CN110590868B - Production process of 2-keto-L-gulonic acid methyl ester - Google Patents
Production process of 2-keto-L-gulonic acid methyl ester Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
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- C07H7/027—Keto-aldonic acids
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Abstract
A method for continuously producing 2-keto-L-gulonic acid methyl ester by taking 2-keto-L-gulonic acid as a raw material comprises the following steps of serially connecting a plurality of heat exchangers to form a feeding heat exchanger, taking a connecting pipe type reactor behind the feeding heat exchanger as an esterification reaction device, connecting a material outlet of the pipe type reactor with a heat medium inlet of a primary heat exchanger formed by combining M heat exchangers in front of the feeding heat exchanger, taking a heat medium outlet of the primary heat exchanger of the feeding heat exchanger as a discharge hole of equipment for producing the 2-keto-L-gulonic acid methyl ester, and adopting an external heat source for a secondary heat exchanger of the feeding heat exchanger formed by combining N heat exchangers behind the feeding heat exchanger, wherein the production steps comprise: material preparation, heating and continuous esterification; the beneficial effects obtained include: the reaction time is obviously shortened, the energy consumption is reduced, the workload of workers is reduced, the dosage of sulfuric acid is obviously reduced, the generation of byproducts is reduced, the product quality is further improved, and the production cost can be further reduced due to the fact that the dosage of alkali for conversion reaction can be further reduced.
Description
Technical Field
The invention relates to a production process of 2-keto-L-gulonic acid methyl ester, in particular to a method for continuously producing 2-keto-L-gulonic acid methyl ester by taking 2-keto-L-gulonic acid as a raw material, belonging to the technical field of vitamin C preparation.
Background
Vitamin C, also known as L-ascorbic acid, is a common raw material medicine, can be used for preventing and treating diseases, has wide application in medicine and clinic, can be used for treating diseases such as ascorbyl disease, cold, cardiovascular defects, hypercholesterolemia, diabetes, dysthymia and the like, and can be used as a reinforcing agent and an antioxidant in the food industry in large quantities.
The production method of vitamin C mainly adopts two-step fermentation to prepare gulonic acid, and then the gulonic acid is chemically converted to generate the vitamin C. At present, the existing conversion process in China is mainly an alkali conversion process, namely 2-keto-L-gulonic acid and methanol generate 2-keto-L-gulonic acid methyl ester under the action of sulfuric acid, and then NaHCO is added 3 Or Na 2 CO 3 The reaction was carried out to convert methyl gulonate into sodium ascorbate. CN101284824A discloses a preparation method of sodium vitamin C, which comprises adding 2-keto-L-gulonic acid into methanol, adding concentrated sulfuric acid catalyst, heating to 60-68 ℃ to carry out esterification reaction for 3-5 hours, and generating 2-keto-L-gulonic acid methyl ester; after the esterification reaction is finished, adding sodium carbonate, reacting for 2-3 hours at the temperature of 60-68 ℃, cooling, and filtering to obtain sodium ascorbate, wherein the mass ratio of the 2-keto-L-gulonic acid to the methanol is 1. CN101735183A discloses a synthesis method of vitamin C sodium salt, which comprises the steps of mixing gulonic acid and methanol solution according to the mass volume ratio of 1; heating the treating fluid to 40-60 ℃ through a resin column for circular esterification reaction; and (2) performing conversion reaction on the esterification solution to obtain the vitamin C sodium salt, wherein the problem of sodium sulfate residue in the produced crude Vc-Na is solved by using resin instead of concentrated sulfuric acid as a catalyst compared with the traditional esterification reaction, and the yield is high, but the process is increased, the operation is complicated, and the time is long.
The preparation of the 2-keto-L-gulonic acid methyl ester in the vitamin C production process belongs to an intermittent production process, the reaction is carried out under normal pressure, the reaction time is long, generally more than 3 hours, the production efficiency is low, in addition, the concentrated sulfuric acid dosage of the traditional 2-keto-L-gulonic acid methyl ester preparation process is large, the mass-to-volume ratio of the concentrated sulfuric acid dosage to the 2-keto-L-gulonic acid is more than 0.027, the production cost is increased, and the quality of a finished product is influenced; in addition, the production equipment has large occupied area and high labor intensity of workers, and is one of the problems to be solved by the existing production process of the 2-keto-L-gulonic acid methyl ester.
Disclosure of Invention
The invention aims to overcome the defects of the prior 2-keto-L-gulonic acid methyl ester production process and provide a 2-keto-L-gulonic acid methyl ester production process which can reduce material consumption and byproduct generation and improve production efficiency, namely a method for continuously producing 2-keto-L-gulonic acid methyl ester by using 2-keto-L-gulonic acid as a raw material.
The purpose of the invention can be realized by the following technical scheme:
a can reduce the consumption of supplies and production technology of methyl ester of 2-keto-L-gulonic acid of the by-product and raise the production efficiency, namely a method for using 2-keto-L-gulonic acid as raw materials to produce 2-keto-L-gulonic acid methyl ester continuously, it adopts the multiple heat exchangers to connect the series connection and form the feed heat exchanger, the back connecting pipe type reactor of the feed heat exchanger is regarded as the esterification reaction unit, the supplies outlet of the tubular reactor connect the heat medium import of the elementary heat exchanger that M heat exchangers make up before the feed heat exchanger, regard heat medium outlet of the elementary heat exchanger of the feed heat exchanger as the discharge port of the apparatus for producing 2-keto-L-gulonic acid methyl ester, the second grade heat exchanger of the feed heat exchanger that N heat exchangers make up after the feed heat exchanger adopts the external heat source, the production step includes:
(1) Ingredients
Adding 2-keto-L-gulonic acid and methanol in a proportioning tank according to the mass-to-volume ratio of 1-keto-L-gulonic acid to 1-7, adding concentrated sulfuric acid according to the mass-to-volume ratio of 2-keto-L-gulonic acid to concentrated sulfuric acid of 1-0.023, starting stirring to uniformly mix the feed liquid;
(2) Heating is carried out
Continuously adding the uniformly mixed feed liquid into a feeding heat exchanger, and heating the mixed feed liquid to 75-110 ℃ through the feeding heat exchanger;
(3) Continuous esterification
The mixed liquid continuously flowing out of the feeding heat exchanger directly enters a tubular reactor for reaction, the reaction temperature is maintained at 75-110 ℃, the pressure is maintained at 0.3-0.7 MPa, the retention time of the liquid in the tubular reactor is controlled to be 15-60 min, the mixed liquid flows out of the tubular reactor, namely, the esterified liquid after the esterification is used as a heat source and is introduced into a primary heat exchanger formed by combining M heat exchangers in front of the feeding heat exchanger, and the mixed liquid is cooled and then enters a conversion process after the mixed liquid and the liquid flowing through the feeding heat exchanger exchange.
In the above process equipment, the first M heat exchangers of the feed heat exchanger are preferably connected in series and each heat exchanger is a primary heat exchanger which is combined in a countercurrent flow manner to form the feed heat exchanger.
In the above process equipment, the last N heat exchangers of the feed heat exchanger are preferably connected in series, and each heat exchanger is a secondary heat exchanger which is combined by countercurrent flow to form the feed heat exchanger.
The invention achieves the following beneficial effects:
(1) The reaction conditions are controlled to be high temperature and high pressure, so that the reaction time is obviously shortened, the esterified liquid after the esterification can also be used as a heat source for heating the liquid material, the heat exchange with the liquid material flowing through the feeding heat exchanger is realized, the requirement of the heating liquid material on heat energy is partially solved, the problem of heat energy waste caused by cooling the esterified liquid after the esterification reaction is finished is reduced, and the energy consumption is reduced;
(2) By adopting the production process of the 2-keto-L-gulonic acid methyl ester, the production process is continuous and automatic, the floor area of production equipment is reduced, the workload of workers is reduced, and 3 workers per shift can be reduced to 2 workers;
(3) Compared with the traditional 2-keto-L-gulonic acid methyl ester preparation process, the method has the advantages that the sulfuric acid consumption is obviously reduced, the generation of byproducts is reduced, the product quality is further improved, in addition, the alkali consumption required by the neutralization of the sulfuric acid in the conversion reaction can be further reduced, the production cost can be further reduced, the sulfate radical content in the subsequent mother liquor is reduced, and the difficulty of wastewater treatment is also reduced.
Drawings
FIG. 1 is a schematic diagram of a process for the continuous production of methyl 2-keto-L-gulonate from 2-keto-L-gulonic acid according to the present invention.
Detailed Description
In order to better illustrate the invention, the following examples are given, but the scope of the invention is not limited thereto, and the scope of the invention is set forth in the claims.
Example 1:
production equipment: the method comprises the following steps that 3 heat exchangers (A1, A2 and A3) are connected in series to form a feeding heat exchanger, a pipe type reactor B connected behind the feeding heat exchanger is used as an esterification reaction device, a material outlet of the pipe type reactor B is connected with a heat medium inlet of a primary heat exchanger formed by the countercurrent flow arrangement of the heat exchanger A1 in front of the feeding heat exchanger, a heat medium outlet of the primary heat exchanger of the feeding heat exchanger is used as a discharge port of equipment for producing 2-keto-L-gulonic acid methyl ester, the rear 2 heat exchangers (A2 and A3) of the feeding heat exchanger are connected in series, and each heat exchanger is a secondary heat exchanger of the feeding heat exchanger formed by countercurrent flow combination;
the method comprises the following specific operations:
adding 2-keto-L-gulonic acid and methanol into a dosing tank according to the mass-to-volume ratio of 1-keto-L-gulonic acid to methanol of 1. The yield of methyl 2-keto-L-gulonate was 95.04%.
Example 2:
production equipment: same as example 1
The method comprises the following specific operations:
adding 2-keto-L-gulonic acid and methanol into a dosing tank according to the mass-to-volume ratio of the 2-keto-L-gulonic acid to the methanol being 1. The yield of methyl 2-keto-L-gulonate was 95.60%.
Example 3:
production equipment: same as example 1
The method comprises the following specific operations:
adding 2-keto-L-gulonic acid and methanol into a dosing tank according to the mass-to-volume ratio of the 2-keto-L-gulonic acid to the methanol being 1. The yield of methyl 2-keto-L-gulonate was 96.16%.
Example 4:
production equipment: same as example 1
The method comprises the following specific operations:
adding 2-keto-L-gulonic acid and methanol into a dosing tank according to the mass-to-volume ratio of the 2-keto-L-gulonic acid to the methanol being 1. The yield of methyl 2-keto-L-gulonate was 97.02%.
Claims (4)
1. A method for continuously producing 2-keto-L-gulonic acid methyl ester by taking 2-keto-L-gulonic acid as a raw material is characterized in that a plurality of heat exchangers are connected in series to form a feed heat exchanger, a connecting pipe type reactor behind the feed heat exchanger is used as an esterification reaction device, a material outlet of the pipe type reactor is connected with a heat medium inlet of a primary heat exchanger formed by combining M heat exchangers in front of the feed heat exchanger, a heat medium outlet of the primary heat exchanger of the feed heat exchanger is used as a discharge hole of equipment for producing the 2-keto-L-gulonic acid methyl ester, a secondary heat exchanger of the feed heat exchanger formed by combining N heat exchangers behind the feed heat exchanger adopts an external heat source, and the production steps comprise:
(1) Ingredients
Adding 2-keto-L-gulonic acid and methanol in a mixing tank according to the mass volume ratio of the 2-keto-L-gulonic acid to the methanol of 1-3-7, adding concentrated sulfuric acid according to the mass volume ratio of the 2-keto-L-gulonic acid to the concentrated sulfuric acid of 1-0.023, and stirring to uniformly mix the feed liquid;
(2) Heating of
Continuously adding the uniformly mixed feed liquid into a feeding heat exchanger, and heating the mixed feed liquid to 75-110 ℃ through the feeding heat exchanger;
(3) Continuous esterification
The mixed liquid continuously flowing out of the feeding heat exchanger directly enters a tubular reactor for reaction, the reaction temperature is maintained at 75-110 ℃, the pressure is maintained at 0.3-0.7 MPa, the retention time of the liquid in the tubular reactor is controlled to be 15-60 min, the mixed liquid flows out of the tubular reactor, namely, the esterified liquid after the esterification is used as a heat source and is introduced into a primary heat exchanger formed by combining M heat exchangers in front of the feeding heat exchanger, and the mixed liquid is cooled and then enters a conversion process after the mixed liquid and the liquid flowing through the feeding heat exchanger exchange.
2. The method of claim 1 for the continuous production of methyl 2-keto-L-gulonate starting from 2-keto-L-gulonic acid, comprising: the front M heat exchangers of the feeding heat exchanger are connected in series, and each heat exchanger is a primary heat exchanger of the feeding heat exchanger formed by countercurrent flow combination.
3. The method for continuously producing methyl 2-keto-L-gulonate from 2-keto-L-gulonic acid as claimed in claim 1 or 2, wherein: the rear N heat exchangers of the feeding heat exchanger are connected in series, and each heat exchanger is a second-stage heat exchanger which is formed by combining countercurrent flow.
4. The method for continuously producing methyl 2-keto-L-gulonate from 2-keto-L-gulonic acid as claimed in claim 1, wherein: the heat exchanger comprises a feeding heat exchanger formed by connecting 3 heat exchangers A1, A2 and A3 in series, a primary heat exchanger formed by the upstream 1 heat exchanger A1 of the feeding heat exchanger in a countercurrent flow mode, and a secondary heat exchanger formed by connecting the downstream 2 heat exchangers A2 and A3 of the feeding heat exchanger in series and combining each heat exchanger in a countercurrent flow mode.
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| CN201910873962.0A CN110590868B (en) | 2019-09-17 | 2019-09-17 | Production process of 2-keto-L-gulonic acid methyl ester |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285342A (en) * | 1999-08-19 | 2001-02-28 | Basf公司 | Process for preparation of 2-keto-gulonoester |
| WO2003018569A1 (en) * | 2001-08-24 | 2003-03-06 | Eastman Chemical Company | Process for ascorbic acids using alkaline earth silicate catalysts |
| CN1412172A (en) * | 2001-10-12 | 2003-04-23 | 伊斯曼化学公司 | Preparation of carboxylic acid ester |
| CN102351699A (en) * | 2011-10-28 | 2012-02-15 | 安徽泰格生物技术股份有限公司 | Gulonate and preparation method thereof |
-
2019
- 2019-09-17 CN CN201910873962.0A patent/CN110590868B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285342A (en) * | 1999-08-19 | 2001-02-28 | Basf公司 | Process for preparation of 2-keto-gulonoester |
| WO2003018569A1 (en) * | 2001-08-24 | 2003-03-06 | Eastman Chemical Company | Process for ascorbic acids using alkaline earth silicate catalysts |
| CN1412172A (en) * | 2001-10-12 | 2003-04-23 | 伊斯曼化学公司 | Preparation of carboxylic acid ester |
| CN102351699A (en) * | 2011-10-28 | 2012-02-15 | 安徽泰格生物技术股份有限公司 | Gulonate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 微通道反应器中进行古龙酸甲酯化反应的研究;安卫红等;《煤炭与化工》;20211031;135-137 * |
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