CN100345856C - Esterification and crystallizing process for producing glucose halfaldehyde lactone - Google Patents
Esterification and crystallizing process for producing glucose halfaldehyde lactone Download PDFInfo
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- CN100345856C CN100345856C CNB2006100185200A CN200610018520A CN100345856C CN 100345856 C CN100345856 C CN 100345856C CN B2006100185200 A CNB2006100185200 A CN B2006100185200A CN 200610018520 A CN200610018520 A CN 200610018520A CN 100345856 C CN100345856 C CN 100345856C
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Abstract
The present invention relates to an esterification and crystallization process method for preparing glucurolactone. In the method, first level concentration dewatering is carried out to obtained oxidised starch digest on the basis of traditional procedures of amylum acid method oxidation and hydrolysis, a first level concentrate is fine dewatered by a water containing agent by the second level, a second level concentrate is added in acetic acid and is esterified at the temperature of 65 to 70 DEG C, and diluted acid is steamed and separated from an esterification reaction mixture which is dewatered by the third level. The mixture which is dewatered by the third level is cooled and crystallized in the mode of dynamic gradient at the speed rate of 1-2 DEG C / hour at the beginning of esterification temperature, the final temperature of crystallization is 25 (+/-) 5 DEG C, and the total crystallization time is less than or equal to a 40 hours; a coarse product of which the glucurolactone content is more than or equal to 90 % is obtained through the filtration of the crystallization mixture, the yield is more than or equal to 18%, and the coarse product can be used in a purification procedure. The method enhances the total yield and the crystallization final temperature of the glucurolactone, and greatly reduces crystallization time and the energy consumption of the crystallization, and accordingly, the production cost of the glucurolactone is reduced.
Description
Technical field
The present invention relates to a kind of acid system and produce the esterification technique method of Glucuronic acid lactone, and the crystallization and purification method of this esterification technique method gained Glucuronic acid lactone.This processing method is the further improvement to existing preparation Glucuronic acid lactone esterification and crystallization processes.
Background technology
Glucuronic acid lactone is called for short Glucuronic acid .gamma.-lactone, and molecular formula is C
6H
8O
6, its chemical ingredients is: D (+)-glucofuranose aldehydic acid gamma lactone [D (+)-Glucofuranurono-6,3-lactone].Glucuronic acid .gamma.-lactone is conventional liver protecting good medicine as a kind of liver detoxification agent and immune function controlling agents; Glucuronic acid .gamma.-lactone and subsequent product thereof still are the main additive of functional drinks and food, diet pill, makeup etc., the effect that has additional physical efficiency, improves anoxic, nourishes skin, delays senility, its market demand have surpassed the demand at field of medicaments in recent years.
Glucuronic acid and Glucuronic acid .gamma.-lactone are from finding existing so far nearly 80 years history.Nineteen twenty-three, M.Bergmann and W.W.Wolff are that raw material obtains and isolate glucuronic acid first with glucose; Nineteen thirty-nine Stacey has delivered the method for its synthesizing glucurolactone.The main starting raw material of preparation Glucuronic acid .gamma.-lactone is starch, trehalose or glucose, and preparation principle mainly is to utilize above-mentioned raw materials at first to prepare glucuronic acid, and glucuronic acid obtains Glucuronic acid .gamma.-lactone through lactonizing.
The main method of existing industrial production Glucuronic acid .gamma.-lactone is the nitric acid oxidation method from starch, this method has been continued to use nineteen fifty-one is prepared glucuronic acid and lactone thereof with acid oxidation starch by G.Serchi and L.Arcangeli production technique, its technological process is: with starch, the mixture of water makes Sumstar 190 with the nitrosonitric acid oxidation, starch oxidation liquid is the heating and pressurizing hydrolysis under acidic conditions, obtain the hydrolyzed solution of Sumstar 190, it is 44～45 o'clock that hydrolyzed solution is evaporated to degree Beaume, directly add the acetic acid esterification, esterification mixture cools to 45 ℃ and leaves standstill and progressively cool to-4～-8 ℃ after 16～20 hours again, be generally decrease temperature crystalline total time 70～80 hours, crystallisate gets rid of filter through high speed centrifugation, and to obtain purity be 80-90% Glucuronic acid lactone crude product, the crude product yield is about 12～15%, total about 5～6 days of production cycle.Crude product is handled through decolouring, recrystallization can obtain purified product, and the total recovery after making with extra care is generally about 10%.The clear 36-12114 of Japanese Patent, clear 38-14556, clear 43-5882 etc. have also reported similar preparation method in succession.The main advantage of this method is that the starting material starch source is wide and price is lower, but this method exists that reaction preference is poor, esterification not exclusively, shortcoming such as the aftertreatment cycle is long, and product separation difficulty, energy consumption height, product yield are low.
Summary of the invention
Technical problem to be solved by this invention is to produce the deficiency that exists in the Glucuronic acid lactone technological process and a kind of esterification and crystallization processes method that acid system prepares Glucuronic acid lactone that be used for is provided at traditional acid system, it can improve esterification yield and crystallization final temperature, simplified the crystallization technological process, thereby reduced production costs.
The present invention for the technical scheme that problem adopted of the above-mentioned proposition of solution is:
Earlier the Sumstar 190 hydrolyzed solution is carried out the one-level dehydration: heating is evaporated to till no visible moisture distillates, and the enriched material degree Beaume is 45～48Be;
Sumstar 190 hydrolyzed solution enriched material is done the secondary dehydration: tell micro-moisture residual in the one-level enriched material by adding band aqua and moisture content azeotropic;
In the secondary enriched material, add acetic acid and carry out esterification;
Do three grades of dehydrations after the esterification: with the esterification uniform temp and 〉=steam light acetic acid under the vacuum tightness of 0.09MPa, steam volume be controlled at add the acetic acid volume 10～30% between;
Mixture after three grades of dehydrations begins from esterification temperature, carry out dynamic gradient cooling crystallization with 1～2 ℃/hour speed, the crystallization final temperature is 25 ± 5 ℃, crystallization total time≤40 hour, crystalline mixture obtains the crude product of Glucuronic acid lactone content 〉=90% through suction filtration, yield 〉=18%, refining with subsequent handling again.
Press such scheme, described one-level dehydration temperaturre is 50～60 ℃, vacuum tightness 〉=0.093Mpa.
Press such scheme, band aqua described in the secondary dehydration is selected any in butylacetate, propyl carbinol, propyl acetate, ethyl acetate, hexanaphthene, the benzene for use, the consumption of band aqua by volume (volume number: milliliter) be 0.5～1.2 times of enriched material weight (weight number: restrain), band water temp≤60 ℃, vacuum tightness is between 0.06～0.09MPa.The band aqua is selected butylacetate the best for use, and butylacetate azeotropic band water is effective, and is water-soluble hardly, and the rate of recovery is more than 98%, and azeotropic component promptly can be recycled after leaving standstill branch water.
Press such scheme, described esterification reaction temperature is 65-70 ℃, 1～2 hour reaction times, under normal pressure, stir, and acetic acid add-on by volume (volume number: milliliter) be 0.8～1.2 times of amount of starch weight (weight number: restrain).
Press such scheme, described three grades of dehydrations promptly steam the light acetic acid of part by decompression and take the moisture that reaction generates out of.
Mechanism of the present invention is: it is a reversible reaction that glucuronic acid is converted into Glucuronic acid lactone through intramolecular dehydration, has water to generate in the reaction product, and glucuronic acid and Glucuronic acid lactone can transform mutually in the aqueous solution.According to the molecular balance theory, effectively help the formation of ester except that the moisture content of moisture content that contains in the de-esterifying precursor system and the generation of removal esterification, in time remove simultaneously the solution loss that the forward and backward moisture content of reaction can reduce or avoid Glucuronic acid .gamma.-lactone, thereby improve the Glucuronic acid .gamma.-lactone yield.The variation of the solubility with temperature of Glucuronic acid .gamma.-lactone in water is bigger, and (40～80 ℃) solubleness is bigger in the high-temperature zone, though solubleness has certain difference, difference is little at cold zone (0～30 ℃).Therefore in crystallisation process, to take all factors into consideration the relation that energy consumption cost and yield increase, simultaneously since at low temperatures the viscosity of crystallizing system be unfavorable for that greatly crystal is separated out and product separation, increase separating energy consumption, therefore need to select suitable crystallization warm eventually.
Beneficial effect of the present invention is: 1. this esterification technique has shortened the esterification starting time by three grades of dehydration operation before and after esterification, has improved the esterification yield.2. this esterification technique reduces by three grades of dehydration operation before and after esterification or has avoided the solution loss of Glucuronic acid .gamma.-lactone in water, thereby improves the crystallization yield of Glucuronic acid .gamma.-lactone.3. this crystallization processes has improved the purity of Glucuronic acid .gamma.-lactone product by dynamic gradient cooling crystallization.4. the crystallization final temperature of this crystallization processes is 25 ± 5 ℃, has not only significantly reduced the crystallization energy consumption, and can obtain the Glucuronic acid .gamma.-lactone coarse crystallization through suction filtration (not needing a large amount of centrifugation apparatus), has simplified the crystallization technical process, has reduced production cost.
Embodiment
The present invention is described in further detail below in conjunction with example.
Embodiment 1
Get Sumstar 190 hydrolyzed solution 900ml (be converted into 100 gram raw starch) and 60 ℃ of temperature, under vacuum tightness 〉=0.09MPa condition hydrolyzed solution is carried out concentrating under reduced pressure, till not having visible moisture and distillating, one-level enriched material degree Beaume is 48Be.Add the 100ml butylacetate in the one-level enriched material, azeotropic dehydration when 60 ℃ and 0.08MPa vacuum tightness distillates to absence of liquid, reclaims butylacetate 99ml.In the secondary enriched material, add the 100ml Glacial acetic acid, stirring esterifications at 70 ℃ reduces pressure after 1 hour and steams the light acetic acid of 20ml, reaction mixture from 70 ℃ of beginnings with 1 ℃/hour rate of temperature fall and under stirring at low speed decrease temperature crystalline, during 30 ℃ of temperature to the crystalline mixture suction filtration, solid is with 2 * 10ml absolute ethanol washing, vacuum-drying gets white crystalline powder 20.4 grams, Glucuronic acid .gamma.-lactone content 92%.
Embodiment 2
Get Sumstar 190 hydrolyzed solution 900ml (be converted into 100 gram raw starch) and 60 ℃ of temperature, under vacuum tightness 〉=0.09MPa condition hydrolyzed solution is carried out concentrating under reduced pressure, till not having visible moisture and distillating, one-level enriched material degree Beaume is 45Be.Add the 120ml butylacetate in the one-level enriched material, azeotropic dehydration when 60 ℃ and 0.08MPa vacuum tightness distillates to absence of liquid, reclaims butylacetate 118ml.Add the 100ml Glacial acetic acid in the secondary enriched material, stirring esterifications at 70 ℃ reduces pressure after 1 hour and steams the light acetic acid of 20ml, reaction mixture from 70 ℃ of beginnings with 1 ℃/hour rate of temperature fall and under stirring at low speed decrease temperature crystalline, during 30 ℃ of temperature to the crystalline mixture suction filtration, solid is with 2 * 10ml absolute ethanol washing, vacuum-drying gets white crystalline powder 23.4 grams, Glucuronic acid .gamma.-lactone content 90%.
Embodiment 3
55 ℃ of temperature, vacuum tightness is under the 0.093MPa condition hydrolyzed solution to be carried out concentrating under reduced pressure to get Sumstar 190 hydrolyzed solution 450ml (be converted into 50 gram raw starch), and till not having visible moisture and distillating, one-level enriched material degree Beaume is 48Be.Add the 50ml ethyl acetate in the one-level enriched material, azeotropic dehydration when 55 ℃ and 0.07MPa vacuum tightness distillates to absence of liquid, reclaims ethyl acetate 45ml.Add the 50ml Glacial acetic acid in the resistates (secondary enriched material), stirring esterifications at 68 ℃ reduces pressure after 1.5 hours and steams the light acetic acid of 10ml, reaction mixture from 68 ℃ of beginnings with 2 ℃/hour rate of temperature fall and under stirring at low speed decrease temperature crystalline, during 20 ℃ of temperature to the crystalline mixture suction filtration, solid 2 * 10ml absolute ethanol washing, vacuum-drying gets white crystalline powder 9.6 grams, Glucuronic acid .gamma.-lactone content 93%.
Embodiment 4
Get Sumstar 190 hydrolyzed solution 900ml (be converted into 100 gram raw starch), under 60 ℃ and vacuum tightness 0.093MPa condition hydrolyzed solution is carried out concentrating under reduced pressure, till not having visible moisture and distillating, one-level enriched material degree Beaume is 48Be.Add the 100ml butylacetate in the one-level enriched material, azeotropic dehydration when 55 ℃ and 0.09MPa vacuum tightness distillates to absence of liquid, reclaims butylacetate 98ml.Add the 120ml Glacial acetic acid in the resistates (secondary enriched material), stirring esterifications at 65 ℃ reduces pressure after 2 hours and steams the light acetic acid of 20ml, reaction mixture from 65 ℃ of beginnings with 1 ℃/hour rate of temperature fall and under stirring at low speed decrease temperature crystalline, during 25 ℃ of temperature to the crystalline mixture suction filtration, solid 2 * 10ml absolute ethanol washing, vacuum-drying gets white crystalline powder 22.5 grams, Glucuronic acid .gamma.-lactone content 92%.
Claims (5)
1. an esterification and a crystallization processes method for preparing Glucuronic acid lactone is characterized in that
Earlier the Sumstar 190 hydrolyzed solution is carried out the one-level dehydration: heating is evaporated to till no visible moisture distillates, and the enriched material degree Beaume is 45～48Be; Sumstar 190 hydrolyzed solution enriched material is done the secondary dehydration: tell micro-moisture residual in the one-level enriched material by adding band aqua and moisture content azeotropic; In the secondary enriched material, add acetic acid and carry out esterification; Do three grades of dehydrations after the esterification: with the esterification uniform temp and 〉=steam light acetic acid under the vacuum tightness of 0.09MPa, steam volume be controlled at add the acetic acid volume 10～30% between; Mixture after three grades of dehydrations begins from esterification temperature, carry out dynamic gradient cooling crystallization with 1～2 ℃/hour speed, the crystallization final temperature is 25 ± 5 ℃, crystallization total time≤40 hour, crystalline mixture obtains the crude product of Glucuronic acid lactone content 〉=90%, yield 〉=18% through suction filtration.
2. by described esterification of claim 1 and crystallization processes method, it is characterized in that described one-level dehydration temperaturre is 50～60 ℃, vacuum tightness 〉=0.093Mpa.
3. by claim 1 or 2 described esterifications and crystallization processes method, it is characterized in that the band aqua described in the secondary dehydration selects any in butylacetate, propyl carbinol, propyl acetate, ethyl acetate, hexanaphthene, the benzene for use.
4. by described esterification of claim 3 and crystallization processes method, it is characterized in that with the consumption of aqua by volume (milliliter) be 0.5～1.2 times of enriched material weight (gram), be with water temp≤60 ℃, vacuum tightness is between 0.06～0.09MPa.
5. by claim 1 or 2 described esterifications and crystallization processes method, it is characterized in that described esterification reaction temperature is 65-70 ℃, 1～2 hour reaction times, under normal pressure, stir, acetic acid add-on by volume (milliliter) is 0.8～1.2 times of amount of starch weight (gram).
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| CN102219809B (en) * | 2010-04-16 | 2014-11-05 | 江苏天士力帝益药业有限公司 | Rectification and crystallization method of glucurolactone |
| KR20200003933A (en) | 2011-03-04 | 2020-01-10 | 뉴젠 세러퓨틱스 인코포레이티드 | Alkyne substituted quinazoline compound and methods of use |
| CN102918029B (en) | 2011-05-17 | 2015-06-17 | 江苏康缘药业股份有限公司 | 4-phenylamino-6-butenamide-7-alkyloxy quinazoline derivatives, preparative method and use thereof |
| CN103882077A (en) * | 2014-03-18 | 2014-06-25 | 陕西科技大学 | Normal temperature crystallization method of glucuronolactone |
| CN104610386A (en) * | 2015-01-12 | 2015-05-13 | 湖北益泰药业有限公司 | Method for increasing production yield of glucurolactone |
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| 葡醛内酯生产工艺研究 周锡堂，等，桂林工学院学报，第23卷第1期 2003 * |
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