CN103951571A - Device for chemical synthesis of asparaginic acid - Google Patents
Device for chemical synthesis of asparaginic acid Download PDFInfo
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- CN103951571A CN103951571A CN201410194931.XA CN201410194931A CN103951571A CN 103951571 A CN103951571 A CN 103951571A CN 201410194931 A CN201410194931 A CN 201410194931A CN 103951571 A CN103951571 A CN 103951571A
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Abstract
The invention discloses a device for chemical synthesis of asparaginic acid. The device for chemical synthesis of asparaginic acid mainly comprises a maleic acid reactor (1), a diammonium maleate reactor (5), a middle-high pressure stainless steel reactor system (8), an asparaginic acid crystallizer (9), a filtration device (10), an ammonia water storage, conveying and metering system (2), a deionized water storage, conveying and metering system (3), a carbon dioxide storage tank (4), a vacuum system (6), a carbon dioxide recovery reactor (7) and matched electrometer equipment, transfer pumps, pipelines, valves and pipe fittings. According to the invention, the pH value and the reaction pressure of the reactor system are adjusted and controlled by the ammonia water storage, conveying and metering system (2), the carbon dioxide storage tank (4) and the carbon dioxide recovery reactor (7) to be in line with various process indexes, so that the reaction mother liquor is recycled and the conversion rate of the feedstock is improved.
Description
Technical field
The invention belongs to the synthetic technical field of chemistry of amino acids, particularly relate to chemosynthesis aspartic acid device.
Background technology
Aspartic acid, aspartic acid (Aspartic acid) claims again amino-succinic acid, is one of main amino acid forming in organism protein.Structural formula is: HOOC-CH2-CH (NH2)-COOH, molecular weight 133.10.
Aspartic acid contains 1 amino and 2 carboxyls, it is the precursor of the amino acid such as synthetic lysine in life entity, Threonine, methionine(Met), Isoleucine and purine, pyrimidine bases, its residue is extensively present in various life entities, brain excitement signal be can transmit, brain and neural metabolic function regulated.
ASPARTIC ACID participates in 2,5-diaminovaleric acid circulation, promote ammonia and carbonic acid gas to generate urea, in reduction blood, the content of ammonia and carbonic acid gas, strengthens liver function, is therefore extensively used as the additive of the medical supplies such as ammonia detoxicant, liver function promotor, fatigue recovery agent and various refreshment drinks.
The dipeptide sweetener aspartame that aspartic acid and L-Phe are synthetic, sugariness is high, heat is low, is suitable for the patients such as diabetes, hypertension, safe and reliable; Take ASPARTIC ACID as the synthetic High-intensity Sweetener Neotame of raw material, be not only applicable to comprise children, pregnant woman, lactating women and obesity, cardiovascular diseases and diabetic subject's all groups, be also applicable to eat the phenylketonuria patient of aspartame.
The racemic modification DL-aspartic acid of aspartic acid is as K
+and Mg
2+carrier; can carry ionogen by Cardiomyocytes; thereby improve myocardium shrinkage function; can also reduce oxygen consumption simultaneously; when coronary artery circulation obstacle anoxic; cardiac muscle is had to provide protection, therefore can be used for synthetic DL-Potassium Magnesium Aspartata salt (Potassium Magnesium Aspartata), can be used for treating the diseases such as irregular pulse, tachycardia, heart failure, myocardial infarction, stenocardia, hepatitis and liver cirrhosis.DL-aspartic acid also can be used as the raw material of synthetic polypeptide, its aminoacid replacement derivative (NMDLA) can be used as the medicine of the neural class disease for the treatment of and cerebral disorders, as the derivative NMDA (NMDA) of aspartic acid obviously strengthens the excitation of optic nerve cell discharge unit, can be used as one of excitor nerve neurotransmitter receptor important in mammalian central nervous system.
At present, D-ASP, as a kind of chiral drug, is subject to people's attention day by day.It is main as synthetic precursor, the intermediate of medicine in medicine is synthetic.Aspoxicillin is first TA-058 injection drug using clinically.Vila etc. be take D-ASP as the synthetic D-ASP-β-azanol (DAH) of precursor.DAH is a kind of medicine for the treatment of virus infection, especially some retrovirus is had to resistance, can be used to treat the difficult and complicated illness such as AIDS, tumour.D-ASP also participates in more synthetic antibiotic side chains, as the side chain of beta-lactam antibiotics, can improve antibiotic anti-microbial activity.
DL-aspartic acid is a kind of important amino acid, as the nutritive ingredient of microbiological culture media, aspect biochemical reagents and clinical medicine, is being widely applied; It can be used as the raw material of synthetic polypeptide, by its synthetic dipeptidase derivant L-aspartyl-L-phenylalanine methylester, is a kind of sweeting agent low in calories; It is the monomer of synthetic poly-aspartic-acid still, and poly aspartic acid is a kind of good boiler scale inhibitor and the agent of plant nutrition absorption enhancement of discovered in recent years, this polymkeric substance, owing to having excellent biodegradability and environment friendly, becomes the substitute in this field at present just day by day.
Chemical method is mainly for the production of the racemic modification DL-aspartic acid of aspartic acid.
At present, in synthetic report both domestic and external, yield is many between 55% to 63%.The method of o-(2,4 ,-dinitrobenzene) azanol ammonification succinate for the report such as the Radhakrishn AS of the U.S., yield is 61%.Mazo, et al.February 16,1999, USP 5,872, and 285 use maleic acid two ammoniums and excessive 4 times of ammoniacal liquor react 1.5-3h under 100-180 ℃, 230-700Psi, and yield is 38-77%.
The Machowski etc. of Poland reacts with NH4Cl by MALEIC ANHYDRIDE and excessive ammonia, reacts in a batch reactor, under 140 ℃, 0.4MPa, reacts 2.5h.After the mixture obtaining is cooled to 70 ℃ with hcl acidifying to pH2.5, then be cooled to room temperature, aspartic acid Precipitation now, by sedimentation and filtration, obtains product after washing at 4 ℃, productive rate is 55%.
The synthetic yield of the employing microwave methods such as Deng Runhua of Chengdu organic chemistry institute is 61.4%.It is raw material that the method adopts benzene methylene ethyl aminoacetate, under phase-transfer catalyst (TEBA) catalysis, carries out halogenating reaction, through hydrolysis, generates aspartic acid racemic modification.
2002, the Xing second place of Zhejiang University waited in a titanium material autoclave, MALEIC ANHYDRIDE is carried out to aminating reaction and synthesized DL-aspartic acid.Study by experiment original synthesis technique has been made to improvement, product yield is brought up to more than 70%, and product separation purify is adopted to maleic acid (toxilic acid) thus replace hydrochloric acid to carry out the utilization that acidizing crystal improved reactant and the pollution that reduces reaction residual.
The Wang Yaquan of University Of Tianjin in 2003 etc. has proposed a kind of chemical synthesis easy, that do not use any catalyzer.Experiment is carried out in the 250ml of polytetrafluoro lining autoclave.Experimental procedure is as follows: 32.5g MALEIC ANHYDRIDE is dissolved in 70ml water, adds ammoniacal liquor to pH8, fill 1MPa nitrogen, then under induction stirring, be heated to 453K, reaction 6h, is cooled to room temperature after reaction, obtains clear crystal, yield 63.1% after filtration.
Above-mentioned these be all laboratory test data and test, there is no the document of related industries gasifying device.
Summary of the invention
Chemosynthesis aspartic acid device disclosed by the invention, exactly in order to address the above problem.
Know-why of the present invention, advantage be by ammoniacal liquor store delivery measurement system (2) and carbon dioxide storage tank (4), carbon dioxide recovery reactor (7) regulates potential of hydrogen, the reaction pressure of controlling reactor assembly to meet every technic index; Filter plant (10) is isolated asparagine acid crystal and reaction mother liquor, and reaction mother liquor returns to maleic acid two ammonium reactor (5) recycles, there is no by product, and feed stock conversion is improved.
Chemosynthesis aspartic acid process unit is mainly by maleic acid reactor (1), maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), aspartic acid crystallizer (9), filter plant (10), ammoniacal liquor storage delivery measurement system (2), deionized water storage delivery measurement system (3), carbon dioxide storage tank (4), vacuum system (6), carbon dioxide recovery reactor (7) and supporting electric instrument equipment, transferpump, pipeline, valve, pipe fitting forms.
Maleic acid reactor (1) and maleic acid two ammonium reactors (5) are the stainless steel stirred reactors of jacketed, or the glass lined stirring reactor of jacketed.
Mesohigh stainless steel reactor system (7) is comprised of the mesohigh stainless steel stirred reactor of electrified heating, cooling structure and supporting electric instrument equipment, transferpump, pipeline, valve, pipe fitting.
Aspartic acid crystallizer (9) is with cooling speed governing stainless steel stirred type crystallizer.
Filter plant (10) is 3-foot stainless steel whizzer, or press filter type strainer, or horizontal type screw settling stainless steel whizzer, Main Function is to isolate asparagine acid crystal and byproduct reaction mother liquor, makes byproduct reaction mother liquor return to maleic acid two ammonium reactor (5) recycles.
Ammoniacal liquor storage delivery measurement system (2) is comprised of the airtight storage tank of low pressure, ammoniacal liquor transferpump, under meter and supporting pipeline, valve, pipe fitting, is mainly quantitatively to add ammoniacal liquor for maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), carbon dioxide recovery reactor (7).
Deionized water storage delivery measurement system (3) is comprised of airtight deionized water storage tank, deionized water transferpump, under meter and supporting pipeline, valve, pipe fitting, is mainly quantitatively to add deionized water for maleic acid reactor (1), maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), carbon dioxide recovery reactor (6).
Carbon dioxide recovery reactor (6) is the airtight stirring stainless steel reactor of low pressure, after quantitatively adding ammoniacal liquor and deionized water, reclaims the carbonic acid gas of mesohigh stainless steel reactor system (8), aspartic acid crystallizer (9) pressure release discharge.
Vacuum system (6) is comprised of vacuum pump and surge tank, and being mainly provides vacuum operating condition for maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (7) and aspartic acid crystallizer (9).
The present invention realizes according to following technical proposals:
Quantitative MALEIC ANHYDRIDE and deionized water generate maleic acid at maleic acid reactor (1).
Maleic acid and quantitatively ammoniacal liquor generate maleic acid two ammoniums at maleic acid two ammonium reactors (5).
Maleic acid two ammoniums and deionized water are configured to certain concentration solution in mesohigh stainless steel reactor system (8), at vacuum state, add ammoniacal liquor, carbon dioxide recovery liquid to regulate the potential of hydrogen of reactor assembly.
By carbon dioxide storage tank (4), add carbonic acid gas again, regulate and control reactor initial reaction pressure.
Start mesohigh stainless steel reactor system (8) and stir and heating installation, regulate potential of hydrogen, temperature of reaction, the reaction pressure of controlling reactor assembly to meet every technic index, reaction reaches setting-up time.
The ammonia soln that has 10% left and right of its volume 20%-50% in carbon dioxide recovery reactor (6), reactor assembly and aspartic acid crystallizer (9) leak into carbon dioxide recovery reactor (6) by the higher carbonic acid gas of pressure, reclaim carbonic acid gas.
The aspartic acid crystallizer (9) that reactor assembly resultant is pressed into vacuum state cools, then adds maleic acid solution to regulate the potential of hydrogen of the interior material of aspartic acid crystallizer (9) that asparagine acid crystal is fully separated out.
Aspartic acid crystallizer (9) material is added to the separated asparagine acid crystal of filter plant (10), and reaction mother liquor enters maleic acid two ammonium reactor (5) recycles.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, be described further, but therefore do not limit protection authority of the present invention.
Accompanying drawing 1 is chemosynthesis aspartic acid process unit combination flow chart of the present invention.
(1) maleic acid reactor, (2) ammoniacal liquor storage delivery measurement system, (3) deionized water storage delivery measurement system, (4) carbon dioxide storage tank, (5) maleic acid two ammonium reactors, (6) vacuum system, (7) carbon dioxide recovery reactor, (8) mesohigh stainless steel reactor system, (9) aspartic acid crystallizer, (10) filter plant in accompanying drawing 1.
Embodiment
Embodiment
Chemosynthesis aspartic acid process unit is mainly by maleic acid reactor (1), maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), aspartic acid crystallizer (9), filter plant (10), ammoniacal liquor storage delivery measurement system (2), deionized water storage delivery measurement system (3), carbon dioxide storage tank (4), vacuum system (6), carbon dioxide recovery reactor (7) and supporting supporting electric instrument equipment, transferpump, pipeline, valve, pipe fitting forms.
Maleic acid reactor (1) and maleic acid two ammonium reactors (5) are the stainless steel electric stirring reactors of 100 liters of jacketeds.
Mesohigh stainless steel reactor system (7) is that the high pressure 316L electric stirring reactor of 50 liters of electrified heatings, cooling structure and supporting supporting electric instrument equipment, transferpump, pipeline, valve, pipe fitting form.
Aspartic acid crystallizer (9) be 100 liters with cooling speed governing stainless steel stirred type crystallizer.
Filter plant (10) is PSD 800 type 3-foot Pig discharging stainless steel whizzers, and Main Function is to isolate asparagine acid crystal and reaction mother liquor, makes reaction mother liquor return to maleic acid two ammonium reactor (5) recycles.
Ammoniacal liquor storage delivery measurement system (2) is comprised of 200 liters of PE storage tanks, J-X40/3.0 plunger tpe ammoniacal liquor volume pump, rotor volume under meter and supporting pipeline, valve, pipe fitting, is mainly quantitatively to add ammoniacal liquor for maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), carbon dioxide recovery reactor (7).
Deionized water storage delivery measurement system (3) is comprised of 1000 liters of PE side's bucket deionized water storage tanks, GM500 mechanical diaphragm type deionized water conveying and metering pump, under meter and supporting pipeline, valve pipe fitting, is mainly quantitatively to add deionized water for maleic acid reactor (1), maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), carbon dioxide recovery reactor (6).
Carbon dioxide recovery reactor (6) is 200 liters of airtight stirring stainless steel reactors of low pressure, after quantitatively adding ammoniacal liquor and deionized water, be made into 50 liters of left and right 10% weak ammonias, for reclaiming the mesolow carbonic acid gas of mesohigh stainless steel reactor system (8) and aspartic acid crystallizer (9) pressure release discharge.
Vacuum system (6) is comprised of the two rotary-vane vaccum pumps of 2XZ-1 and 10 liters of glass surge flasks, and being mainly provides vacuum operating condition for mesohigh stainless steel reactor system (7) and aspartic acid crystallizer (9).
The invention process step is as follows:
Weigh 10 kilograms of MALEIC ANHYDRIDE and 10 kilograms of deionized waters in maleic acid reactor (1), heating hydrolysis generates maleic acid solution.
10 kilograms of maleic acid solution are joined to maleic acid two ammonium reactors (5), be evacuated to-0.05MPa, start and stir, then add 8.6 kilogram of 20% ammoniacal liquor, reaction generates 18.6 kilograms of maleic acid two ammonium solutions.
By be evacuated to-0.08MPa of mesohigh stainless steel reactor system (8), add mesohigh stainless steel reactor system (8) to be configured to homogeneous solution 18.6 kilograms of maleic acid two ammonium solutions and 4.4 kilograms of deionized waters, solution within vacuum state adds a small amount of ammoniacal liquor or carbon dioxide recovery reactor, the potential of hydrogen PH7.5-8.5 of adjusting reactor assembly.
Open carbon dioxide storage tank (4) valve and add carbonic acid gas, regulate and control reactor initial reaction pressure 0.5MPa-1.0 MPa.
Start mesohigh stainless steel reactor system (8) and stir and heating installation, regulate 100 ℃-180 ℃ of potential of hydrogen PH7.5-8.5, the temperature of reaction, the reaction pressure 1.0MPa-2.5 MPa that control reactor assembly, set reaction times 2-8 hour.
Reactor assembly reaction finishes, the aspartic acid crystallizer (9) that resultant is pressed into vacuum state cools to 10 ℃-50 ℃, add again maleic acid solution to regulate the potential of hydrogen PH to 2.5-4.0 of the interior material of aspartic acid crystallizer (9), aspartic acid sufficient crystallising is separated out.
In carbon dioxide recovery reactor (6), there is its ammonia soln of 50 liter 10%, absorb the higher carbon dioxide of pressure that mesohigh stainless steel reactor system (8) and aspartic acid crystallizer (9) leak into, reclaim carbonic acid gas.
Start PSD 800 type 3-foot Pig discharging stainless steel whizzers (10), aspartic acid crystallizer (9) material is added to the separated asparagine acid crystal of whizzer (10) and reaction mother liquor, and reaction mother liquor enters maleic acid two ammonium reactor (5) recycles.
Claims (9)
1. chemosynthesis aspartic acid process unit, is characterized in that: mainly maleic acid reactor (1), maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), aspartic acid crystallizer (9), filter plant (10), ammoniacal liquor storage delivery measurement system (2), deionized water storage delivery measurement system (3), carbon dioxide storage tank (4), vacuum system (6), carbon dioxide recovery reactor (7) and supporting electric instrument equipment, transferpump, pipeline, valve, pipe fitting, consist of.
2. chemosynthesis aspartic acid device according to claim 1, it is characterized in that: maleic acid reactor (1) and maleic acid two ammonium reactors (5) are the stainless steel stirred reactors of jacketed, or the glass lined stirring reactor of jacketed.
3. chemosynthesis aspartic acid device according to claim 1, is characterized in that: mesohigh stainless steel reactor system (7) is comprised of the mesohigh stainless steel stirred reactor of electrified heating, cooling structure and supporting electric instrument equipment, transferpump, pipeline, valve, pipe fitting.
4. chemosynthesis aspartic acid device according to claim 1, is characterized in that: aspartic acid crystallizer (9) is with cooling speed governing stainless steel stirred type crystallizer.
5. chemosynthesis aspartic acid device according to claim 1, it is characterized in that: filter plant (10) is 3-foot stainless steel whizzer, or press filter type strainer, or horizontal type screw settling stainless steel whizzer, Main Function is to isolate asparagine acid crystal and reaction mother liquor, makes reaction mother liquor return to maleic acid two ammonium reactor (5) recycles.
6. chemosynthesis aspartic acid device according to claim 1, it is characterized in that: ammoniacal liquor storage delivery measurement system (2) is comprised of the airtight storage tank of low pressure, ammoniacal liquor transferpump, under meter and supporting pipeline, valve, pipe fitting, is mainly quantitatively to add ammoniacal liquor for maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), carbon dioxide recovery reactor (7).
7. chemosynthesis aspartic acid device according to claim 1, it is characterized in that: deionized water storage delivery measurement system (3) is comprised of airtight deionized water storage tank, deionized water transferpump, under meter and supporting pipeline, valve, pipe fitting, is mainly quantitatively to add deionized water for maleic acid reactor (1), maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (8), carbon dioxide recovery reactor (6).
8. chemosynthesis aspartic acid device according to claim 1, it is characterized in that: carbon dioxide recovery reactor (6) is the airtight stirring stainless steel reactor of low pressure, after quantitatively adding ammoniacal liquor and deionized water, reclaim the carbonic acid gas of mesohigh stainless steel reactor system (8), aspartic acid crystallizer (9) pressure release discharge.
9. chemosynthesis aspartic acid device according to claim 1, it is characterized in that: vacuum system (6) is comprised of vacuum pump and surge tank, is mainly to provide vacuum operating condition for maleic acid two ammonium reactors (5), mesohigh stainless steel reactor system (7) and aspartic acid crystallizer (9).
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| CN201410194931.XA CN103951571A (en) | 2014-05-11 | 2014-05-11 | Device for chemical synthesis of asparaginic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805808A (en) * | 2022-05-31 | 2022-07-29 | 郑伟雄 | Preparation method of polyaspartic acid potassium and application of polyaspartic acid potassium in plant growth promoter |
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2014
- 2014-05-11 CN CN201410194931.XA patent/CN103951571A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805808A (en) * | 2022-05-31 | 2022-07-29 | 郑伟雄 | Preparation method of polyaspartic acid potassium and application of polyaspartic acid potassium in plant growth promoter |
| CN114805808B (en) * | 2022-05-31 | 2023-12-08 | 杨凌德尔生物科技有限公司 | Preparation method of potassium polyaspartate and application of potassium polyaspartate in plant growth promoter |
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Application publication date: 20140730 |