CN101798327A - Preparation process of 2-keto-D-glucolactone - Google Patents
Preparation process of 2-keto-D-glucolactone Download PDFInfo
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- CN101798327A CN101798327A CN200910065989A CN200910065989A CN101798327A CN 101798327 A CN101798327 A CN 101798327A CN 200910065989 A CN200910065989 A CN 200910065989A CN 200910065989 A CN200910065989 A CN 200910065989A CN 101798327 A CN101798327 A CN 101798327A
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Abstract
The invention relates to a preparation process of 2-keto-D-glucolactone, comprising the following steps of: firstly, fully mixing 2-keto-D-gluconic acid and low-molecule alcohol in the proportion that 2.5-3.5 L of the low-molecule alcohol is added in the 1 kg of the 2-keto-D-gluconic acid; then, continuously esterifying for 30-120 minutes at the temperature of 40-55 DEG C by using strong-acidity cation exchange resins as catalysts, wherein the weight of the strong-acidity cation exchange resins is 0.1-2 times of the weight of the 2-keto-D-gluconic acid; after esterification, transferring the esterified solution into a crystallizing and freezing tank for cooling to 0-5 DEG C; and then centrifugally separating to obtain the 2-keto-D-glucolactone. The invention has the advantages of short reaction time, low reaction temperature and energy saving, reduces energy consumption and production cost, improves economic benefit and greatly improves the production capacity.
Description
Technical field
The invention belongs to a kind of technology of intermediate of synthetic sodium D-isoascorbate, relate in particular to the preparation technology of 2-keto-D-gluconic acid ester.
Prior art
Sodium isoascorbate has another name called SODIUM ISOVITAMIN C, molecular formula C
6H
7O
6Na, this product is a kind of novel food product antioxygen, anticorrosion, preservation agent, can reduce the oxidation of food effectively, prevent that its color from taking off change, meat product and seafood are helped the look effect, also can suppress simultaneously the generation of carcinogenic substance nitrite in the food, hypotensive, diuresis, toxicide effect are medically being arranged; This product very is widely used in the food such as meat, fruit, beverage at present, also can be used for industries such as wool spinning, plating, feed processing, Treatment of Industrial Water and petrochemical complex; But it is a kind of rising metabolism oxidation inhibitor, and its anticorrosion antioxidant effect substantially exceeds vitamins C, but price is less than its 1/2nd.
The 2-keto-D-gluconic acid is the important intermediate of synthetic sodium D-isoascorbate, and the esterification of 2-keto-D-gluconic acid is the committed step of the synthetic sodium D-isoascorbate of preparation, and its esterification formula is
In industrial production, realize this reaction process, generally be under the effect that is catalyzer, to carry out with the inorganic acid, traditional method is to adopt operating method intermittently, be about in 2-keto-D-gluconic acid and low mass molecule alcohol, the disposable by a certain percentage input reactor of strong inorganic acid catalyst, under certain temperature and pressure, through 3～5 hours esterification time, reaction finished.This intermittent process is because low mass molecule alcohol is to drop into once, and esterification reaction process is finished in a long time, low mass molecule alcohol has occupied the effective volume of reactor, its consumption is higher, energy consumption is also high simultaneously, because of having adopted mineral acid such as sulfuric acid or hydrochloric acid to make catalyzer, easily forms the inorganic acid ester by product in process of production in addition, in subsequent technique, generate not easy-clear of sodium sulfate or sodium-chlor, make the corresponding raising of production cost; And mineral acid has strong oxidizing property, has reduced the color and luster of product on the one hand, also is unfavorable for environmental protection on the other hand; It is low to adopt this technology to carry out esterification gained acid esters purity at last, has only 90%.
Summary of the invention
The object of the present invention is to provide and a kind ofly make catalyzer with storng-acid cation exchange resin, adopt the preparation technology of the 2-keto-D-gluconic acid ester of continuous esterification, thereby reduce the consumption of low mass molecule alcohol and energy in the esterification process significantly, can not produce the inorganic acid ester by product, improve the purity of 2-keto-D-gluconic acid esterification efficient and ester greatly, solid quality base is provided for the conversion of sodium D-isoascorbate is synthetic.
In order to achieve the above object by the following technical solutions: a kind of preparation technology of 2-keto-D-gluconic acid ester: at first with 2-keto-D-gluconic acid and low mass molecule alcohol thorough mixing, ratio is that 1kg 2-keto-D-gluconic acid adds 2.5～3.5L low mass molecule alcohol; Be catalyzer then with the storng-acid cation exchange resin, in 40～55 ℃ temperature range, carry out continuous esterification by storng-acid cation exchange resin, the weight of storng-acid cation exchange resin is 0.1～2 times of weight of 2-keto-D-gluconic acid, and the reaction times is 30～120 minutes; After esterification is finished, change esterifying liquid over to the crystallization freezing jar and be cooled to 0～5 ℃, carry out centrifugation, both got 2-keto-D-gluconic acid ester.
Described low mass molecule alcohol is methyl alcohol or ethanol.
The described low mass molecule alcohol of root is a methyl alcohol.
Described storng-acid cation exchange resin is a strongly acidic styrene type cation exchange resin.
Described strongly acidic styrene type cation exchange resin is D001 or 001 * 7.
Technological merit of the present invention is: the one, and serialization adds methyl alcohol, and the reaction times is short, and temperature of reaction is low, saves energy; The 2nd, replace inorganic acid to avoid corrosion with storng-acid cation exchange resin to the containing metal reactor as catalyzer, and can not produce the inorganic acid ester by product, and reduce the technology of follow-up removing by product, be convenient to recovery set and use, reduce energy consumption and production costs, increase economic efficiency; The 3rd, compare with interrupter method, shorten the reaction times greatly, save energy and alcohol consumption, increase substantially throughput; The 4th, adopt the purity height of this technology gained 2-keto-D-gluconic acid ester, reach more than 99%.
Table 1,2,3 data contrasts for preparation technology of the present invention and interrupter method preparation technology.
Table 1
| Operating method | 2-ketone group-D-gluconic acid throwing amount (Kg) | Methyl alcohol charging capacity (L) | Reaction times (h) | Methyl esters purity (%) | Esterification yield (%) |
| Periodical operation | ??120 | ??460 | ??4 | ??90 | ??92.5 |
| The present invention | ??250 | ??650 | ??0.5 | ??99.2 | ??99.3 |
Table 2
| Operating method | 2-ketone group-D-gluconic acid throwing amount (Kg) | Methyl alcohol charging capacity (L) | Reaction times (h) | Methyl esters purity (%) | Esterification yield (%) |
| Periodical operation | ??120 | ??500 | ??4 | ??89.5 | ??92.0 |
| The present invention | ??250 | ??870 | ??2.0 | ??99.5 | ??99.5 |
Table 3
| Operating method | 2-ketone group-D-gluconic acid throwing amount (Kg) | Methyl alcohol charging capacity (L) | Reaction times (h) | Methyl esters purity (%) | Esterification yield (%) |
| Periodical operation | ??120 | ??480 | ??4 | ??89.2 | ??92.8 |
| The present invention | ??250 | ??750 | ??1.5 | ??99.2 | ??99.7 |
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Embodiment 1
A kind of preparation technology of 2-keto-D-gluconic acid ester, at first with 2-keto-D-gluconic acid and low mass molecule alcohol thorough mixing, ratio is that 1kg 2-keto-D-gluconic acid adds 2.5～3.5L low mass molecule alcohol; In 40～55 ℃ temperature range, carry out continuous esterification by storng-acid cation exchange resin then, the weight of storng-acid cation exchange resin is 0.1～2 times of weight of 2-keto-D-gluconic acid, and the reaction times is 30～120 minutes; After esterification is finished, change esterifying liquid over to the crystallization freezing jar and be cooled to 0～5 ℃, carry out centrifugation, both got 2-keto-D-gluconic acid ester.
Described 2-keto-D-gluconic acid is the 2-keto-D-gluconic acid underflow that is concentrated into terminal point; Described low mass molecule alcohol is 99.5% low mass molecule alcohol; Described storng-acid cation exchange resin is a strongly acidic styrene type cation exchange resin.
Described low mass molecule alcohol is methyl alcohol or ethanol; Described strongly acidic styrene type cation exchange resin is D001 or 001 * 7.
Embodiment 2
A kind of preparation technology of 2-keto-D-gluconic acid ester at first drops into 250kg 2-keto-D-gluconic acid and 650L methyl alcohol in the dissolving vessel, starts agitator and heat temperature raising, makes its thorough mixing even; Then when temperature reaches 45 ℃ in the dissolving vessel jar, continuously squeeze into pump and to carry out continuous esterification in the ion exchange column, fill 500kg large hole strong acid styrene system cation exchange resin D001 in the ion exchange column, the reaction times is 30 minutes, and temperature is 45 ℃; The esterification yield of last acid reaches 99.3%, esterifying liquid is changed in the crystallization freezing jar again, is cooled to 0 ℃, carries out centrifugation, has both got 2-keto-D-gluconic acid ester, and isolated methyl esters purity reaches 99.2%, the methanol mother liquor recycling.
Embodiment 3
A kind of preparation technology of 2-keto-D-gluconic acid ester at first drops into 250kg 2-keto-D-gluconic acid and 870L methyl alcohol in the dissolving vessel, starts agitator and heat temperature raising, makes its thorough mixing even; Then when temperature reaches 40 ℃ in the dissolving vessel jar, continuously squeeze into pump and to carry out continuous esterification in the ion exchange column, fill 250kg large hole strong acid styrene system cation exchange resin D001 in the ion exchange column, the reaction times is 120 minutes, and temperature is 40 ℃; The esterification yield of last acid reaches 99.5%, esterifying liquid is changed in the crystallization freezing jar again, is cooled to 5 ℃, carries out centrifugation, has both got 2-keto-D-gluconic acid ester, and isolated methyl esters purity reaches 99.5% methanol mother liquor recycling.
Embodiment 4
A kind of preparation technology of 2-keto-D-gluconic acid ester at first drops into 250kg 2-keto-D-gluconic acid and 750L methyl alcohol in the dissolving vessel, starts agitator and heat temperature raising, makes its thorough mixing even; Then when temperature reaches 55 ℃ in the dissolving vessel jar, continuously squeeze into pump and to carry out continuous esterification in the ion exchange column, fill 25kg strongly acidic styrene type cation exchange resin 001 * 7 in the ion exchange column, the reaction times is 90 minutes, and temperature is 55 ℃; The esterification yield of last acid reaches 99.7%, esterifying liquid is changed in the crystallization freezing jar again, is cooled to 3 ℃, carries out centrifugation, has both got 2-keto-D-gluconic acid ester, and isolated methyl esters purity reaches 99.2%.
Embodiment 5
A kind of preparation technology of 2-keto-D-gluconic acid ester at first drops into 200kg 2-keto-D-gluconic acid and 700L ethanol in the dissolving vessel, starts agitator and heat temperature raising, makes its thorough mixing even; Then when temperature reaches 50 ℃ in the dissolving vessel jar, continuously squeeze into pump and to carry out continuous esterification in the ion exchange column, fill 100kg strongly acidic styrene type cation exchange resin D001 in the ion exchange column, the reaction times is 80 minutes, and temperature is 50 ℃; The esterification yield of last acid reaches 99.0%, esterifying liquid is changed in the crystallization freezing jar again, is cooled to 2 ℃, carries out centrifugation, has both got 2-keto-D-gluconic acid ester, the recycling of ethanol mother liquor.
Embodiment 6
A kind of preparation technology of 2-keto-D-gluconic acid ester at first drops into 300kg 2-keto-D-gluconic acid and 750L ethanol in the dissolving vessel, starts agitator and heat temperature raising, makes its thorough mixing even; Then when temperature reaches 45～50 ℃ in the dissolving vessel jar, continuously squeeze into pump and to carry out continuous esterification in the ion exchange column, fill 450kg strongly acidic styrene type cation exchange resin 001 * 7 in the ion exchange column, the reaction times is 90～100 minutes; The esterification yield of last acid reaches 99.1%, esterifying liquid is changed in the crystallization freezing jar again, is cooled to 4 ℃, carries out centrifugation, has both got 2-keto-D-gluconic acid ester.
Embodiment 7
A kind of preparation technology of 2-keto-D-gluconic acid ester at first drops into 150kg 2-keto-D-gluconic acid and 400L ethanol in the dissolving vessel, starts agitator and heat temperature raising, makes its thorough mixing even; Then when temperature reaches 50～55 ℃ in the dissolving vessel jar, continuously squeeze into pump and to carry out continuous esterification in the ion exchange column, fill 200kg strongly acidic styrene type cation exchange resin 001 * 7 in the ion exchange column, the reaction times is 40～60 minutes; The esterification yield of last acid reaches more than 99%, esterifying liquid is changed in the crystallization freezing jar again, is cooled to 0 ℃, carries out centrifugation, has both got 2-keto-D-gluconic acid ester, the recycling of ethanol mother liquor.
Claims (5)
1. the preparation technology of a 2-keto-D-gluconic acid ester is characterized in that: at first with 2-keto-D-gluconic acid and low mass molecule alcohol thorough mixing, ratio is that 1kg 2-keto-D-gluconic acid adds 2.5～3.5L low mass molecule alcohol; Be catalyzer then with the storng-acid cation exchange resin, in 40～55 ℃ temperature range, carry out continuous esterification by storng-acid cation exchange resin, the weight of storng-acid cation exchange resin is 0.1～2 times of weight of 2-keto-D-gluconic acid, and the reaction times is 30～120 minutes; After esterification is finished, change esterifying liquid over to the crystallization freezing jar and be cooled to 0～5 ℃, carry out centrifugation, both got 2-keto-D-gluconic acid ester.
2. the preparation technology of 2-keto-D-gluconic acid ester according to claim 1 is characterized in that: described low mass molecule alcohol is methyl alcohol or ethanol.
3. the preparation technology of 2-keto-D-gluconic acid ester according to claim 2 is characterized in that: described low mass molecule alcohol is a methyl alcohol.
4. according to the preparation technology of the described 2-keto-D-gluconic acid of claim 1 ester, it is characterized in that: described storng-acid cation exchange resin is a strongly acidic styrene type cation exchange resin.
5. according to the preparation technology of the described 2-keto-D-gluconic acid of claim 2 ester, it is characterized in that: described strongly acidic styrene type cation exchange resin is D001 or 001 * 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424695A (en) * | 2011-10-28 | 2012-04-25 | 安徽泰格生物技术股份有限公司 | Sodium methyl gulonate and preparation method thereof |
| CN108129427A (en) * | 2017-12-29 | 2018-06-08 | 郑州拓洋生物工程有限公司 | ISOASCORBIC ACID potassium and its preparation method and application |
| CN110423229A (en) * | 2019-08-08 | 2019-11-08 | 安徽丰原发酵技术工程研究有限公司 | It is a kind of to prepare ascorbic method by the alkali conversion method of raw material of 2-KLG |
| CN114522743A (en) * | 2022-03-09 | 2022-05-24 | 欧尚元(天津)有限公司 | Method for preparing sodium isoascorbate and decalcification method and system thereof |
-
2009
- 2009-08-28 CN CN200910065989A patent/CN101798327A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424695A (en) * | 2011-10-28 | 2012-04-25 | 安徽泰格生物技术股份有限公司 | Sodium methyl gulonate and preparation method thereof |
| CN108129427A (en) * | 2017-12-29 | 2018-06-08 | 郑州拓洋生物工程有限公司 | ISOASCORBIC ACID potassium and its preparation method and application |
| CN110423229A (en) * | 2019-08-08 | 2019-11-08 | 安徽丰原发酵技术工程研究有限公司 | It is a kind of to prepare ascorbic method by the alkali conversion method of raw material of 2-KLG |
| CN114522743A (en) * | 2022-03-09 | 2022-05-24 | 欧尚元(天津)有限公司 | Method for preparing sodium isoascorbate and decalcification method and system thereof |
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Application publication date: 20100811 |