CN116162665A - Method and device for preparing L-glufosinate-ammonium from D, L-glufosinate-ammonium reaction solution - Google Patents
Method and device for preparing L-glufosinate-ammonium from D, L-glufosinate-ammonium reaction solution Download PDFInfo
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- glufosinate
- ammonium
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 61
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 claims abstract description 139
- 239000012535 impurity Substances 0.000 claims abstract description 65
- 238000001914 filtration Methods 0.000 claims abstract description 38
- 230000002210 biocatalytic effect Effects 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 136
- 238000000108 ultra-filtration Methods 0.000 claims description 84
- 238000001728 nano-filtration Methods 0.000 claims description 71
- 239000012528 membrane Substances 0.000 claims description 40
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 claims description 31
- 239000003814 drug Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 235000002639 sodium chloride Nutrition 0.000 claims description 22
- 238000007670 refining Methods 0.000 claims description 20
- 239000005561 Glufosinate Substances 0.000 claims description 19
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 102000004190 Enzymes Human genes 0.000 claims description 14
- 108090000790 Enzymes Proteins 0.000 claims description 14
- 238000010612 desalination reaction Methods 0.000 claims description 13
- 239000012466 permeate Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 102000004674 D-amino-acid oxidase Human genes 0.000 claims description 9
- 108010003989 D-amino-acid oxidase Proteins 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000011033 desalting Methods 0.000 claims description 8
- IAJOBQBIJHVGMQ-SCSAIBSYSA-N (2R)-glufosinate Chemical compound C[P@@](O)(=O)CC[C@@H](N)C(O)=O IAJOBQBIJHVGMQ-SCSAIBSYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 102000016938 Catalase Human genes 0.000 claims description 2
- 108010053835 Catalase Proteins 0.000 claims description 2
- 108030000198 L-amino-acid dehydrogenases Proteins 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000012452 mother liquor Substances 0.000 abstract description 4
- 239000005456 alcohol based solvent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000008595 infiltration Effects 0.000 description 17
- 238000001764 infiltration Methods 0.000 description 17
- 229940079593 drug Drugs 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 9
- 239000010413 mother solution Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 102000003929 Transaminases Human genes 0.000 description 7
- 108090000340 Transaminases Proteins 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000005515 coenzyme Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011026 diafiltration Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
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- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- YLGMSFUVQDSUEG-UHFFFAOYSA-N 4-(hydroxymethylphosphanyl)-2-oxobutanoic acid Chemical compound OCPCCC(=O)C(O)=O YLGMSFUVQDSUEG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/001—Amines; Imines
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
- C12P41/001—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by metabolizing one of the enantiomers
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Abstract
The invention discloses a method and a device for preparing L-glufosinate-ammonium from a D, L-glufosinate-ammonium reaction solution, which are characterized by comprising the following steps: (1) Ultra-filtering organic impurities and nano-filtering to remove salt from the D, L-glufosinate reaction solution to obtain a D, L-glufosinate refined solution with the solute molecular weight of 150-6000 Da; (2) And performing biocatalytic conversion on the refined D, L-glufosinate-ammonium refined solution to obtain L-glufosinate-ammonium conversion solution. The method not only can shorten the process flow and avoid the use of alcohol solvents, but also can avoid the generation of low-quality D, L-glufosinate-ammonium crystallization mother liquor from the source, reduce the process energy consumption and improve the product yield.
Description
Technical Field
The invention relates to a method for preparing L-glufosinate-ammonium from a D, L-glufosinate-ammonium reaction solution, belonging to the technical fields of pesticide chemical industry and membrane separation.
Background
The glufosinate is a phosphonic acid non-selective contact herbicide and has the characteristics of high efficiency, broad spectrum, low toxicity and environmental protection. Glufosinate exists in two optical isomers of D-glufosinate and L-glufosinate, but only L-glufosinate has herbicidal activity.
The preparation method of the L-glufosinate-ammonium comprises a chemical method and a biological method. The biocatalysis method is an important trend for industrially preparing the L-glufosinate-ammonium due to the advantages of mild reaction conditions, high stereoselectivity and the like. At present, most of biocatalysis methods take 2-oxo-4- (hydroxymethyl phosphino) butyric acid (PPO) as a substrate, and the L-glufosinate-ammonium is asymmetrically synthesized through ammonification reaction, but the method also has the defects of low PPO conversion rate and high reaction temperature. The current industrial production scheme is basically a biocatalytic conversion process using D, L-glufosinate as raw material, which benefits from the mature mass production state of D, L-glufosinate.
Chinese patent CN 112626142A and international patent WO2017151573A1 disclose a process for preparing L-glufosinate-ammonium from D, L-glufosinate-ammonium by two-step biocatalytic conversion, respectively, but only the process is described, and no actual production is combined, and in particular, the purity requirements of the raw materials D, L-glufosinate-ammonium are not mentioned.
In practice, since the enzyme value involved in the biocatalytic conversion is high due to the large amount of inorganic salts and organic polymer, pigment and other impurities existing in the chemically synthesized D, L-glufosinate reaction solution, it is necessary to perform purification and purification to remove organic impurities and inorganic salts and the like from the chemically synthesized D, L-glufosinate reaction solution in order to avoid adverse effects of inorganic salt impurities and organic impurities in the D, L-glufosinate reaction solution on the catalytic conversion efficiency. Therefore, the existing enterprises generally crystallize and refine the chemically synthesized D, L-glufosinate reaction liquid to form crystals with the purity of more than 95 percent, and then take the refined D, L-glufosinate crystals with the purity of more than 95 percent as raw materials to produce the L-glufosinate through biocatalysis conversion. The refining process of glufosinate-ammonium is divided into a traditional chemical method and a membrane method:
(1) Traditional chemical method: CN107434811A, CN 102268037A provides two kinds of glufosinate-ammonium esterification purification processes, and the purity of the obtained D, L-glufosinate-ammonium can reach more than 95% after being dried. However, the pure technology is complex and difficult to control, and the yield and quality difference among batches are large; the energy consumption is extremely high, a crystallization mother solution is generated, the ratio of D, L-glufosinate in the mother solution is about 10-25%, so that the yield of the D, L-glufosinate for preparing the L-glufosinate is limited by the generation of the mother solution, and the mother solution with high salt content and organic impurities often enters the market for sale in a low-quality product, and once the mother solution is used in a large amount, the soil environment is influenced.
(2) Membrane separation method: patent document CN 105859772A provides a membrane separation and purification method of glufosinate-ammonium reaction solution, which comprises diluting the glufosinate-ammonium reaction solution several times, separating and purifying the reaction solution by using a multistage nanofiltration process and a reverse osmosis process, evaporating, crystallizing and drying the nanofiltration concentrated solution to prepare glufosinate-ammonium raw medicine. Because organic impurities are not removed pertinently, and ammonium chloride and sodium chloride are removed only to 3% -4%, the purity of the obtained glufosinate-ammonium is 92.3% -96.3%. Patent document CN 110577554A provides a method for treating glufosinate-ammonium reaction liquid by a membrane separation technology, which adopts an ultrafiltration, nanofiltration, reverse osmosis and electrodialysis integrated membrane technology and evaporation coupling to purify the glufosinate-ammonium reaction liquid, and the purity of the glufosinate-ammonium raw medicine obtained through crystallization and drying ranges from 95.6% to 96.2%. Besides the crystallization treatment, various separation processes are combined.
In summary, it is necessary to develop a new process for efficiently preparing L-glufosinate from the reaction solution of D, L-glufosinate.
Disclosure of Invention
Aiming at the defects of the existing process for preparing the L-glufosinate-ammonium from the D, L-glufosinate-ammonium reaction solution, the invention aims to provide a novel process for preparing the L-glufosinate-ammonium from the D, L-glufosinate-ammonium reaction solution through, and the process does not need crystallization and purification before biocatalysis conversion, shortens the process flow, reduces the energy consumption and can reduce the environmental pollution caused by crystallization mother solution.
In the prior art, D, L-glufosinate is taken as a raw material to prepare L-glufosinate by two-step biocatalytic conversion, more researches at present are focused on the aspect of enzyme catalytic systems, and according to the conventional industry cognition, the purity of D, L-glufosinate in solid raw material medicines of D, L-glufosinate is required to reach 95% in order to ensure that the enzyme activity is not greatly influenced by impurities, which is also the reason that the refining and purifying process research of D, L-glufosinate in the prior art aims at reaching the purity of 95%, and the intensive research on specific impurities in the reaction liquid of D, L-glufosinate has obvious influence on the catalytic conversion is neglected. In the research of preparing the L-glufosinate by two-step biocatalytic conversion by taking the D, L-glufosinate as a raw material, the inventor finds that under specific refining conditions, even if the D, L-glufosinate as a catalytic conversion raw material does not adopt a solid raw material with the purity of 95%, the ideal L-glufosinate yield can be obtained, the process can be greatly simplified, the energy consumption is obviously reduced, and the unexpected effect of further improving the yield is obtained on the premise of omitting the working procedure, which possibly indicates that the existence of most of impurities with the molecular mass of 150-6000Da has little or negligible influence on the enzyme activity.
Based on this finding, the present application provides a process for preparing L-glufosinate from a reaction solution of D, L-glufosinate, characterized by the steps of:
(1) Ultra-filtering organic impurities and nano-filtering to remove salt from the D, L-glufosinate reaction solution to obtain a D, L-glufosinate refined solution with the solute molecular weight of 150-6000 Da;
(2) And performing biocatalytic conversion on the refined D, L-glufosinate-ammonium refined solution to obtain L-glufosinate-ammonium conversion solution.
Preferably, the step (1) is performed with ultrafiltration and nanofiltration for salt removal to obtain a D, L-glufosinate-ammonium refined solution with a solute molecular weight of 150-2000Da, so that the yield of the L-glufosinate-ammonium can reach 95% without affecting the purity basically. More preferably a D, L-glufosinate-ammonium refined solution with a solute molecular weight of 150-1000.
The step (1) of carrying out ultrafiltration and nanofiltration and desalination processes on the D, L-glufosinate reaction liquid can be as follows: ultrafiltering with ultrafilter membrane with molecular weight cut-off of 1000-6000 and Da to eliminate organic impurity, and ultrafiltering the ultrafiltered permeate with nanofiltration membrane with molecular weight cut-off of 150-300Da to eliminate salt. The method can also be as follows: nanofiltration and desalination are carried out by using a nanofiltration membrane with the molecular weight cutoff of 150-300Da, and ultrafiltration and filtration of organic impurities are carried out on the concentrated solution with the cutoff side nanofiltration after desalination by using an ultrafiltration membrane with the molecular weight cutoff of 1000-6000 Da. I.e. the order of the removal of organic impurities and the desalting steps can be varied, the inventors have found that there is no essential difference.
The organic impurity removing process in the step (1) adopts a one-stage or multi-stage ultrafiltration organic impurity removing process, the same or different organic roll-type ultrafiltration membranes are used for each stage of ultrafiltration organic impurities, and the operating pressure range for ultrafiltration organic impurity removing is 0.4-4.0 MPa. And (2) in the step (1), the nanofiltration salt is filtered by adopting one-stage or multi-stage nanofiltration, each stage nanofiltration membrane is the same or different machine-rolled nanofiltration membranes, and the nanofiltration salt operation pressure range is 0.4-10.0 MPa.
In the invention, the biocatalytic conversion method in the step (2) is to convert and produce L-glufosinate-ammonium by taking D, L-glufosinate-ammonium as a raw material under an enzyme catalytic system. The enzyme catalytic system comprises D-amino acid oxidase for converting D-glufosinate to PPO, and L-amino acid dehydrogenase and catalase for converting PPO to L-glufosinate. Each enzyme in the enzyme catalytic system is in a form selected independently from: refined enzyme; cell-free or crude cell extract; liquid, powder or fixed form; whole cells or whole fermentation broth, lyophilized cells, or any combination thereof.
In the present invention, the method may further comprise the steps of: (3) And (3) carrying out ultrafiltration on the L-glufosinate-ammonium conversion solution obtained in the step (2) to remove organic impurities, thereby obtaining a refined L-glufosinate-ammonium aqueous solution. Or still further comprising the steps of: (4) Concentrating and crystallizing the refined L-glufosinate-ammonium water solution in the step (3) to obtain an L-glufosinate-ammonium original drug or directly preparing an L-glufosinate-ammonium water agent.
And (3) concentrating and crystallizing in the step (4) comprising concentrating, dehydrating and cooling for crystallizing. The concentration dehydration operation temperature is 70-90 ℃, and the mass fraction of the concentrated solution L-glufosinate is 65-85%. The crystallization temperature of the cooling crystallization is 5-10 ℃.
The invention also provides a device for preparing L-glufosinate by using the D, L-glufosinate reaction solution, and in one embodiment, the device comprises:
the first ultrafiltration device has a molecular weight cutoff of 1000-6000Da and is used for removing organic impurities from the D, L-glufosinate reaction solution;
the nanofiltration device has a molecular weight cutoff of 150-300Da and is connected to the permeation side of the first ultrafiltration device and is used for desalting the first ultrafiltration permeate;
the biocatalytic conversion device is connected to the interception side of the nanofiltration device and is used for biocatalytic conversion of the D, L-glufosinate-ammonium refined solution after desalination of the organic impurities are removed;
the second ultrafiltration device is connected to the outlet of the biocatalysis conversion device and is used for refining the conversion liquid;
and the concentrating and crystallizing device is connected to the permeation side of the second ultrafiltration device and is used for concentrating and crystallizing the permeate of the second ultrafiltration device.
In another embodiment of the apparatus for preparing L-glufosinate from a reaction solution of D, L-glufosinate, the apparatus comprises:
the nanofiltration device has a molecular weight cutoff of 150-300Da and is used for desalting the D, L-glufosinate reaction solution;
the first ultrafiltration device has a molecular weight cutoff of 1000-6000Da, is connected to the cutoff side of the nanofiltration device, and is used for removing organic impurities from desalted D, L-glufosinate-ammonium reaction liquid;
the biocatalytic conversion device is connected to the permeation side of the first ultrafiltration device and is used for biocatalytic conversion of the D, L-glufosinate-ammonium refined solution after desalination and removal of organic impurities;
the second ultrafiltration device is connected to the outlet of the biocatalysis conversion device and is used for refining the conversion liquid;
and the concentrating and crystallizing device is connected to the permeation side of the second ultrafiltration device and is used for concentrating and crystallizing the permeate of the second ultrafiltration device.
Compared with the prior art, the method has the following advantages:
(1) Because ultrafiltration and nanofiltration are adopted to remove organic impurities and remove salt, the crystallization and purification process of D, L-glufosinate-ammonium is omitted, the process flow is simplified, the operation is convenient, and the production cost is reduced.
(2) By the method, the yield of the L-glufosinate can reach more than 80%, and the ideal yield can reach more than 95%, and the problem of byproduct low-quality D, L-glufosinate crystallization mother liquor in the preparation process of the L-glufosinate can be radically solved.
(3) The method has the advantages that no esterification process or crystallization process can be used for continuous production, the efficiency is low, the method is coupled with electricity and automatic control, the partial continuous automatic production can be realized, and the production efficiency is greatly improved.
(4) The L-glufosinate can be prepared by freely selecting water aqua or raw medicines according to market demands, and the proportion can be adjusted at will.
(5) The mass fraction of the L-glufosinate can reach more than 95%, the ratio of the L-glufosinate to the glufosinate can reach more than 97%, and the unconverted D-glufosinate is very little.
Drawings
FIG. 1 is a diagram showing a preparation process of L-glufosinate-ammonium from a D, L-glufosinate-ammonium reaction solution;
FIG. 2 is a diagram showing another preparation process of L-glufosinate from a reaction solution of D, L-glufosinate according to the invention.
Detailed Description
The invention is shown in fig. 1 and 2, wherein the technical process and the device for preparing L-glufosinate by using the D, L-glufosinate reaction solution are characterized in that the D, L-glufosinate reaction solution is used as a raw material, organic impurities are ultra-filtered by an ultrafiltration system, nanofiltration and desalination are carried out by a nanofiltration system to obtain a D, L-glufosinate refined solution, and the refined solution is not required to be crystallized and purified like the traditional process, but the D, L-glufosinate refined solution is directly added into a biocatalysis system to be subjected to two-step catalytic conversion, and D-glufosinate in the refined solution is converted into L-glufosinate to obtain the L-glufosinate conversion solution. The L-glufosinate conversion liquid is subjected to ultrafiltration system to remove organic impurities according to requirements to obtain L-glufosinate refined liquid, and then is concentrated and crystallized by an evaporation crystallization system to obtain the L-glufosinate raw medicine. Compared with the prior art, the process is greatly shortened, the D, L-glufosinate containing crystallization mother liquor with the folding percentage of 10-25% is not generated, the glufosinate loss caused by the crystallization mother liquor is avoided, the mass fraction of the L-glufosinate in the obtained L-glufosinate raw medicine can reach more than 95%, the total glufosinate ratio of the L-glufosinate can reach more than 97%, and the D-glufosinate conversion rate is improved.
The D, L-glufosinate reaction solution can be any one of acidolysis ammoniation solution of glufosinate amino nitrile, alkaline hydrolysis solution of glufosinate amino nitrile and aqueous solution of acid hydrolysis solution after esterification, desalting and then hydrolysis. Preferably, the mass fraction of glufosinate in the D, L-glufosinate reaction solution is 1-38%, the mass fraction of inorganic salt is 0.5-30%, and the pH value of the solution is 1.5-14; the inorganic salt is one or more of ammonium chloride, sodium chloride, potassium chloride, ammonium sulfate, sodium sulfate and potassium sulfate.
1. Device for preparing L-glufosinate
1. Example 1
An apparatus for preparing L-glufosinate from a reaction solution of D, L-glufosinate corresponding to the embodiment shown in FIG. 2 comprises the following apparatus units:
the first ultrafiltration device has a molecular weight cutoff of 1000-6000Da and is used for removing organic impurities from the D, L-glufosinate reaction solution;
the nanofiltration device has a molecular weight cutoff of 150-300Da and is connected to the permeation side of the first ultrafiltration device and used for desalting the first ultrafiltration permeate;
the biocatalytic conversion device is connected to the interception side of the nanofiltration device and is used for biocatalytic conversion of the D, L-glufosinate-ammonium refined solution after desalination of the organic impurities are removed;
the second ultrafiltration device is connected to the outlet of the biocatalysis conversion device and is used for refining the conversion liquid;
and the concentrating and crystallizing device is connected to the permeation side of the second ultrafiltration device and is used for concentrating and crystallizing the permeate of the second ultrafiltration device.
Example 2
In another embodiment of an apparatus for preparing L-glufosinate from a D, L-glufosinate reaction solution, as shown in FIG. 1, the apparatus comprises:
the nanofiltration device has a molecular weight cutoff of 150-300Da and is used for desalting the D, L-glufosinate reaction solution;
the first ultrafiltration device has a molecular weight cut-off of 1000-6000Da and is connected to the cut-off side of the nanofiltration device and is used for removing organic impurities from the desalted D, L-glufosinate-ammonium reaction solution;
the biocatalysis conversion device is connected to the permeation side of the first ultrafiltration device and is used for biocatalysis transfer of the D, L-glufosinate-ammonium refined solution after desalination and removal of organic impurities;
the second ultrafiltration device is connected to the outlet of the biocatalysis conversion device and is used for refining the conversion liquid;
and the concentrating and crystallizing device is connected to the permeation side of the second ultrafiltration device and is used for concentrating and crystallizing the permeate of the second ultrafiltration device.
2. Process for preparing L-glufosinate
The glufosinate reaction solution adopted in the following examples is an ammoniated solution of glufosinate amino nitrile acid hydrolysate after ammoniation, and the main components are as follows: 25% of glufosinate, 7% of ammonium chloride and 7% of sodium chloride.
Example 1
And (3) refining: directly ultrafiltering the glufosinate reaction solution to remove organic impurities, wherein the ultrafiltration membrane is made of polyamide, the molecular weight cut-off is 1000Da, the filtration pressure is 3.8MPa, the ultrafiltration concentration is 20 times, 3.2 times of the mass of the concentrated solution is added for diafiltration after the concentration is finished, and the 1# ultrafiltrate, namely the organic impurity removal solution, is obtained on the permeation side of an ultrafiltration system, and the 1# ultrafiltrate concentrate is obtained on the cut-off side; removing organic impurity liquid, carrying out nanofiltration and salting, wherein the nanofiltration membrane is made of polyamide, the molecular weight cut-off is 150Da, the filtration pressure is 6.5MPa, constant volume infiltration is adopted, the infiltration water amount is 3.3 times of the mass of the nanofiltration stock solution, and the nanofiltration concentrated solution, namely the D, L-glufosinate refined solution, is obtained on the nanofiltration cut-off side.
Step (2) catalytic conversion: and (3) adding D amino acid oxidase, transaminase, coenzyme and the like into the D, L-glufosinate refined solution after 1-time dilution, and controlling the reaction temperature to be 15-45 ℃, the pH range to be 6.5-10 and the reaction time to be 3-42 hours to obtain the L-glufosinate conversion solution.
And (3) refining: and then ultra-filtering organic impurities from the conversion solution, wherein the ultrafiltration membrane is made of alumina, the filtering pressure is 0.4MPa, concentrating 10 times, adding water with the mass of 5 times that of the concentrated solution for infiltration, and fully recovering L-glufosinate in the concentrated solution to obtain 2# ultrafiltrate and 2# ultrafiltrate concentrate.
After the treatment, the components of each unit are as follows:
(4) And (3) evaporating and crystallizing: concentrating the 2# ultrafiltrate by steam at 70-90 ℃ until the mass fraction of the L-glufosinate is 65-85%, crystallizing at 5-10 ℃ and drying to obtain the L-glufosinate original drug. The purity of the detected L-glufosinate-ammonium original drug is 97%, and the proportion of the L-glufosinate-ammonium in the total glufosinate-ammonium is 99%. The yield was 95.55% based on the finally obtained L-glufosinate.
Example 2 (expansion of ultrafiltration molecular weight of # 1, decrease in conversion, yield, purity)
And (3) refining: directly ultrafiltering the glufosinate reaction solution to remove organic impurities, wherein the ultrafiltration membrane is made of polyamide, the molecular weight cut-off is 2000Da, the filtration pressure is 3.8MPa, the ultrafiltration concentration is 20 times, 3.2 times of the mass of the concentrated solution is added for diafiltration after the concentration is finished, and the 1# ultrafiltrate, namely the organic impurity removal solution, is obtained on the permeation side of an ultrafiltration system, and the 1# ultrafiltrate concentrate is obtained on the cut-off side; removing organic impurity liquid, carrying out nanofiltration and salting, wherein the nanofiltration membrane is made of polyamide, the molecular weight cut-off is 150Da, the filtration pressure is 6.5MPa, constant volume infiltration is adopted, the infiltration water amount is 3.3 times of the mass of the nanofiltration stock solution, and the nanofiltration concentrated solution, namely the D, L-glufosinate refined solution, is obtained on the nanofiltration cut-off side.
Step (2) catalytic conversion: and (3) adding D amino acid oxidase, transaminase, coenzyme and the like into the D, L-glufosinate refined solution after 1-time dilution, and controlling the reaction temperature to be 15-45 ℃, the pH range to be 6.5-10 and the reaction time to be 3-42 hours to obtain the L-glufosinate conversion solution.
And (3) refining: and then ultra-filtering organic impurities from the conversion solution, wherein the ultrafiltration membrane is made of alumina, the filtering pressure is 0.4MPa, concentrating 10 times, adding water with the mass of 5 times that of the concentrated solution for infiltration, and fully recovering L-glufosinate in the concentrated solution to obtain 2# ultrafiltrate and 2# ultrafiltrate concentrate.
After the treatment, the components of each unit are as follows: the components of each unit obtained were as follows:
and (4) evaporating and crystallizing: concentrating the 2# ultrafiltrate by steam at 70-90 ℃ until the mass fraction of the L-glufosinate is 65-85%, crystallizing at 5-10 ℃ and drying to obtain the L-glufosinate original drug. The purity of the detected L-glufosinate-ammonium original drug is 96.5%, and the proportion of the L-glufosinate-ammonium is 98%. The yield was 95.20% based on the finally obtained L-glufosinate.
Example 3 (nanofiltration followed by ultrafiltration)
And (3) refining: firstly, carrying out nanofiltration and salt removal on glufosinate reaction liquid, wherein a nanofiltration membrane is made of polyamide, the molecular weight cut-off is 150Da, the filtration pressure is 6.5MPa, constant volume infiltration is adopted, the infiltration water amount is 3.3 times of the mass of nanofiltration stock solution, and nanofiltration concentrated solution is obtained on the nanofiltration cut-off side; the nanofiltration concentrated solution is subjected to ultrafiltration to remove organic impurities, the ultrafiltration membrane is made of polyamide, the molecular weight cut-off is 1000Da, the filtration pressure is 3.8MPa, the ultrafiltration concentration is 20 times, the concentrated solution is added with water with 3.8 times of the mass for diafiltration after the concentration is finished, and the 1# ultrafiltrate, namely the solution for removing the organic impurities, namely the D, L-glufosinate refined solution is obtained on the permeation side of an ultrafiltration system.
Step (2) catalytic conversion: and (3) adding D amino acid oxidase, transaminase, coenzyme and the like into the D, L-glufosinate refined solution after 1-time dilution, and controlling the reaction temperature to be 15-45 ℃, the pH range to be 6.5-10 and the reaction time to be 8-32 hours to obtain the L-glufosinate conversion solution.
And (3) refining: and then carrying out ultrafiltration on the conversion liquid to remove organic impurities, wherein the ultrafiltration membrane is made of alumina, the filtration pressure is 0.4MPa, the concentration is 10 times, the 5.3 times mass of water of the concentrated liquid is added for infiltration, and the L-glufosinate-ammonium in the concentrated liquid is fully recovered to obtain 2# ultrafiltrate and 2# ultrafiltrate concentrate.
After the treatment, the components of each unit are as follows: the components of each unit obtained were as follows:
and (4) evaporating and crystallizing: concentrating the 2# ultrafiltrate by steam at 70-90 ℃ until the mass fraction of the L-glufosinate is 65-85%, crystallizing at 5-10 ℃ and drying to obtain the L-glufosinate original drug. The purity of the detected L-glufosinate-ammonium original drug is 96.4%, and the proportion of the L-glufosinate-ammonium is 98.8%. The yield was 95.45% based on the finally obtained L-glufosinate.
Example 4 (increased ultrafiltration 4000Da, nanofiltration 200 Da)
And (3) refining: directly ultrafiltering the glufosinate reaction solution to remove organic impurities, wherein the ultrafiltration membrane is made of polyamide, the molecular weight cut-off is 4000Da, the filtration pressure is 3.8MPa, the ultrafiltration concentration is 20 times, 3.2 times of the mass of the concentrated solution is added for diafiltration after the concentration is finished, and the 1# ultrafiltrate, namely the organic impurity removal solution, is obtained on the permeation side of an ultrafiltration system, and the 1# ultrafiltrate concentrate is obtained on the cut-off side; removing organic impurity liquid, carrying out nanofiltration and salting, wherein the nanofiltration membrane is made of polyamide, the molecular weight cut-off is 200Da, the filtration pressure is 6.5MPa, constant volume infiltration is adopted, the infiltration water amount is 3.3 times of the mass of the nanofiltration stock solution, and the nanofiltration concentrated solution, namely the D, L-glufosinate refined solution, is obtained on the nanofiltration cut-off side.
Step (2) catalytic conversion: and (3) adding D amino acid oxidase, transaminase, coenzyme and the like into the D, L-glufosinate refined solution after 1-time dilution, and controlling the reaction temperature to be 15-45 ℃, the pH range to be 6.5-10 and the reaction time to be 3-42 hours to obtain the L-glufosinate conversion solution.
And (3) refining: and then ultra-filtering organic impurities from the conversion solution, wherein the ultrafiltration membrane is made of alumina, the filtering pressure is 0.4MPa, concentrating 10 times, adding water with the mass of 5 times that of the concentrated solution for infiltration, and fully recovering L-glufosinate in the concentrated solution to obtain 2# ultrafiltrate and 2# ultrafiltrate concentrate.
After the treatment, the components of each unit are as follows: the components of each unit obtained were as follows:
(4) And (3) evaporating and crystallizing: concentrating the 2# ultrafiltrate by steam at 70-90 ℃ until the mass fraction of the L-glufosinate is 65-85%, crystallizing at 5-10 ℃ and drying to obtain the L-glufosinate original drug. The purity of the detected L-glufosinate-ammonium original drug is 97 percent, and the proportion of the L-glufosinate-ammonium is 98 percent. The yield was 88.71% based on the finally obtained L-glufosinate.
Example 5 (molecular weight expansion ultrafiltration nanofiltration, conversion, purity unchanged, yield reduced)
And (3) refining: directly ultrafiltering the glufosinate reaction solution to remove organic impurities, wherein the ultrafiltration membrane is made of polyamide, the molecular weight cut-off is 6000Da, the filtration pressure is 3.8MPa, the ultrafiltration concentration is 20 times, 3.2 times of the mass of the concentrated solution is added for diafiltration after the concentration is finished, and the 1# ultrafiltrate, namely the organic impurity removal solution, is obtained on the permeation side of an ultrafiltration system, and the 1# ultrafiltrate concentrate is obtained on the cut-off side; removing organic impurity liquid, carrying out nanofiltration and salting, wherein the nanofiltration membrane is made of polyamide, the molecular weight cut-off is 300Da, the filtration pressure is 6.5MPa, constant volume infiltration is adopted, the infiltration water amount is 3.3 times of the mass of the nanofiltration stock solution, and the nanofiltration concentrated solution, namely the D, L-glufosinate refined solution, is obtained on the nanofiltration cut-off side.
Step (2) catalytic conversion: and (3) adding D amino acid oxidase, transaminase, coenzyme and the like into the D, L-glufosinate refined solution after 1-time dilution, and controlling the reaction temperature to be 15-45 ℃, the pH range to be 6.5-10 and the reaction time to be 3-42 hours to obtain the L-glufosinate conversion solution.
And (3) refining: and then ultra-filtering organic impurities from the conversion solution, wherein the ultrafiltration membrane is made of alumina, the filtering pressure is 0.4MPa, concentrating 10 times, adding water with the mass of 5 times that of the concentrated solution for infiltration, and fully recovering L-glufosinate in the concentrated solution to obtain 2# ultrafiltrate and 2# ultrafiltrate concentrate.
After the treatment, the components of each unit are as follows: the components of each unit obtained were as follows:
(4) And (3) evaporating and crystallizing: concentrating the 2# ultrafiltrate by steam at 70-90 ℃ until the mass fraction of the L-glufosinate is 65-85%, crystallizing at 5-10 ℃ and drying to obtain the L-glufosinate original drug. The purity of the detected L-glufosinate-ammonium original drug is 97 percent, and the proportion of the L-glufosinate-ammonium is 99 percent. The yield was 83.9% based on the finally obtained L-glufosinate.
Comparative example 1 (conventional process)
The glufosinate-ammonium aminonitrile is first acid hydrolyzed to obtain glufosinate-ammonium hydrochloride water solution, and the solution is evaporated and concentrated until the water content of the material is below 10%, so as to obtain concentrated mother solution. And (3) carrying out esterification reaction on the concentrated mother solution and methanol under the catalysis of acid, controlling the esterification rate to be higher than 95% in the reflux, cooling to 10 ℃, and filtering to remove solid inorganic salt to obtain filtrate. And (3) after recovering alcohol from the filtrate, adding hydrochloric acid, stirring and refluxing, concentrating until the water content of the material is less than 1%, then evaporating and concentrating until the water content of the material is less than 10%, adding methanol for refluxing and dispersing, cooling, filtering to obtain a hydrochloride crude product, and drying to obtain the glufosinate-ammonium hydrochloride crude product. Adding the obtained crude product of glufosinate-ammonium hydrochloride into methanol with the mass being 10 times that of the glufosinate-ammonium hydrochloride, introducing ammonia gas, adjusting the pH value to 8-9, cooling to 10 ℃, filtering, drying filter cakes, and obtaining a white glufosinate-ammonium product, and detecting the purity of D, L-glufosinate-ammonium and the crystallization rate to be 85%. And re-dissolving the D, L-glufosinate with the purity of 95% into a 10% mass fraction aqueous solution, sequentially adding D amino acid oxidase, transaminase, coenzyme and the like, controlling the reaction temperature to be 15-45 ℃, the pH range to be 6.5-10 and the reaction time to be 3-42 hours to obtain an L-glufosinate conversion solution, carrying out solid-liquid separation on the conversion solution, evaporating, crystallizing and drying to obtain an L-glufosinate raw medicine, and detecting the purity of the L-glufosinate raw medicine to be 97% and the proportion of the L-glufosinate to be 98%. The yield was 80.83% based on the finally obtained L-glufosinate.
Comparative example 2 (preparation of D, L-glufosinate-ammonium by membrane separation and crystallization, preparation of L-glufosinate-ammonium by re-dissolution, unchanged product quality, lower yield)
Directly ultrafiltering the glufosinate reaction solution to remove organic impurities, wherein an ultrafiltration membrane is made of polyamide, the molecular weight cutoff is 1500Da, the filtration pressure is 3.8MPa, ultrafiltration concentration is 20 times, 3.2 times of the mass of the concentrated solution is added after concentration is finished, so as to obtain organic impurity removing solution, nanofiltration salt is carried out on the organic impurity removing solution, the nanofiltration membrane is made of polyamide, the molecular weight cutoff is 150Da, the filtration pressure is 6.5MPa, constant volume infiltration is adopted, the infiltration water amount is 3.3 times of the mass of the nanofiltration raw solution, so as to obtain D, L-glufosinate refined solution, the D, L-glufosinate refined solution is concentrated to D at 70-80 ℃, and then methanol which is 8 times of the mass of the glufosinate is added, and then ammonia gas is introduced to adjust the pH value to 7.5, then the temperature is slowly reduced, the D, L-glufosinate solid is stirred and separated out, the D, L-glufosinate raw medicine is obtained through solid-liquid separation and drying, the purity of the D, L-glufosinate raw medicine is detected, the crystallization rate is 90%, the obtained D, L-glufosinate raw medicine is redissolved and added with D-amino acid oxidase, transaminase, coenzyme and the like successively, the reaction temperature is controlled to 15-45 ℃, the pH value range is 6.5-10, the reaction time is controlled to 3-42 h, the L-glufosinate conversion liquid is obtained, the conversion liquid is subjected to ultrafiltration for organic impurities, the ultrafiltration membrane is made of alumina, the filtration pressure is 0.4MPa, the concentrated liquid is added with 5 times mass of water for filtration after 10 times concentration, and the L-glufosinate in the concentrated liquid is fully recovered. The components of each unit obtained were as follows:
the ultrafiltrate is evaporated, concentrated, crystallized and dried to obtain the L-glufosinate-ammonium original drug, and the purity of the L-glufosinate-ammonium original drug is 97.5 percent and the proportion of the L-glufosinate-ammonium is 99 percent after detection. The yield was 86% based on the finally obtained L-glufosinate.
As is clear from comparison of examples 1-5 with comparative examples 1 and 2, the yields of L-glufosinate were significantly improved in examples 1-5 and in examples 1-4 compared with comparative example 2 when the purity and ratio of the L-glufosinate were comparable to those of comparative examples 1 and 2 after simplifying the process.
Claims (18)
1. A method for preparing L-glufosinate from a D, L-glufosinate reaction solution is characterized by comprising the following steps:
(1) Ultra-filtering organic impurities and nano-filtering to remove salt from the D, L-glufosinate reaction solution to obtain a D, L-glufosinate refined solution with the solute molecular weight of 150-6000 Da;
(2) And performing biocatalytic conversion on the refined D, L-glufosinate-ammonium refined solution to obtain L-glufosinate-ammonium conversion solution.
2. The method of claim 1, wherein the step (1) is performed with ultrafiltration of organic impurities and nanofiltration of salt to obtain a D, L-glufosinate-ammonium refined solution with a solute molecular weight of 150-2000 Da.
3. The method according to claim 1, wherein the D, L-glufosinate reaction solution is any one of acidolysis ammoniation solution of glufosinate-aminonitrile, alkaline hydrolysis solution of glufosinate-aminonitrile, and aqueous solution of acid hydrolysis solution after esterification, desalination and hydrolysis.
4. The method of claim 1, wherein the mass fraction of glufosinate in the D, L-glufosinate reaction solution is 1-38%, the mass fraction of inorganic salt is 0.5-30%, and the pH of the solution is 1.5-14; the inorganic salt is one or more of ammonium chloride, sodium chloride, potassium chloride, ammonium sulfate, sodium sulfate and potassium sulfate.
5. The method according to claim 1, wherein the step (1) comprises the steps of ultra-filtering organic impurities and nano-filtering salt from the reaction solution of D, L-glufosinate: ultrafiltering with ultrafilter membrane with cut-off molecular weight of 1000-6000Da to eliminate organic impurity, and ultrafiltering the ultrafiltered permeate with nanofiltration membrane with cut-off molecular weight of 150-300Da to eliminate salt.
6. The method according to claim 1, wherein the step (1) comprises the steps of ultra-filtering organic impurities and nano-filtering salt from the reaction solution of D, L-glufosinate: nanofiltration and desalination are carried out by using a nanofiltration membrane with the interception molecular weight of 150-300Da, and ultrafiltration and filtration of organic impurities are carried out by using a nanofiltration concentrated solution with the interception side after desalination and an ultrafiltration membrane with the interception molecular weight of 1000-6000 Da.
7. The method of claim 1, wherein the step (1) is performed by using one or more stages of ultrafiltration process for removing organic impurities, each stage of ultrafiltration process uses the same or different organic roll-type ultrafiltration membranes, and the ultrafiltration operation pressure range for removing organic impurities is 0.4-4.0 mpa.
8. The method of claim 1, wherein the nanofiltration salt in the step (1) is filtered by one or more stages of nanofiltration membranes, each stage of nanofiltration membranes are the same or different machine-rolled nanofiltration membranes, and the nanofiltration salt operation pressure range is 0.4-10.0 mpa.
9. The method according to claim 1, wherein the biocatalytic conversion method in the step (2) is to convert D-glufosinate to produce L-glufosinate by using D, L-glufosinate as a raw material under an enzyme catalytic system.
10. The process according to claim 9, wherein the enzyme catalytic system comprises a D-amino acid oxidase for converting D-glufosinate to PPO, and an L-amino acid dehydrogenase, catalase for converting PPO to L-glufosinate.
11. The method of claim 9, wherein each enzyme in the enzyme catalytic system is in a form independently selected from the group consisting of: refined enzyme; cell-free or crude cell extract; liquid, powder or fixed form; whole cells or whole fermentation broth, lyophilized cells, or any combination thereof.
12. The method of claim 1, further comprising the step of: (3) And (3) carrying out ultrafiltration refining on the L-glufosinate-ammonium conversion solution obtained in the step (2) to obtain an L-glufosinate-ammonium refined solution.
13. The method of claim 12, further comprising the step of: (4) Concentrating and crystallizing the refined L-glufosinate-ammonium solution obtained in the step (3) to obtain an original L-glufosinate-ammonium medicament or directly preparing an L-glufosinate-ammonium aqua.
14. The method of claim 13, wherein the concentrating the crystals in step (4) comprises concentrating, dehydrating, and cooling the crystals.
15. The method of claim 14, wherein the concentration and dehydration operation temperature is 70-90 ℃ and the mass fraction of the concentrated liquid L-glufosinate is 65-85%.
16. The method of claim 14, wherein the crystallization temperature of the reduced temperature crystallization is 5-10 ℃.
17. The device for preparing the L-glufosinate-ammonium from the D, L-glufosinate-ammonium reaction solution is characterized by comprising:
the first ultrafiltration device has a molecular weight cutoff of 1000-6000Da and is used for removing organic impurities from the D, L-glufosinate reaction solution;
the nanofiltration device has a molecular weight cutoff of 150-300Da and is connected to the permeation side of the first ultrafiltration device and used for desalting the first ultrafiltration permeate;
the biocatalytic conversion device is connected to the interception side of the nanofiltration device and is used for biocatalytic conversion of the D, L-glufosinate-ammonium refined solution after desalination of the organic impurities are removed;
the second ultrafiltration device is connected to the outlet of the biocatalysis conversion device and is used for refining the L-glufosinate conversion liquid;
and the concentrating and crystallizing device is connected to the permeation side of the second ultrafiltration device and is used for concentrating and crystallizing the permeate of the second ultrafiltration device.
18. The device for preparing the L-glufosinate-ammonium from the D, L-glufosinate-ammonium reaction solution is characterized by comprising:
the nanofiltration device has a molecular weight cutoff of 150-300Da and is used for desalting the D, L-glufosinate reaction solution;
the first ultrafiltration device has a molecular weight cut-off of 1000-6000Da and is connected to the cut-off side of the nanofiltration device and is used for removing organic impurities from the desalted D, L-glufosinate-ammonium reaction solution;
the biocatalytic conversion device is connected to the permeation side of the first ultrafiltration device and is used for biocatalytic conversion of the D, L-glufosinate-ammonium refined solution after desalination and removal of organic impurities;
the second ultrafiltration device is connected to the outlet of the biocatalysis conversion device and is used for refining the L-glufosinate conversion liquid;
and the concentrating and crystallizing device is connected to the permeation side of the second ultrafiltration device and is used for concentrating and crystallizing the permeate of the second ultrafiltration device.
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