℃, and adding gulonic acid and methanol liquid from the top end of the reactor at a molar ratio of 1:10 and an airspeed of 3h-1The acid value of the gulonic acid methyl ester solution obtained after the reaction is 0.030mg/KOH/g, and the conversion rate of the reaction gulonic acid is 98.2 percent
Example 4
Filling 1 section, 2 section, 3 section and 4 section of catalyst in a fixed bed reactor (an equal diameter cylindrical reactor, the diameter of the bottom is 5cm, the filling height can be 20cm), wherein the used 1 section of catalyst is Cat-D002-1:8, the 2 section of catalyst is Cat-D002-1:5, the 3 section of catalyst is Cat-D002-1:3, and the 4 section of catalyst is Cat-D002-1:0.2, and each section is the same in height and is 5 cm. The catalyst particles used were 20 mesh. Heating the reactor to 55 ℃, and adding gulonic acid and methanol liquid from the top end of the reactor at a molar ratio of 1:2 and an airspeed of 1.5h-1The acid value of the methyl gulonic acid solution obtained after the reaction was 0.013mg/KOH/g, and the conversion of gulonic acid by the reaction was 99.2%.
Example 5:
in a fixed bed reactor (equal diameter cylindrical reactor, bottom diameter is 5cm, can fill height is 20cm), 1-stage, 2-stage, 3-stage, 4-stage catalyst is filled from bottom to top, wherein the 1-stage catalyst is Cat-D006-1:7, the 2-stage catalyst is Cat-D006-1:6, the 3-stage catalyst is Cat-D006-1:3, and the 4-stage catalyst is Cat-D006-1:0.8, each stage has the same height and is 5 cm. The catalyst particles used were 4 mesh. Heating the reactor to 55 ℃, and adding gulonic acid and methanol liquid from the top end of the reactor, wherein the molar ratio of the gulonic acid to the methanol liquid isThe space velocity of 1:3 is 1h-1The acid value of the methyl gulonic acid solution obtained after the reaction was 0.022mg/KOH/g, and the conversion of the reaction was 98.7%.
Comparative example:
in a fixed bed reactor (cylindrical reactor of equal diameter, bottom diameter 5cm, can be packed height 20cm), the D006 catalyst was packed. The catalyst packing height was 20 cm. Heating the reactor to 55 ℃, and adding gulonic acid and methanol liquid from the top end of the reactor, wherein the molar ratio of the gulonic acid to the methanol liquid is 1:3, and the space velocity is 1h-1The acid value of the methyl gulonic acid solution obtained after the reaction was 0.338mg/KOH/g, and the conversion of the reaction gulonic acid was 80.0%.
Claims (10)
1. A synthetic method of gulonic acid methyl ester is characterized in that a material formed by mixing acidic ion exchange resin and polytetrafluoroethylene particles is used as a catalyst and filled in a fixed bed reactor to catalyze gulonic acid and methanol to react and dehydrate to prepare gulonic acid methyl ester;
the catalyst is prepared by physically and uniformly mixing acidic ion exchange resin and polytetrafluoroethylene particles, wherein the mass ratio of the acidic ion exchange resin to the polytetrafluoroethylene particles is 1:9-1: 0.2, and the catalyst is marked as Cat-A-X: Y, wherein A is the type of the acidic ion resin, and X: y is the mass ratio of the acidic ion exchange resin to the polytetrafluoroethylene particles; the catalyst filling mode is that the catalyst is filled in four sections in the fixed bed, and the catalyst is sequentially 1 section, 2 section, 3 section and 4 section from the bottom of the fixed bed;
the ranges of X and Y of the four different catalysts are different;
wherein X: Y =1:9-1:7 in the 1-stage catalyst, X: Y is 1: <7-1:5 in the 2-stage catalyst, X: Y is 1: <5-1:3 in the 3-stage catalyst, and X: Y is 1: <3-1:0.2 in the 4-stage catalyst.
2. A method of synthesis according to claim 1, characterized in that: the acidic ion exchange resin is one or more of A15, A16, D001, D002 and D006.
3. A method of synthesis according to claim 1, characterized in that:
the synthesis reaction of gulonic acid methyl ester is carried out in a fixed bed reactor, and gulonic acid and methanol liquid are introduced from the top end of the reactor.
4. A synthesis method according to claim 1 or 3, characterized in that: the reaction temperature is 40-120 deg.CoC, the mass space velocity is 0.5-3h-1。
5. A synthesis method according to claim 1 or 3, characterized in that: the reaction temperature is 50-60%oC, mass space velocity of 1h-1。
6. A synthesis method according to claim 1 or 3, characterized in that: the molar ratio of the gulonic acid to the methanol is 1:1 to 1: 10.
7. A synthesis method according to claim 1 or 3, characterized in that: the molar ratio of the gulonic acid to the methanol is 1: 3.
8. A method of synthesis according to claim 1, characterized in that: the height of each section of bed from top to bottom is 1/4 of the filling height of the reactor.
9. A method of synthesis according to claim 1, characterized in that: the particle diameter of the acidic ion exchange resin is the same as that of the polytetrafluoroethylene particles, and is between 4 meshes and 20 meshes.
10. A method of synthesis according to claim 9, characterized in that: the grain diameter is 8 meshes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770761A (en) * | 1996-11-08 | 1998-06-23 | Chinese Petroleum Corporation | Process for ethyl acetate production |
| DE19938980A1 (en) * | 1999-08-19 | 2001-02-22 | Basf Ag | Process for the preparation of 2-keto-L-gulonic acid esters |
| CN101927185A (en) * | 2010-08-09 | 2010-12-29 | 上海华震科技有限公司 | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate |
| CN101735183B (en) * | 2010-01-26 | 2012-02-29 | 河北维尔康制药有限公司 | Method for synthesizing vitamin C sodium salt |
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- 2018-01-31 CN CN201810096475.3A patent/CN110092719B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770761A (en) * | 1996-11-08 | 1998-06-23 | Chinese Petroleum Corporation | Process for ethyl acetate production |
| DE19938980A1 (en) * | 1999-08-19 | 2001-02-22 | Basf Ag | Process for the preparation of 2-keto-L-gulonic acid esters |
| CN101735183B (en) * | 2010-01-26 | 2012-02-29 | 河北维尔康制药有限公司 | Method for synthesizing vitamin C sodium salt |
| CN101927185A (en) * | 2010-08-09 | 2010-12-29 | 上海华震科技有限公司 | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate |
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