CN103130669B - Potassium aspartate preparation method - Google Patents
Potassium aspartate preparation method Download PDFInfo
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- CN103130669B CN103130669B CN201310063773.XA CN201310063773A CN103130669B CN 103130669 B CN103130669 B CN 103130669B CN 201310063773 A CN201310063773 A CN 201310063773A CN 103130669 B CN103130669 B CN 103130669B
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Abstract
The invention provides a potassium aspartate preparation method. The method comprises the following steps: 1, reacting aspartic acid with potassium hydroxide according to a mass ratio of 1:0.6-0.75; 2, carrying out three-stage filtration of a product obtained after the reaction in step 1 through one-time filtration by active carbon and two-time filtration by a filter membrane, and taking the obtained filtrate; 3, adding an organic solvent to the filtrate at -10-0DEG C, and cooling at -30 - -20DEGC; and 4, filtering, taking the obtained filter cake, and drying. The method allows the optimum water application amount to be obtained through the difference of the solubility of aspartic acid in water at different temperatures in order to reduce the solvent application amount and improve the yield. A filter system is increased to reduce impurities. A drying method is changed to select a best boiling drying method in order to reach the purposes comprising working hour saving, energy consumption reduction and effective water control. The method has the advantages of short production operation steps, low cost, short time consumption, high yield, and high content, and is very suitable for the industrialized production.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of preparation method of salt of Aspartic Acid.
Background technology
Aspartic acid, chemical name is ASPARTIC ACID potassium, molecular formula is C
4h
6kNO
4, molecular weight is 171, structural formula is
Aspartic acid is the sylvite of Aspartic Acid, is electrolyte complementary medical.Potassium magnessium aspartape is the mixing double salt of Aspartic Acid sylvite and magnesium salts composition, can improve myocardium shrinkage function, and can lower oxygen consumption, improves myocardial cell's energy metabolism.Aspartic Acid and cell have very strong avidity; can be used as the carrier that potassium ion enters cell; potassium ion is returned in cell; promote cell depolarization and cellular metabolism; maintain myocardial contraction, thereby improve myocardium shrinkage function, and reduce oxygen-consumption; thereby under anoxic condition, heart is had to provide protection.
Domestic have Potassium magnessium aspartape compound injection and oral preparations to go on the market, and is all widely used at present in clinical practice, and infective use is stable, and application prospect is extensive.Potassium magnessium aspartape is the mixing double salt of Aspartic Acid sylvite and magnesium salts composition, can improve myocardium shrinkage function, and can lower oxygen consumption, improves myocardial cell's energy metabolism.The sixties, foreign applications all had certain curative effect in the various hepatitis for the treatment of, liver cirrhosis and hyperammonemia, the end of the seventies, domestic application effect of potassium-magnesium aspartate heart disorder, cardiac insufficiency and acute, chronic hepatitis, hyperbilirubinemia etc. obtained better effects, and progressively play a part toxicity reduction the nineties in antineoplastic microbiotic chemotherapy.At present, Potassium magnessium aspartape is mainly used in following aspect clinically:
Cardiovascular systems: irregular pulse, the concurrent ventricular premature contraction of chronic heart failure, acute myocardial infarction;
Hypertension, Diabetes with Hypertension exist potassium magnesium metabolic disturbance, complicated hypertension disease;
Viral myocarditis (Radix Astragali injection associating Aspartic Acid);
Central nervous system: pulmonary encephalopathy, acute cerebral infarction, hepatogenic encephalopathy, chronic viral hepatitis B removing jaundice subcutaneous ulcer;
Endocrine system: diabetic polyneuropathy becomes;
Respiratory system: Asthmatic Diseases in Children.And application in the elderly's surgery anesthesia.
The synthetic method of the aspartic acid of bibliographical information has following several:
Chinese patent CN1439629A discloses an a kind of left-handed aspartic acid raw material and has utilized the made preparation of this raw material and preparation method, the preparation method of the left-handed aspartic acid described in it, be characterised in that the sylvite of getting recipe quantity is in retort, dissolve by suitable quantity of water, add again appropriate methyl alcohol or ethanol, add lentamente a more left-handed Aspartic Acid of recipe quantity, stir, with a left-handed Aspartic Acid or sylvite adjusting pH8, filter, filtrate is cooling, slowly add methyl alcohol or ethanol, stir, if desired as entered an a small amount of left-handed aspartic acid, make crystallization, centrifugation, dry and get final product.In the actual production of the method technique, exist preparation cycle long, efficiency is low, the low deficiency that waits of product yield, and general yield is lower than 70%, especially on large production.As in the unique left-handed aspartic acid raw material Preparation Example l relating to of CN1439629A, a described left-handed aspartic acid preparation technology will reach increase yield (as 70%) will increase very a large amount of ethanol or the consumption of methyl alcohol, and certainly will greatly increase production cost, and roll up ethanol or methanol usage will affect the feasibility of actual production.
Chinese patent CN101234992A discloses a kind of preparation method of aspartic acid, particular content: Yu Shuizhong adds recipe quantity potassium hydroxide, under stirring, add L mono-Aspartic Acid or DL-Aspartic Acid, heating makes reaction, filters, and filtrate is steamed near dry, under stirring, be added in the dehydrated alcohol of-25 DEG C～00C, place, get solid, through pulverizing, centrifugal (or filter), be drying to obtain.Although the method increases on yield, because length concentrated consuming time, the power consumption of water in system are large, and the same time consumption and energy consumption of vacuum-drying weak effect is large, and overall cost is higher.So can not meet the demand of suitability for industrialized production.In the technology of preparing of existing aspartic acid, or in preparation process, use water dissolution raw material then to add and make its crystallization with organic solvent, then carry out vacuum-drying, this processes expend organic solvent amount is large, yield is low, and cost is higher; Or reaction solution tentatively concentrates, concentrated solution carries out solvent crystallization processing, and the time that this concentration method needs is long, consumes energy also large; Or use boulton process, the operating time is long, and the large cost of energy consumption is high; These drawbacks that existing method exists, become the difficult problem that the needs of this products production solve.
Summary of the invention
The present invention seeks to for the existing weak point of existing aspartic acid preparation field, the object of the invention is to reach by the screening and optimizing of the ratio to solvent, solvent temperature the object that reduces solvent usage quantity and improve yield.Propose that a kind of production operation step is brief, cost is lower, consuming time shorter, yield is higher, content is higher, is applicable to very much the preparation method of the aspartic acid of suitability for industrialized production.
For the technical scheme that realizes the object of the invention is:
A preparation method for aspartic acid, comprises step:
1) mass ratio 1:0.6～0.75 of Aspartic Acid and potassium hydroxide, reacts,
2) step 1) is reacted the product that the obtains three-stage filtration through a gac, twice filter membrane, gets filtrate;
3) at temperature-10～0 DEG C, in filtrate, add organic solvent, then cooling at-30～-20 DEG C;
4) filter, get filter cake, dry.
Wherein, in described step 1), Aspartic Acid is to be dissolved in the water, and then reacts with potassium hydroxide, and the mass ratio of described Aspartic Acid and water is 1:0.5～0.8, and temperature control when Aspartic Acid is dissolved in the water is 30～45 DEG C.
Preferably, the mass ratio of described Aspartic Acid and water is 1:0.7, and temperature control when Aspartic Acid is dissolved in the water is 40 DEG C.
Wherein, when in described step 1), Aspartic Acid reacts with potassium hydroxide, the pH value of system is 6.0～8.0.In this process, pH is an index more intuitively, and pH regulates control by potassium hydroxide add-on.Therefore in process the control of potassium hydroxide addition within the specific limits, to guarantee that Aspartic Acid reacts completely.
Wherein, described step 2) in twice filter membrane in, primary is the filter membrane of 0.8～1 μ m, secondary is 0.4～0.5 μ m filter membrane.Described activated carbon filtration is first to use activated carbon decolorizing, then filters through carbon filter.
Wherein, in described step 3), organic solvent is selected from the one in ethanol, ethylene glycol, acetone; Described organic solvent quality is 1～2 times of Aspartic Acid quality.
Wherein, in described step 3), the cooling time is 2～4 hours.
Wherein, filter cake organic solvent washing in described step 4), described organic solvent is selected from the one in ethanol, ethylene glycol, acetone.When washing, the consumption of volume, according to conventional consumption, is generally 0.2～2 times of filter cake quality.
Preferably, in described step 4), be dried as fluidized drying at 30～40 DEG C.The dry time is 3.5 hours.
Beneficial effect of the present invention:
By Aspartic Acid dissolubility difference under differing temps in water, optimize best water consumption and reached the object that reduces solvent usage quantity and yield.Reach by increasing filtering system the object that reduces impurity.By changing drying means, optimize fluid-bed drying and reached the object of saving man-hour, reduction energy consumption, effectively controlling moisture.Production operation step is brief, cost is lower, consuming time shorter, yield is higher, content is higher, is applicable to very much suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 7 preparation methods' schema.
Embodiment
Following specific embodiment is for the present invention is described, but is not used for limiting the scope of the invention.
Embodiment 1
133.1g Aspartic Acid is dissolved in 80g purified water, and 30 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 80g, now system pH8.0, reaction solution adds 30 DEG C of decolouring 30min of 8.55g gac at 40 DEG C of temperature, filtered while hot, through the three-stage filtration of carbon filter filtration, 1 μ m filter membrane (material is PTFE), 0.45 μ m filter membrane (material is PTFE), obtain filtrate respectively.
Filtrate proceeds in crystallizer (triangular flask, specification is 1000ml), slowly adds the aqueous solution of organic solvent 95% ethanol of three times of water yields, and solution is muddy gradually, controls temperature-10～-8 DEG C, until add.Keep temperature-25 DEG C, time 2 h, then filters.Filtration obtains white products, and by a small amount of ethanolic soln 30ml washing with alcohol, then drying under reduced pressure 8 hours at 30 DEG C.Weight loss on drying 7.2%, obtains aspartic acid finished product.The product that the present embodiment obtains, through structure detection, conforms to bibliographical information, is strictly aspartic acid.Yield 95.3%, content 95.8%.(product weight=(dropping into the weight * 171.19/133.1 of Aspartic Acid) * yield) embodiment 2
133.1g Aspartic Acid is dissolved in 93g purified water, and 30 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 100g, system pH7.5, reaction solution adds 30 DEG C of decolouring 30min of 8.55g gac at 40 DEG C of temperature, and filtered while hot is passed through respectively the three-stage filtration of gac, 1 μ m filter membrane, 0.45 μ m filter membrane, obtains filtrate.
In filtrate, slowly add the aqueous solution of organic solvent 95% ethanol of three times of water yields, solution is muddy gradually, controls temperature-9 DEG C, until add.Keep temperature-20 DEG C, 2.5 hours time, then filter.Filtration obtains white products, and by solvent 30ml washing with alcohol, then drying under reduced pressure 8.5 hours at 30 DEG C.Weight loss on drying 6.8%, obtains aspartic acid product yield 97.2%, content 96.4%.
Embodiment 3
133.1g Aspartic Acid is dissolved in 106g purified water, and 30 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 93g, system pH7.0, reaction solution is filtered while hot at 40 DEG C of temperature, passes through respectively the three-stage filtration of gac, 1 μ m filter membrane, 0.45 μ m filter membrane, obtains filtrate.
In filtrate, slowly add the aqueous solution of organic solvent 95% ethanol of three times of water yields, solution is muddy gradually, controls temperature-9 DEG C, until add.Keep temperature-20 DEG C, 2.5 hours time, then centrifuging.Filtration obtains white products, and with 30ml washing with alcohol filter cake, then drying under reduced pressure 9 hours at 30 DEG C.Weight loss on drying 7.0%, obtains aspartic acid product yield 96.1%, content 96.1%.
Embodiment 4
133.1g Aspartic Acid is dissolved in 93g purified water, and 40 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 90g, system pH7.5, reaction solution is filtered while hot at 40 DEG C of temperature, passes through respectively the three-stage filtration of gac, 1 μ m filter membrane, 0.45 μ m filter membrane, obtains filtrate.
In filtrate, slowly add the aqueous solution of organic solvent 95% ethanol of three times of water yields, solution is muddy gradually, controls temperature-5 DEG C, until add.Keep temperature-25 DEG C, 2.5 hours time, then centrifuging.Then filter.Filtration obtains white products, and by solvent 30ml washing with alcohol, 30 DEG C of drying under reduced pressure 8.5 hours.Weight loss on drying 6.8%, obtains aspartic acid product yield 98.6%, content 96.6%.
Embodiment 5
133.1g Aspartic Acid is dissolved in 93g purified water, and 45 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 80g, system pH7.5, reaction solution is filtered while hot under temperature 45 C, passes through respectively the three-stage filtration of gac, 1 μ m filter membrane, 0.45 μ m filter membrane, obtains filtrate.
In filtrate, slowly add the aqueous solution of organic solvent 95% ethanol of three times of water yields, solution is muddy gradually, controls 0 DEG C of temperature, until add.Keep temperature-25 DEG C, 3 hours time, then centrifuging.Filtration obtains white products, and with 30ml washing with alcohol filter cake, then drying under reduced pressure 8.5 hours at 30 DEG C.Weight loss on drying 6.8%, obtains aspartic acid product yield 98.1%, content 96.3%.
Embodiment 6
133.1g Aspartic Acid is dissolved in 93g purified water, and 40 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 85g, system pH7.5, reaction solution is filtered while hot at 40 DEG C of temperature, passes through respectively the three-stage filtration of gac, 1 μ m filter membrane, 0.45 μ m filter membrane, obtains filtrate.
In filtrate, slowly add the aqueous solution of organic solvent 95% ethanol of three times of water yields, solution is muddy gradually, controls temperature-2 DEG C, until add.Keep temperature-25 DEG C, 3 hours time, then centrifuging.Filtration obtains white products, and with solvent 30ml washing with alcohol filter cake, then drying under reduced pressure 8.5 hours at 35 DEG C.Weight loss on drying 6.8%, obtains aspartic acid finished product.Yield 97.4%, content 98.6%.
Embodiment 7
Referring to Fig. 1.133.1g Aspartic Acid is dissolved in 93g purified water, and 40 DEG C are stirred to dissolving completely.Add the potassium hydroxide reaction of 93g, system pH7.5, reaction solution adds 30 DEG C of decolouring 30min of 8.55g gac at 40 DEG C of temperature, and filtered while hot is passed through respectively the three-stage filtration of gac (carbon filter), 1 μ m filter membrane, 0.45 μ m filter membrane, obtains filtrate.
In filtrate, slowly add the aqueous solution of organic solvent 95% ethanol of three times of water yields, solution is muddy gradually, controls 0 DEG C of temperature, until add.Keep temperature-25 DEG C, 3 hours time, then centrifuging.Filtration obtains white products, and with solvent 30ml washing with alcohol filter cake, then fluidized drying 3.5 hours at 30 DEG C.Weight loss on drying 6.8%, obtains aspartic acid yield 97.1%, 98.5% content.
Time of drying in embodiment 7 is short.Embody fluidized drying than short this advantage of drying under reduced pressure time.
Claims (2)
1. a preparation method for aspartic acid, is characterized in that, comprises step:
1) mass ratio of Aspartic Acid and potassium hydroxide is 1:0.6～0.75, reacts; Wherein, Aspartic Acid is to be dissolved in the water, and then reacts with potassium hydroxide, and the mass ratio of described Aspartic Acid and water is 1:0.7, and temperature control when Aspartic Acid is dissolved in the water is 40 DEG C; When Aspartic Acid reacts with potassium hydroxide, the pH value of system is 7.5;
2) step 1) is reacted the product that the obtains three-stage filtration through a gac, twice filter membrane, gets filtrate; In twice filter membrane, primary is the filter membrane of 0.8～1 μ m, and secondary is 0.4～0.5 μ m filter membrane;
3) at temperature-10～0 DEG C, in filtrate, add organic solvent, then cooling at-30～-20 DEG C, the cooling time is 3 hours; Described organic solvent is selected from the one in ethanol, ethylene glycol, acetone; Described organic solvent quality is 1～2 times of Aspartic Acid quality;
4) filter, get filter cake, dry, be dried as fluidized drying at 30～40 DEG C, the dry time is 3.5 hours.
2. preparation method as claimed in claim 1, is characterized in that, filter cake organic solvent washing in described step 4); Described organic solvent is selected from the one in ethanol, ethylene glycol, acetone.
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| CN104262185A (en) * | 2014-10-09 | 2015-01-07 | 中国食品发酵工业研究院 | Method for solid-phase synthesis of potassium aspartate at room temperature |
| CN106187799B (en) * | 2016-06-30 | 2018-12-14 | 宜兴市前成生物有限公司 | A method of preparing DL-lysine hydrochloride |
| CN109053478A (en) * | 2018-08-22 | 2018-12-21 | 上海青平药业有限公司 | A kind of preparation method of potassium L-aspartate magnesium salts |
Citations (6)
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|---|---|---|---|---|
| JPH09163993A (en) * | 1995-12-15 | 1997-06-24 | Mitsubishi Chem Corp | Production of l-aspartic acid |
| GB2343449A (en) * | 1998-11-09 | 2000-05-10 | Ass Octel | Alkylation of amino acids |
| CN1439629A (en) * | 2003-03-21 | 2003-09-03 | 于航 | Laevo potassium aspartate material and preparation therefrom and preparing method thereof |
| CN101234992A (en) * | 2008-03-10 | 2008-08-06 | 北京京卫信康医药科技发展有限公司 | Method for preparing aspartic acid |
| CN101239925A (en) * | 2008-03-10 | 2008-08-13 | 北京京卫信康医药科技发展有限公司 | Method for preparing magnesium aspartate |
| CN102875403A (en) * | 2012-10-31 | 2013-01-16 | 宜兴市前成生物有限公司 | Method for preparing potassium L-aspartate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495658B2 (en) * | 2001-02-06 | 2002-12-17 | Folia, Inc. | Comonomer compositions for production of imide-containing polyamino acids |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09163993A (en) * | 1995-12-15 | 1997-06-24 | Mitsubishi Chem Corp | Production of l-aspartic acid |
| GB2343449A (en) * | 1998-11-09 | 2000-05-10 | Ass Octel | Alkylation of amino acids |
| CN1439629A (en) * | 2003-03-21 | 2003-09-03 | 于航 | Laevo potassium aspartate material and preparation therefrom and preparing method thereof |
| CN101234992A (en) * | 2008-03-10 | 2008-08-06 | 北京京卫信康医药科技发展有限公司 | Method for preparing aspartic acid |
| CN101239925A (en) * | 2008-03-10 | 2008-08-13 | 北京京卫信康医药科技发展有限公司 | Method for preparing magnesium aspartate |
| CN102875403A (en) * | 2012-10-31 | 2013-01-16 | 宜兴市前成生物有限公司 | Method for preparing potassium L-aspartate |
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