CN109485673B - Method for separating L-glufosinate-ammonium and gluconic acid by using ion exchange resin - Google Patents
Method for separating L-glufosinate-ammonium and gluconic acid by using ion exchange resin Download PDFInfo
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- CN109485673B CN109485673B CN201811519965.6A CN201811519965A CN109485673B CN 109485673 B CN109485673 B CN 109485673B CN 201811519965 A CN201811519965 A CN 201811519965A CN 109485673 B CN109485673 B CN 109485673B
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- glufosinate
- ammonium
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 title claims abstract description 86
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000000174 gluconic acid Substances 0.000 title claims abstract description 56
- 235000012208 gluconic acid Nutrition 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 9
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000003480 eluent Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000013375 chromatographic separation Methods 0.000 claims abstract description 11
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000012045 crude solution Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 10
- 238000005406 washing Methods 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 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 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 238000010170 biological method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000005561 Glufosinate Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 230000002210 biocatalytic effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- IAJOBQBIJHVGMQ-SCSAIBSYSA-N (2R)-glufosinate Chemical compound C[P@@](O)(=O)CC[C@@H](N)C(O)=O IAJOBQBIJHVGMQ-SCSAIBSYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UYQVCLAMCWIBKC-UHFFFAOYSA-N OOP(=O)(OC)CCC(N)C(=O)O Chemical compound OOP(=O)(OC)CCC(N)C(=O)O UYQVCLAMCWIBKC-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for separating L-glufosinate-ammonium and gluconic acid by using ion exchange resin, which comprises the following steps: taking L-glufosinate-ammonium crude liquid containing L-glufosinate-ammonium and gluconic acid, and adjusting the pH value of the crude liquid to 1-4 to obtain feed liquid; adding the feed liquid into an exchange column filled with strong acid type cation exchange resin, performing chromatographic separation, and collecting an effluent liquid containing gluconic acid; stopping adding the feed liquid when the concentration of the L-glufosinate-ammonium in the feed liquid reaches 5-10% of the concentration of the L-glufosinate-ammonium in the feed liquid detected at the bottom of the exchange column; then, the resin is washed by deionized water, then the L-glufosinate-ammonium is desorbed by using alkali liquor as an eluent, and the eluent is collected to obtain an L-glufosinate-ammonium solution. According to the invention, the pH value of the L-glufosinate-ammonium crude liquid is firstly adjusted, and then the strong acid type cation exchange resin is utilized for chromatographic separation, so that the high-efficiency separation of the L-glufosinate-ammonium and the gluconic acid is realized, and the separation efficiency is high.
Description
Technical Field
The invention relates to the technical field of L-glufosinate-ammonium production, in particular to a method for separating L-glufosinate-ammonium and gluconic acid by using ion exchange resin.
Background
Glufosinate (glufosinate), which refers to the compound 2-amino-4- [ hydroxy (methyl) phosphono ] -butyric acid. Glufosinate-ammonium is a broad-spectrum contact-type herbicide developed in 80 s by Hoechst (Hoechst) (later belonging to Bayer), belongs to phosphonic acid herbicides, has the action target of glutamine synthetase, and has the characteristics of high activity, good absorption, wide weed control spectrum, low toxicity, good environmental compatibility and the like.
Glufosinate has two optical isomers, L-glufosinate and D-glufosinate. However, only the L-form is phytotoxic and has herbicidal activity 2-fold that of the racemic mixture. Therefore, the development of the preparation process of the L-glufosinate-ammonium has very important significance.
The methods for preparing L-glufosinate are mainly divided into two main categories: chemical and biological methods. The chemical method comprises chemical chiral synthesis and chemical chiral resolution, and the biological method comprises biocatalytic chiral synthesis and biocatalytic chiral resolution. Compared with a chemical method, the biological method has the advantages of strict stereoselectivity, mild reaction conditions and the like, and is a potential advantageous method for producing the L-glufosinate-ammonium.
In the patent application with application publication numbers CN106916857A and CN108588045A, the present group developed two methods for producing L-glufosinate, which use 2-carbonyl-4- (hydroxymethyl phosphonyl) butyric acid or its salt as a substrate, and produce L-glufosinate by an enzyme catalysis system in the presence of an amino donor, and the reaction solution after the reaction mainly contains L-glufosinate, gluconic acid and inorganic salts, which brings about the problem of separation and purification of the product L-glufosinate and the byproduct gluconic acid.
The invention patent application with the application publication number of CN108484665A uses an ion exchange method to separate and purify L-glufosinate-ammonium, but the enzyme conversion solution does not contain gluconic acid, and does not relate to the separation of L-glufosinate-ammonium and gluconic acid. Hilmar Mildenberger et al (U.S. patent application No. 5153355) disclose a process for the multistage countercurrent liquid-liquid extraction separation of L-glufosinate-ammonium from an aqueous solution of L-glutamic acid using at least two different water-soluble polymers or at least one water-soluble salt and one water-soluble polymer.
In summary, in the conventional methods for separating and purifying L-glufosinate-ammonium, no method for separating and purifying L-glufosinate-ammonium reaction liquid produced by chemical or biological methods is reported.
Disclosure of Invention
The invention provides a method for separating L-glufosinate-ammonium and gluconic acid by using ion exchange resin, which is simple to operate, has renewable raw materials, good separation effect and high yield.
The specific technical scheme is as follows:
a method for separating L-glufosinate and gluconic acid using an ion exchange resin, comprising the steps of:
(1) taking L-glufosinate-ammonium crude liquid containing L-glufosinate-ammonium and gluconic acid, and adjusting the pH value of the crude liquid to 1-4 to obtain feed liquid;
(2) adding the feed liquid into an exchange column filled with strong acid type cation exchange resin, performing chromatographic separation, and collecting an effluent liquid containing gluconic acid;
(3) stopping adding the feed liquid when the concentration of the L-glufosinate-ammonium in the feed liquid reaches 5-10% of the concentration of the L-glufosinate-ammonium in the feed liquid detected at the bottom of the exchange column; then, the resin is washed by deionized water, then the L-glufosinate-ammonium is desorbed by using alkali liquor as an eluent, and the eluent is collected to obtain an L-glufosinate-ammonium solution.
The crude L-glufosinate-ammonium solution is obtained by pretreating a reaction solution for producing L-glufosinate-ammonium under the catalysis of an enzyme catalysis system by using 2-carbonyl-4- (hydroxymethyl phosphonyl) butyric acid or salt thereof as a substrate in the presence of an amino donor. The L-glufosinate-ammonium crude liquid contains L-glufosinate-ammonium and gluconic acid, wherein the pretreatment aims at removing ammonium ions and can be realized by adopting a conventional method. The concentration in the step (3) is a mass concentration or a molar concentration.
The pH value of the L-glufosinate-ammonium crude liquid after adjustment has great influence on the separation effect of the L-glufosinate-ammonium and the gluconic acid on the strong acid cation exchange resin. Preferably, in the step (1), the pH value is 2-3. More preferably, the pH value is 2-2.5.
Further, in the step (1), the acid used for adjusting the pH value of the crude liquid is one or a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Further, in the step (2), the type of the strong acid type cation exchange resin is JK006, HZ001, D001, 001 × 7, HZ016, 001 × 8 or HD-8.
More preferably, the strong acid type cation exchange resin is type JK006, HZ001, 001 × 7, HZ016 or 001 × 8.
Further, in the step (2), the height-diameter ratio of the exchange column is 2-50: 1.
Further, in the step (2), the flow rate of the feeding liquid is 0.5-4.0 BV/h; the temperature is 10-60 ℃; too low a flow rate takes a long time and too high a flow rate may result in insufficient exchange.
Further, in the step (3), the volume of the deionized water is 2-8 BV, and the flow rate of the alkali liquor elution is 0.5-4 BV/h; deionized water is used to wash out other components sufficiently, and too low an elution flow rate takes time and too high an elution flow rate may be insufficient and costly.
Further, in the step (3), the alkali liquor is an aqueous solution of one of ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, in the step (3), the alkali liquor is ammonia water; wherein the mass fraction of ammonia is 1-10%. The elution efficiency is ensured by keeping a certain mass fraction of ammonia, and the ammonium salt solution of the L-glufosinate-ammonium can be directly obtained after the ammonia water is eluted.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the pH value of the L-glufosinate-ammonium crude liquid is firstly adjusted, and then the strong acid type cation exchange resin is utilized for chromatographic separation, so that the high-efficiency separation of the L-glufosinate-ammonium and the gluconic acid is realized, and the separation efficiency is high.
(2) The raw materials in the method are easy to obtain and can be repeatedly utilized; good separation effect, high yield and remarkable industrial application prospect.
Detailed Description
The following further describes embodiments of the present invention with reference to specific examples. The following embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Example 1
Adjusting the pH value of a crude liquid containing L-glufosinate-ammonium and gluconic acid to 1.5, wherein the concentration of the L-glufosinate-ammonium is 63.4g/L, the concentration of the gluconic acid is 68.6g/L, taking 10.0g of pretreated JK006 resin, filling the pretreated JK006 resin into an exchange column with the diameter ratio of 15 multiplied by 300mm, and the ratio of height to diameter is 4.7: 1, pumping the crude liquid into an exchange column at the flow rate of 1.0BV/h at the temperature of 25 ℃ for chromatographic separation, and collecting effluent liquid containing gluconic acid; after L-glufosinate-ammonium leaks through the tail end of the ion exchange column, 5BV of deionized water is used for washing the resin, and 3BV of alkali liquor with the ammonia content of 3.2-3.5% is used for desorbing the L-glufosinate-ammonium at the flow rate of 1BV/h after the washing process is finished to obtain the eluent containing the L-glufosinate-ammonium.
16.1ml of crude liquid containing L-glufosinate-ammonium and gluconic acid is pumped in the steps, the concentrations of the L-glufosinate-ammonium and the gluconic acid in the eluent are respectively 25.1g/L and 0.2g/L, and the yield of the L-glufosinate-ammonium is 91.4%.
Example 2
Adjusting the pH value of a crude liquid containing L-glufosinate-ammonium and gluconic acid to 2.3, wherein the concentration of the L-glufosinate-ammonium is 63.4g/L, the concentration of the gluconic acid is 68.6g/L, taking 10.0g of pretreated JK006 resin, filling the pretreated JK006 resin into an exchange column with the diameter ratio of 15 multiplied by 300mm, and the ratio of height to diameter is 4.7: 1; pumping the crude liquid into an exchange column at the flow rate of 1.0BV/h at the temperature of 25 ℃ for chromatographic separation, and collecting an effluent liquid containing gluconic acid; after L-glufosinate-ammonium leaks through the tail end of the ion exchange column, 5BV of deionized water is used for washing the resin, and after the washing process is finished, 3BV of alkali liquor with the ammonia content of 3.2-3.5% is used for desorbing the L-glufosinate-ammonium at the rate of 1BV/h to obtain the eluent containing the L-glufosinate-ammonium.
21.6ml of crude liquid containing L-glufosinate-ammonium and gluconic acid is pumped in the steps, the concentrations of the L-glufosinate-ammonium and the gluconic acid in the eluent are 33.9g/L and 0.3g/L respectively, and the yield of the L-glufosinate-ammonium is 92.2%.
Example 3
Adjusting the pH value of a crude liquid containing L-glufosinate-ammonium and gluconic acid to 2.3, wherein the concentration of the L-glufosinate-ammonium is 63.4g/L, the concentration of the gluconic acid is 68.6g/L, taking 10.0g of pretreated HZ001 resin, filling the resin into an exchange column with the diameter ratio of 15 multiplied by 300mm, and the ratio of height to diameter is 4.5: 1, pumping the crude liquid into an exchange column at the flow rate of 1.0BV/h at the temperature of 25 ℃ for chromatographic separation, and collecting an effluent liquid containing gluconic acid; after L-glufosinate-ammonium leaks through the tail end of the ion exchange column, washing the resin with 5BV of deionized water, and desorbing the L-glufosinate-ammonium with 3BV of alkali liquor with the ammonia content of 3.2-3.5% after the washing process is finished to obtain the eluent containing the L-glufosinate-ammonium.
In the steps, 26.3ml of crude liquid containing L-glufosinate-ammonium and gluconic acid is pumped in, the concentrations of the L-glufosinate-ammonium and the gluconic acid in the eluent are 41.7g/L and 0.2g/L respectively, and the yield of the L-glufosinate-ammonium is 89.8%.
Example 4
Adjusting the pH value of a crude liquid containing L-glufosinate-ammonium and gluconic acid to 2.3, wherein the concentration of the L-glufosinate-ammonium is 63.4g/L, the concentration of the gluconic acid is 68.6g/L, taking 40.0g of pretreated HZ001 resin, filling the resin into an exchange column with the diameter ratio of 15 multiplied by 300mm, and the ratio of height to diameter is 18: 1, pumping the crude liquid into an exchange column at the flow rate of 2.0BV/h at the temperature of 25 ℃ for chromatographic separation, and collecting effluent liquid containing gluconic acid; after L-glufosinate-ammonium leaks through the tail end of the ion exchange column, 5BV of deionized water is used for washing the resin, and 3BV of alkali liquor with the ammonia content of 3.2-3.5% is used for desorbing the L-glufosinate-ammonium at the flow rate of 1BV/h after the washing process is finished to obtain the eluent containing the L-glufosinate-ammonium.
106.4ml of crude liquid containing L-glufosinate-ammonium and gluconic acid is pumped in the steps, the concentrations of the L-glufosinate-ammonium and the gluconic acid in the eluent are 42.3g/L and 0.2g/L respectively, and the yield of the L-glufosinate-ammonium is 90.2%.
Example 5
Adjusting the pH value of a crude liquid containing L-glufosinate-ammonium and gluconic acid to 2.3, wherein the concentration of the L-glufosinate-ammonium is 63.4g/L, the concentration of the gluconic acid is 68.6g/L, taking 40.0g of pretreated HZ001 resin, filling the resin into an exchange column with the diameter ratio of 15 multiplied by 300mm, and the ratio of height to diameter is 18: 1, pumping the crude liquid into an exchange column at the flow rate of 2.0BV/h at the temperature of 25 ℃ for chromatographic separation, and collecting effluent liquid containing gluconic acid; after L-glufosinate-ammonium leaks through the tail end of the ion exchange column, 5BV of deionized water is used for washing the resin, and after the washing process is finished, 5BV of alkali liquor with the ammonia content of 3.2-3.5% is used for desorbing the L-glufosinate-ammonium at the flow rate of 1.5BV/h to obtain the eluent containing the L-glufosinate-ammonium.
104.5ml of crude liquid containing L-glufosinate-ammonium and gluconic acid is pumped in the steps, the concentrations of the L-glufosinate-ammonium and the gluconic acid in the eluent are respectively 25.9g/L and 0.1g/L, and the yield of the L-glufosinate-ammonium is 92.5%.
Example 6
Adjusting the pH value of a crude liquid containing L-glufosinate-ammonium and gluconic acid to 2.3, wherein the concentration of the L-glufosinate-ammonium is 63.4g/L, the concentration of the gluconic acid is 68.6g/L, taking 10.0g of pretreated HZ001 resin, filling the resin into an exchange column with the diameter ratio of 15 multiplied by 300mm, and the ratio of height to diameter is 4.5: 1, pumping the crude liquid into an exchange column at the flow rate of 1.0BV/h at the temperature of 25 ℃ for chromatographic separation, and collecting an effluent liquid containing gluconic acid; after L-glufosinate-ammonium leaks through the tail end of the ion exchange column, 5BV of deionized water is used for washing the resin, and after the washing process is finished, 5BV of 1mol/L sodium hydroxide solution is used for desorbing the L-glufosinate-ammonium at the flow rate of 1.5BV/h to obtain the eluent containing the L-glufosinate-ammonium.
25.6ml of crude liquid containing L-glufosinate-ammonium and gluconic acid is pumped in the steps, the concentrations of the L-glufosinate-ammonium and the gluconic acid in the eluent are 24.9g/L and 0.1g/L respectively, and the yield of the L-glufosinate-ammonium is 91.8%.
Claims (6)
1. A method for separating L-glufosinate-ammonium and gluconic acid by using ion exchange resin, which is characterized by comprising the following steps:
(1) taking L-glufosinate-ammonium crude liquid containing L-glufosinate-ammonium and gluconic acid, and adjusting the pH value of the crude liquid to 2-2.5 to obtain feed liquid;
(2) adding the feed liquid into an exchange column filled with strong acid type cation exchange resin, performing chromatographic separation, and collecting an effluent liquid containing gluconic acid; the height-diameter ratio of the exchange column is 2-50: 1; the types of the strong acid type cation exchange resin are JK006 and HZ 001;
(3) stopping adding the feed liquid when the concentration of the L-glufosinate-ammonium in the feed liquid reaches 5-10% of the concentration of the L-glufosinate-ammonium in the feed liquid detected at the bottom of the exchange column; then, the resin is washed by deionized water, then the L-glufosinate-ammonium is desorbed by using alkali liquor as an eluent, and the eluent is collected to obtain an L-glufosinate-ammonium solution.
2. The method for separating L-glufosinate-ammonium and gluconic acid according to claim 1, wherein the acid used for adjusting the pH of the crude solution in the step (1) is one or a mixed acid of two or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
3. The method for separating L-glufosinate-ammonium and gluconic acid from the ion exchange resin according to claim 1, wherein in the step (2), the flow rate of the feed liquid is 0.5 to 4.0 BV/h; the temperature is 10-60 ℃.
4. The method for separating L-glufosinate-ammonium and gluconic acid according to claim 1, wherein the volume of the deionized water in the step (3) is 2 to 8BV, and the flow rate of the alkali solution elution is 0.5 to 4 BV/h.
5. The method for separating L-glufosinate and gluconic acid from an ion exchange resin according to claim 1, wherein in step (3), the alkali solution is an aqueous solution of one of ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
6. The method for separating L-glufosinate-ammonium and gluconic acid according to claim 5, wherein in the step (3), the alkali solution is ammonia water; wherein the mass fraction of ammonia is 1-10%.
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