CN112358499A - Synthesis method of glufosinate-ammonium - Google Patents
Synthesis method of glufosinate-ammonium Download PDFInfo
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- 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 title claims abstract description 47
- 238000001308 synthesis method Methods 0.000 title claims abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 90
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 58
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- -1 methyl ester acetal Chemical class 0.000 claims abstract description 39
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical compound CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 30
- MCLITRXWHZUNCQ-UHFFFAOYSA-N methylcyanamide Chemical compound CNC#N MCLITRXWHZUNCQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 25
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000005086 pumping Methods 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000001728 nano-filtration Methods 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 26
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 239000005561 Glufosinate Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 238000011033 desalting Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 5
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract 1
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 77
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000005562 Glyphosate Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 4
- 229940097068 glyphosate Drugs 0.000 description 4
- 230000002363 herbicidal effect Effects 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of glufosinate-ammonium. Comprises the following steps; 1. pumping the diethyl methylphosphite, acrolein, acetic acid and a catalyst I into a secondary reactor for continuous reaction to generate methyl ester acetal; 2. continuously reacting the methyl ester acetal with mixed liquid of sodium cyanide, ammonium chloride, ammonia water and a catalyst II through a three-stage reactor to generate methyl cyanamide; 3. cyanylation hydrolysis of methyl amino, and evaporation of the product after hydrolysis through a film to obtain glufosinate-ammonium; 4. reacting glufosinate-ammonium acid with ammonia gas to generate a glufosinate-ammonium crude product; 5. and separating the crude glufosinate-ammonium product by a secondary nanofiltration membrane, distilling and crystallizing to obtain a glufosinate-ammonium finished product. The synthesis method adopts continuous reaction, the liquid holdup in the synthesis process is small, the production process is safe and efficient, and the process operation is simple; the problems of long reaction time, low efficiency, high loss and low purity of the traditional kettle type intermittent reaction are solved.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of glufosinate-ammonium.
Background
Glufosinate-ammonium is a broad-spectrum contact-type biocidal herbicide developed successfully by eggfu, germany in the 80's of the 20 th century. Glufosinate belongs to phosphonic acid herbicides and can inhibit glutamine synthetase in plant nitrogen metabolic pathways, so that metabolism of plants is interfered, and the plants die. The glufosinate-ammonium has the characteristics of wide herbicidal spectrum, low toxicity, high activity, good environmental compatibility and the like, and the speed of playing the active action is slower than that of paraquat and is better than that of glyphosate. The herbicide can be used as a non-selective herbicide with coexistence of glyphosate and paraquat, and has wide application prospect. Many weeds are sensitive to glufosinate and can be used as a substitute for glyphosate in areas where glyphosate is resistant.
Due to the above-mentioned advantages of glufosinate-ammonium salts, the preparation thereof has received attention in recent years. The prior production process of glufosinate ammonium salt comprises the following steps: high pressure catalytic synthesis, the Czochralski method, and the Abuzov-Michael synthesis. The scholak-zerlington method comprises the following: firstly, deacidifying an amino nitrile compound, adding alcohol to dissolve the amino nitrile compound, removing ammonium chloride and sodium chloride, adding alcohol and acid to refine to prepare glufosinate-ammonium hydrochloride, then introducing ethylene oxide to prepare glufosinate-ammonium phosphate, and introducing ammonia to generate glufosinate-ammonium salt. Wherein, alcohol is required to be added for 4-5 times, the solvent is added in a large amount, and the ethylene oxide belongs to toxic and harmful gases.
The glufosinate-ammonium synthesis method mainly used in China is a Spthox-Zerlington method and mainly comprises the following steps: phosphorus trichloride, triethyl phosphite and a lattice reagent are firstly used for synthesizing diethyl methylphosphite, the diethyl methylphosphite and sodium cyanide react to generate an amino nitrile compound, and the amino nitrile compound is reduced by hydrochloric acid, introduced with ethylene oxide, aminated and the like to generate glufosinate ammonium salt. In patent CN102268037A, a process for purifying glufosinate ammonium is disclosed, which utilizes hydrochloric acid to convert an aminonitrile compound into glufosinate hydrochloride, and then introduces ethylene oxide gas to generate glufosinate-ammonium, and the glufosinate-ammonium reacts with ammonia gas to generate glufosinate ammonium; the method needs to introduce toxic and harmful gas ethylene oxide, and repeated crystallization is carried out through alcohol precipitation, so that the solvent consumption is high, and the synthesis yield of the glufosinate-ammonium salt is low.
Chinese patent CN201110160129 discloses a process for purifying glufosinate-ammonium, which comprises adding alcohol R1OH into glufosinate-ammonium hydrochloride to perform esterification reaction to obtain an esterified product of glufosinate-ammonium hydrochloride, then adding the obtained esterified product of glufosinate-ammonium hydrochloride into a hydrochloric acid aqueous solution to perform hydrolysis reaction to obtain glufosinate-ammonium hydrochloride, then adding glufosinate-ammonium hydrochloride into alcohol R2OH, introducing ethylene oxide to react to obtain glufosinate-ammonium, then adding glufosinate-ammonium into R3OH, and introducing ammonia gas to obtain glufosinate-ammonium. In the third step of the method, when the glufosinate-ammonium acid is prepared from the glufosinate-ammonium hydrochloride, ethylene oxide is used, and the ethylene oxide is gas at normal temperature and normal pressure, has a low flash point, is inflammable and explosive, so that the method is high in danger and has high requirements on equipment. Therefore, there is still a need for further improvements in the process for the preparation of glufosinate-ammonium.
Disclosure of Invention
The invention aims to provide a synthesis method of glufosinate-ammonium, which solves the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the glufosinate-ammonium is prepared with diethyl methyl phosphite, acraldehyde, acetic acid, sodium cyanide, ammonia water, ammonium chloride, hydrochloric acid and ammonia and through multistage continuous reaction in a continuous flow reactor.
Further, the synthesis method of glufosinate-ammonium comprises the following steps;
(1) precooling diethyl methylphosphite, mixing and stirring acrolein, acetic acid and the catalyst I, and precooling; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor for reaction to prepare methyl ester acetal; (2) continuously reacting the methyl ester acetal with mixed liquid of sodium cyanide, ammonium chloride, ammonia water and a catalyst II through a three-stage reactor to generate methyl cyanamide; (3) cyanylation hydrolysis of methyl amino, and evaporation of the product after hydrolysis through a film to obtain glufosinate-ammonium; (4) reacting glufosinate-ammonium acid with ammonia gas to generate a glufosinate-ammonium crude product; (5) and separating the crude glufosinate-ammonium product by a secondary nanofiltration membrane, distilling and crystallizing to obtain a glufosinate-ammonium finished product.
The chemical reaction equation for glufosinate synthesis is as follows:
CH3P(OEt)2+CH2CHCHO+HAC→CH3P(O)(OEt)CH2CHCHOAc
CH3P(O)(OEt)CH2CHCHOAc+NaCN+NH4Cl→CH3P(O)(OEt)CH2CH2CH(CN)NH2
CH3P(O)(OEt)CH2CH2CH(CN)NH2+HCl+H2O→CH3P(O)(OH)CH2CH2CH(NH2)COOH
CH3P(O)(OH)CH2CH2CH(NH2)COOH+NH3→CH3P(O)(OH)CH2CH2CH(NH2)COONH4
further, the synthesis method of glufosinate-ammonium comprises the following steps;
(1) cooling diethyl methylphosphite to-5-0 ℃; mixing acrolein, acetic acid and a catalyst I, stirring, and cooling to-5-0 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 9-11 ℃, and the temperature of a second-stage reactor is 14-16 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) feeding the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing sodium cyanide, ammonium chloride, ammonia water and a catalyst II, stirring until the materials are dissolved, and pumping into a first-stage reactor; the temperature of the first-stage reactor is 14-16 ℃, the temperature of the second-stage reactor is 18-22 ℃, and the temperature of the third-stage reactor is 28-32 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) allowing the methyl cyanamide prepared in the step (2) to enter a two-stage continuous reactor, adding hydrochloric acid into the first-stage reactor, performing two-stage continuous reaction to prepare an ammonium oxalate solution, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing ammonia gas into the reactor, and reacting to obtain a glufosinate crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
Further, the synthesis method of glufosinate-ammonium comprises the following steps;
(1) cooling diethyl methylphosphite to-5-0 ℃; mixing acrolein, acetic acid and a catalyst I, stirring, and cooling to-5-0 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 9-11 ℃, and the temperature of a second-stage reactor is 14-16 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) feeding the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing sodium cyanide, ammonium chloride, ammonia water and a catalyst II, stirring until the materials are dissolved, and pumping into a first-stage reactor; the temperature of the first-stage reactor is 14-16 ℃, the temperature of the second-stage reactor is 18-22 ℃, and the temperature of the third-stage reactor is 28-32 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) introducing the methyl cyanamide prepared in the step (2) into a two-stage continuous reactor, adding hydrochloric acid into a first-stage reactor, wherein the temperature of the first-stage reactor is 78-82 ℃, and the temperature of a second-stage reactor is 105-115 ℃; preparing an ammonium oxalate solution through two-stage continuous reaction, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing ammonia gas into the reactor, and reacting at the temperature of 30-40 ℃ to obtain a glufosinate-ammonium crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
Further, the molar ratio of the diethyl methylphosphite, the acrolein, the acetic acid, the sodium cyanide, the ammonium chloride, the ammonia water, the hydrochloric acid and the ammonia is 1: 1: 1: 1: 1: 1.5: 2: 1.
further, the catalyst I in the step (1) is an organic phosphorus catalyst.
Further, the catalyst II in the step (1) is a phase transfer catalyst.
Further, the phase transfer catalyst is any one or more of 18-crown-6, 15-crown-5, tetrabutylammonium bromide, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
Further, the mass concentration of the hydrochloric acid in the step (3) is 30-35%.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the step of synthesizing the intermediate methyl ester acetal, acetic anhydride in the old process is replaced by acetic acid, the acetic anhydride is a toxic substance easy to prepare and controlled by the ministry of public security, the purchase and the use are limited, and the price of the acetic anhydride is higher; the acetic acid raw material has wide source and low price. And the methyl ester acetal is synthesized without solvent, so that the yield of the synthesis method is greatly improved compared with the synthesis process using ethanol as solvent in the traditional process.
(2) The invention adopts continuous reaction to synthesize glufosinate-ammonium, adopts an automatic multistage reactor and a multistage temperature control reaction mode in the synthesis process, has less liquid holdup in the reaction process, safe and efficient production process, and improves the problems of long reaction time, low efficiency and high loss in the traditional kettle type intermittent reaction.
(3) In the invention, the glufosinate-ammonium acid and the inorganic salt are separated by adopting the nanofiltration membrane, and then the high-purity glufosinate-ammonium is directly obtained by introducing ammonia gas, so that the process is simple. The traditional process adopts the following two ways to process the step: 1. distilling most of acid water, adding ammonia water, centrifugally separating inorganic salt, distilling again, and adding a large amount of methanol for recrystallization; the method has the advantages of complicated steps, high energy consumption and large wastewater production. 2. Distilling most of acid water, centrifugally separating out inorganic salt, adding methanol to dissolve, introducing ethylene oxide or propylene oxide to remove hydrogen chloride, and then introducing ammonia to generate glufosinate-ammonium.
(4) In the process of synthesizing glufosinate-ammonium, no waste residue is generated, the treatment capacity of solid hazardous wastes is greatly reduced, and the method meets the requirement of environmental protection.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of a multi-stage reaction for continuous synthesis of glufosinate-ammonium in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis method of glufosinate-ammonium
Preparing raw materials: the catalyst II is 18-crown ether-6; the mass solubility of the hydrochloric acid solution was 30%. The specific synthesis method comprises the following steps;
(1) 13.6g of diethyl methylphosphite are cooled to-5 ℃; mixing 5.61g of acrolein, 6g of acetic acid and 0.01g of catalyst I, stirring, and cooling to-5 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 9 ℃, and the temperature of a second-stage reactor is 14 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) putting the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing 4.91g of sodium cyanide, 5.35g of ammonium chloride, 26.2g of ammonia water and 0.005g of 18-crown ether-6, stirring until the materials are dissolved, and pumping the dissolved sodium cyanide, ammonium chloride, ammonia water and 18-crown ether-6 mixed solution into a first-stage reactor; the temperature of the first-stage reactor is 15 ℃, the temperature of the second-stage reactor is 18 ℃, and the temperature of the third-stage reactor is 28 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) allowing the methyl cyanamide prepared in the step (2) to enter a two-stage continuous reactor, adding 24.3g of hydrochloric acid into a first-stage reactor, wherein the temperature of the first-stage reactor is 78 ℃ and the temperature of a second-stage reactor is 105 ℃; preparing an ammonium oxalate solution through two-stage continuous reaction, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing 1.7g of ammonia gas into the reactor, and reacting at 30 ℃ to obtain a glufosinate-ammonium crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
Example 2
Synthesis method of glufosinate-ammonium
Preparing raw materials: the catalyst II is 15-crown ether-5; the mass solubility of the hydrochloric acid solution was 30%. The specific synthesis method comprises the following steps;
(1) 13.6g of diethyl methylphosphite are cooled to-3 ℃; mixing 5.61g of acrolein, 6g of acetic acid and 0.01g of catalyst I, stirring, and cooling to-3 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 10 ℃, and the temperature of a second-stage reactor is 15 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) putting the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing 4.9g of sodium cyanide, 5.35g of ammonium chloride, 26.2g of ammonia water and 0.005g of 15-crown ether-5, stirring until the materials are dissolved, and pumping the dissolved sodium cyanide, ammonium chloride, ammonia water and 15-crown ether-5 mixed solution into a first-stage reactor; the temperature of the first-stage reactor is 15 ℃, the temperature of the second-stage reactor is 20 ℃, and the temperature of the third-stage reactor is 30 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) allowing the methyl cyanamide prepared in the step (2) to enter a two-stage continuous reactor, adding 24.3g of hydrochloric acid into a first-stage reactor, wherein the temperature of the first-stage reactor is 80 ℃ and the temperature of a second-stage reactor is 107 ℃; preparing an ammonium oxalate solution through two-stage continuous reaction, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing 1.7g of ammonia gas into the reactor, and reacting at 35 ℃ to obtain a glufosinate-ammonium crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
Example 3
Synthesis method of glufosinate-ammonium
Preparing raw materials: the catalyst II is selected from dodecyl trimethyl ammonium chloride; the mass solubility of the hydrochloric acid solution is 32%. The specific synthesis method comprises the following steps;
(1) 13.6g of diethyl methylphosphite are cooled to 0 ℃; mixing 56.1g of acrolein, 6g of acetic acid and 0.01g of catalyst I, stirring, and cooling to 0 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 10 ℃, and the temperature of a second-stage reactor is 15 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) putting the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing 4.9g of sodium cyanide, 5.35g of ammonium chloride, 26.2g of ammonia water and 0.01g of dodecyl trimethyl ammonium chloride, stirring until the materials are dissolved, and pumping the dissolved mixed solution of the sodium cyanide, the ammonium chloride, the ammonia water and the dodecyl trimethyl ammonium chloride into a first-stage reactor; the temperature of the first-stage reactor is 15 ℃, the temperature of the second-stage reactor is 20 ℃, and the temperature of the third-stage reactor is 30 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) allowing the methyl cyanamide prepared in the step (2) to enter a two-stage continuous reactor, adding 24.3g of hydrochloric acid into a first-stage reactor, wherein the temperature of the first-stage reactor is 80 ℃ and the temperature of a second-stage reactor is 110 ℃; preparing an ammonium oxalate solution through two-stage continuous reaction, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing 1.7g of ammonia gas into the reactor, and reacting at 35 ℃ to obtain a glufosinate-ammonium crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
Example 4
Synthesis method of glufosinate-ammonium
Preparing raw materials: catalyst II is selected to be tetrabutylammonium bromide; the mass solubility of the hydrochloric acid solution was 35%. The specific synthesis method comprises the following steps;
(1) 13.6g of diethyl methylphosphite are cooled to 0 ℃; mixing 5.61g of acrolein, 6g of acetic acid and 0.01g of catalyst I, stirring, and cooling to-5 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 11 ℃, and the temperature of a second-stage reactor is 16 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) putting the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing 4.9g of sodium cyanide, 5.35g of ammonium chloride, 26.2g of ammonia water and 0.01g of catalyst II, stirring until the materials are dissolved, and pumping the dissolved mixed solution of the sodium cyanide, the ammonium chloride, the ammonia water and the catalyst II into a first-stage reactor; the temperature of the first-stage reactor is 16 ℃, the temperature of the second-stage reactor is 22 ℃, and the temperature of the third-stage reactor is 32 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) allowing the methyl cyanamide prepared in the step (2) to enter a two-stage continuous reactor, adding 24.3g of hydrochloric acid into a first-stage reactor, wherein the temperature of the first-stage reactor is 80 ℃ and the temperature of a second-stage reactor is 110 ℃; preparing an ammonium oxalate solution through two-stage continuous reaction, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing 1.7g of ammonia gas into the reactor, and reacting at 40 ℃ to obtain a glufosinate-ammonium crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
Comparative example 1
Preparing raw materials: catalyst II is selected to be tetrabutylammonium bromide; the mass solubility of the hydrochloric acid solution is 35 percent; the addition amounts of diethyl methylphosphite, acrolein, acetic acid, sodium cyanide, ammonium chloride, ammonia water, hydrochloric acid and ammonia were the same as in example 4; the specific synthesis method comprises the following steps;
(1) synthesis of methyl ester acetal: putting quantitative diethyl methylphosphite, acetic acid and an organic phosphorus catalyst into a dry anhydrous oxygen-free reaction kettle, stirring, dropwise adding acrolein at the temperature of 11 ℃ for 8 hours, and after dropwise adding, keeping the temperature at the temperature of 16 ℃ for reaction for 1 hour to obtain methyl ester acetal;
(2) synthesis of methyl cyanamide: putting quantitative sodium cyanide, ammonium chloride, ammonia water and tetrabutylammonium bromide into a reaction kettle, stirring until the materials are dissolved, dropwise adding methyl ester acetal at the temperature of 15 ℃, keeping the temperature and reacting for 1h at the temperature of 20 ℃ to obtain the methyl cyanamide, wherein the dropwise adding time is 10 h;
(3) synthesis of glufosinate-ammonium: adding hydrochloric acid into a reaction kettle, heating to 80 ℃, adding methyl cyanamide, refluxing for 1h, and distilling to obtain glufosinate-ammonium; adding methanol for dissolving, separating out salt through a nanofiltration membrane, introducing ammonia gas into the glufosinate-ammonium acid solution, and crystallizing to obtain the finished product glufosinate-ammonium.
Comparative example 2
Putting 13.6g of diethyl methylphosphite, 1.2g of acetic anhydride and ethanol into a dry anhydrous and oxygen-free reaction kettle, and dropwise adding 5.6g of acrolein at the temperature of-5 ℃ to obtain methylal;
putting 4.9g of sodium cyanide, 5.9g of ammonium chloride and 32g of ammonia water into a reaction kettle, stirring, dissolving the materials, and then dropwise adding methyl acetal at the temperature of 20 ℃ to obtain methyl cyanamide;
50g of hydrochloric acid is put into a reaction kettle, and the mass solubility of the hydrochloric acid solution is 35%; adding methyl cyanamide, heating to 100 ℃, refluxing for 1h, after refluxing, distilling acid water, adding ammonia water to adjust the pH value to 7, separating salt, distilling water, adding a large amount of methanol to dissolve, and crystallizing to obtain the finished product glufosinate-ammonium.
Comparative example 3
13.6g of diethyl methylphosphite and 100g of ethanol are firstly put into a dry anhydrous and oxygen-free reaction kettle, and 5.6g of acrolein is dripped at the temperature of minus 5 ℃ to obtain the methyl phosphorus acetal; adding the methyl phosphorus acetal into a certain amount of dilute acid, and distilling ethanol and water to obtain methyl acetal;
putting 4.9g of sodium cyanide, 5.9g of ammonium chloride and 32g of ammonia water into a reaction kettle, stirring, dissolving the materials, and then dropwise adding methyl acetal at the temperature of 15 ℃ to obtain methyl cyanamide;
50g of hydrochloric acid is put into a reaction kettle, and the mass solubility of the hydrochloric acid solution is 35%; adding methyl cyanamide, heating to 100 ℃, refluxing for 2h, distilling to remove acid water, adding methanol, heating to reflux, cooling to 30 ℃, separating out salt to obtain mother liquor, adding hydrochloric acid, heating to 100 ℃, refluxing for 2h, distilling to remove acid water, adding ethanol, and recrystallizing to obtain glufosinate-ammonium hydrochloride; adding into methanol, introducing 32g ethylene oxide (or propylene oxide), centrifuging to obtain glufosinate-ammonium acid, adding methanol, and introducing 12g ammonia gas to obtain glufosinate-ammonium.
Integrated data analysis
Examples 1 to 4 are technical solutions of the present invention; comparative example 1 is a batch reaction in a kettle type, and the rest is the same as example 4; comparative example 2 is a synthesis example in which acetic anhydride was used instead of acetic acid and a large amount of solvent was used; comparative example 3 is a synthesis example using ethylene oxide and propylene oxide in the conventional process. The yield of glufosinate prepared in examples 1-4 and comparative examples 1-3 is calculated as shown in table 1 below, and the purity detection data of glufosinate prepared by each group is shown in table 1 below;
TABLE 1
As can be seen from the data in Table 1, the glufosinate content of the products prepared in examples 1-4 reaches 96%, and the yield is about 92%; the content and yield of the glufosinate prepared by the comparative examples 2-3 are respectively 94.9%/91.2% and 94.3%/0.1%, and the content and yield of the glufosinate prepared by the comparative examples 2-3 are lower than those of the examples 1-4, so that the glufosinate synthesis process provided by the invention can replace the synthesis process of dangerous goods such as a large amount of solvents, propylene oxide, ethylene oxide and the like and acetic anhydride controlled goods used in the traditional process, and has high yield and high purity. Compared with the example 4, the comparative example 1 shows that the continuous-stage reaction provided by the invention has lower loss and higher yield of glufosinate-ammonium compared with the kettle type batch reaction.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A synthesis method of glufosinate-ammonium, which is characterized in that; the glufosinate-ammonium is mainly prepared by carrying out multistage continuous reaction on diethyl methylphosphite, acrolein, acetic acid, sodium cyanide, ammonia water, ammonium chloride, hydrochloric acid and ammonia in a continuous flow reactor.
2. The method for synthesizing glufosinate-ammonium according to claim 1, characterized in that: comprises the following steps;
(1) precooling diethyl methylphosphite, mixing and stirring acrolein, acetic acid and the catalyst I, and precooling; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor for reaction to prepare methyl ester acetal;
(2) continuously reacting the methyl ester acetal with mixed liquid of sodium cyanide, ammonium chloride, ammonia water and a catalyst II through a three-stage reactor to generate methyl cyanamide;
(3) cyanylation hydrolysis of methyl amino, and evaporation of the product after hydrolysis through a film to obtain glufosinate-ammonium;
(4) reacting glufosinate-ammonium acid with ammonia gas to generate a glufosinate-ammonium crude product;
(5) and separating the crude glufosinate-ammonium product by a secondary nanofiltration membrane, distilling and crystallizing to obtain a glufosinate-ammonium finished product.
3. The method for synthesizing glufosinate-ammonium according to claim 2, characterized in that: comprises the following steps;
(1) cooling diethyl methylphosphite to-5-0 ℃; mixing acrolein, acetic acid and a catalyst I, stirring, and cooling to-5-0 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 9-11 ℃, and the temperature of a second-stage reactor is 14-16 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) feeding the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing sodium cyanide, ammonium chloride, ammonia water and a catalyst II, stirring until the materials are dissolved, and pumping into a first-stage reactor; the temperature of the first-stage reactor is 14-16 ℃, the temperature of the second-stage reactor is 18-22 ℃, and the temperature of the third-stage reactor is 28-32 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) allowing the methyl cyanamide prepared in the step (2) to enter a two-stage continuous reactor, adding hydrochloric acid into the first-stage reactor, performing two-stage continuous reaction to prepare an ammonium oxalate solution, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing ammonia gas into the reactor, and reacting to obtain a glufosinate crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
4. The method for synthesizing glufosinate-ammonium according to claim 3, characterized in that: comprises the following steps;
(1) cooling diethyl methylphosphite to-5-0 ℃; mixing acrolein, acetic acid and a catalyst I, stirring, and cooling to-5-0 ℃; pumping the cooled mixed solution of diethyl methylphosphite, acrolein and acetic acid into a two-stage continuous reactor, wherein the temperature of a first-stage reactor is 9-11 ℃, and the temperature of a second-stage reactor is 14-16 ℃; two-stage continuous reaction to prepare methyl ester acetal;
(2) feeding the methyl ester acetal prepared in the step (1) into a three-stage continuous reactor, mixing sodium cyanide, ammonium chloride, ammonia water and a catalyst II, stirring until the materials are dissolved, and pumping into a first-stage reactor; the temperature of the first-stage reactor is 14-16 ℃, the temperature of the second-stage reactor is 18-22 ℃, and the temperature of the third-stage reactor is 28-32 ℃; carrying out three-stage continuous reaction to obtain methyl cyanamide;
(3) introducing the methyl cyanamide prepared in the step (2) into a two-stage continuous reactor, adding hydrochloric acid into a first-stage reactor, wherein the temperature of the first-stage reactor is 78-82 ℃, and the temperature of a second-stage reactor is 105-115 ℃; preparing an ammonium oxalate solution through two-stage continuous reaction, and evaporating the ammonium oxalate solution through a film device to obtain ammonium oxalate;
(4) allowing the glufosinate acid to enter a next-stage reactor, introducing ammonia gas into the reactor, and reacting at the temperature of 30-40 ℃ to obtain a glufosinate-ammonium crude product;
(5) and (3) separating and desalting the coarse glufosinate ammonium product by a secondary nanofiltration membrane, distilling, and crystallizing methanol to obtain a finished glufosinate ammonium product.
5. The method for synthesizing glufosinate-ammonium according to claim 4, characterized in that: the molar ratio of the diethyl methylphosphite, the acrolein, the acetic acid, the sodium cyanide, the ammonium chloride, the ammonia water, the hydrochloric acid and the ammonia is 1: 1: 1: 1: 1: 1.5: 2: 1.
6. the method for synthesizing glufosinate-ammonium according to claim 4, wherein; in the step (1), the catalyst I is an organic phosphorus catalyst.
7. The method for synthesizing glufosinate-ammonium according to claim 4, characterized in that: and the catalyst II in the step (1) is a phase transfer catalyst.
8. The method for synthesizing glufosinate-ammonium according to claim 7, characterized in that: the phase transfer catalyst is any one or more of 18-crown-6, 15-crown-5, tetrabutylammonium bromide, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
9. The method for synthesizing glufosinate-ammonium according to claim 4, characterized in that: the mass concentration of the hydrochloric acid in the step (3) is 30-35%.
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