CN113185548A - Glyphosate synthesis method for improving utilization rate of dimethyl phosphite - Google Patents
Glyphosate synthesis method for improving utilization rate of dimethyl phosphite Download PDFInfo
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 114
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 114
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000001308 synthesis method Methods 0.000 title claims abstract description 39
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 276
- 239000004471 Glycine Substances 0.000 claims abstract description 142
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 31
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 123
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- 238000007259 addition reaction Methods 0.000 claims description 50
- 238000006482 condensation reaction Methods 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000012691 depolymerization reaction Methods 0.000 claims description 40
- 230000020477 pH reduction Effects 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 25
- -1 hydrogen ions Chemical class 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 238000007792 addition Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 4
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229960002449 glycine Drugs 0.000 description 117
- 238000003756 stirring Methods 0.000 description 67
- 239000000843 powder Substances 0.000 description 33
- 238000001816 cooling Methods 0.000 description 32
- 239000007795 chemical reaction product Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 26
- 238000001914 filtration Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 17
- 239000003513 alkali Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 230000003301 hydrolyzing effect Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 10
- WBTIFBJEYFLFFW-UHFFFAOYSA-N 2-(hydroxymethylazaniumyl)acetate Chemical class OCNCC(O)=O WBTIFBJEYFLFFW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VURVYGFWNNGSMX-UHFFFAOYSA-N 2-aminoacetic acid;2-(phosphonomethylamino)acetic acid Chemical compound NCC(O)=O.OC(=O)CNCP(O)(O)=O VURVYGFWNNGSMX-UHFFFAOYSA-N 0.000 description 1
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229960001269 glycine hydrochloride Drugs 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- COQRGFWWJBEXRC-UHFFFAOYSA-N hydron;methyl 2-aminoacetate;chloride Chemical compound Cl.COC(=O)CN COQRGFWWJBEXRC-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
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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 provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite. The method for synthesizing the glyphosate takes dimethyl phosphite, triethylamine, paraformaldehyde and glycine as raw materials, promotes the complete reaction of a formaldehyde substrate in a reaction system by increasing the addition amount of the triethylamine and the glycine in the reaction raw materials, reduces the generation of a byproduct namely glyphosine, realizes the improvement of the utilization rate of the dimethyl phosphite, and recycles the redundant glycine for application, thereby reducing the overall raw material consumption of the glyphosate and reducing the production cost. The molar ratio of the dimethyl phosphite to the triethylamine to the paraformaldehyde to the glycine is 1 (0.82-0.99) to 1.60-1.80 to 0.88-1.17.
Description
Technical Field
The invention belongs to the field of pesticide chemical industry, particularly relates to a synthesis method of glyphosate, and particularly relates to a synthesis method of glyphosate for improving the utilization rate of dimethyl phosphite.
Background
The glyphosate is an efficient, non-selective and biocidal organophosphorus herbicide raw material drug, acts on each part of a plant through the absorption of roots, stems and leaves, has no adverse effect on crop seeds, fruits, organisms and soil, and is a herbicide with the largest global market dosage and the widest application in the crop field.
At present, two main ways for realizing industrialization of glyphosate production routes are as follows: firstly, the domestic production method which takes the glycine as the raw material is common; secondly, the method takes iminodiacetic acid (IDA) as raw material. The production line of the glycine mainly takes paraformaldehyde, glycine and dimethyl phosphite as raw materials, triethylamine as a catalyst and methanol as a solvent. Calculated by formaldehyde, the raw material molar ratio is glycine: dimethyl phosphite: formaldehyde: triethylamine 1 (1-1.2) and triethylamine 1.9-2 (0.9-1) are prepared by four steps of depolymerization, addition, condensation and hydrolysis. Wherein, the steps of depolymerization, addition and condensation are synthetic steps, and the obtained synthetic liquid is added with hydrochloric acid for hydrolysis, crystallization and separation to obtain glyphosate; recovering a gas phase solvent methanol during hydrolysis, and obtaining methylal and chloromethane as byproducts; neutralizing the acid mother liquor obtained by crystallization and separation with liquid alkali, recycling triethylamine for reuse, and using the remaining alkali mother liquor as phosphorus resource. The yield in the glyphosate production industry is generally about 75 percent based on glycine, and the effective utilization rate of dimethyl phosphite is only about 65 percent.
However, since the addition reaction ratio of glycine to formaldehyde is 1 (1.9-2), the reaction products are mono-substituted hydroxymethyl glycine and di-substituted hydroxymethyl glycine, and the ratio is about 1: 3. The incomplete reaction of formaldehyde exists in the organic reaction, the incomplete reaction of formaldehyde and dimethyl phosphite can generate side reaction in the next condensation reaction, the reaction speed is high, and the reaction raw materials are consumed, so that the utilization of the dimethyl phosphite is reduced; during the condensation reaction, dimethyl phosphite and disubstituted hydroxymethyl glycine can generate side reaction to cause more glyphosate precursors, if the dosage of dimethyl phosphite is reduced, the proportion of dimethyl phosphite consumed by formaldehyde is increased, and the overall yield is reduced because the hydroxymethyl glycine reaction is incomplete; meanwhile, in the prior art, the synthetic solution is directly acidified and hydrolyzed, the incompletely reacted N-hydroxymethyl glycine and enamine compound are decomposed into glycine during acidification, the glycine is dissolved in a water phase and is difficult to recover, and finally the glycine enters the glyphosate mother solution to be directly treated as waste liquid, so that the waste of glycine raw materials is caused.
CN 108329349A discloses a method for hydrolyzing and recovering triethylamine in the synthesis process of glyphosate, which is characterized in that in the prior art, part of methanol is removed firstly after the synthesis is finished, then a certain amount of hydrogen chloride gas is introduced, triethylamine hydrochloride is crystallized and separated out under the freezing condition, and the consumption of liquid caustic soda and the content of sodium chloride in mother liquor are reduced. The method improves the recovery method of catalyst triethylamine, has no benefit on improving the utilization rate of main raw materials of dimethyl phosphite and glycine, and easily causes material loss of solvent and intermediate during solid-liquid separation during synthesis of the solution, thereby influencing the yield of glyphosate.
CN 110128469A discloses a method for separating hydrogen chloride and methyl chloride by firstly pressurizing and condensing non-condensable gas in dimethyl phosphite tail gas, and the separated hydrogen chloride is applied to glyphosate production. Carrying out acidolysis reaction on hydrogen chloride gas and synthetic solution in a hydrolysis kettle, heating for desolventizing, deacidifying, cooling for crystallizing, carrying out solid-liquid separation by a washing device, and drying to obtain glyphosate technical product. Can reduce the water carried in the reaction system, reduce the steam consumption during the solvent recovery and reduce the waste water amount. Although the patent utilizes hydrogen chloride to acidify the synthetic liquid, the invention does not relate to the purpose and the method for improving the utilization rate of raw materials dimethyl phosphite and glycine, and the phenomenon that the synthetic liquid can return to the glycine through acidification is not found.
The document of recovery and utilization of glycine in the 2 nd phase glyphosate production of pesticide 51 introduces that the pH value of the reaction liquid is adjusted by an acidifying agent to recover glycine, the generated enamine compound is decomposed and reduced into glycine to precipitate a solution, and the glycine is filtered and recovered to be used for the synthesis of the next batch of glyphosate, wherein concentrated sulfuric acid has dehydration property, plays a role in drying and has the best use effect. However, the water content in the synthesis solution greatly affects the recovery rate of glycine, and glycine cannot be crystallized after the water content is more than 5%.
The problems of low dimethyl phosphite utilization rate and glycine waste exist in the existing glycine method for synthesizing glyphosate. Therefore, how to provide a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite, wherein the synthesis method promotes addition reaction to generate more mono-substituted hydroxymethyl glycine and reduces the generation of di-substituted hydroxymethyl glycine by adjusting the amount of reaction raw materials, so that the generation of a byproduct of glyphos is reduced; the synthesis method can decompose and reduce the enamine compound generated by the condensation reaction and unreacted hydroxymethyl glycine into glycine, and carry out alcohol precipitation and recovery for reuse, thereby realizing the purposes of improving the utilization rate of dimethyl phosphite, reducing the overall raw material consumption of glyphosate and reducing the production cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite, which comprises the following steps:
(1) mixing paraformaldehyde, triethylamine and methanol to carry out depolymerization reaction;
(2) mixing glycine with the product obtained after the depolymerization reaction in the step (1) to perform an addition reaction;
(3) mixing the product obtained after the addition reaction in the step (2) with dimethyl phosphite for condensation reaction;
(4) sequentially carrying out acidification, alcohol precipitation and solid-liquid separation on the product obtained after the condensation reaction in the step (3), and reusing glycine obtained by the solid-liquid separation in the addition reaction in the step (2);
(5) carrying out hydrolysis reaction on the reaction liquid obtained by the solid-liquid separation in the step (4), and carrying out post-treatment to obtain a glyphosate finished product;
the molar ratio of the dimethyl phosphite to the triethylamine, the paraformaldehyde and the glycine is 1 (0.82-0.99) to 1.6-1.8 to 0.88-1.17.
In the method for synthesizing glyphosate in the prior art, the molar ratio of dimethyl phosphite to triethylamine, paraformaldehyde to glycine is 1 (0.8-0.81): (1.6-1.8): 0.8-0.87). According to the invention, the addition of glycine is increased by 10-35%, the complete reaction of a formaldehyde substrate is promoted, more mono-substituted hydroxymethyl glycine is generated, and the generation of di-substituted hydroxymethyl glycine is reduced, so that the generation of a byproduct, namely glyphosine is reduced, and the utilization rate of dimethyl phosphite is increased; in addition, the invention increases the addition amount of the glycine and the addition amount of the triethylamine by 1.3-23%, and maintains the pH value of the reaction system to be 8-9.
The invention ensures the utilization rate of dimethyl phosphite and the purity of the obtained glyphosate by simultaneously increasing the addition amount of triethylamine and glycine.
Specifically, the molar ratio of dimethyl phosphite to triethylamine in the present invention is 1 (0.82-0.99), and may be, for example, 1:0.82, 1:0.83, 1:0.84, 1:0.85, 1:0.86, 1:0.87, 1:0.88, 1:0.89, 1:0.9, 1:0.91, 1:0.92, 1:0.93, 1:0.94, 1:0.95, 1:0.96, 1:0.97, 1:0.98 or 1:0.99, but not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable, and 1 (0.85-0.9) is preferable.
The molar ratio of dimethyl phosphite to paraformaldehyde in the present invention is 1 (1.6-1.8), and may be, for example, 1:1.6, 1:1.65, 1:1.7, 1:1.75 or 1:1.8, but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and 1 (1.6-1.7) is preferable.
The molar ratio of dimethyl phosphite to paraformaldehyde in the invention refers to the molar ratio of dimethyl phosphite to paraformaldehyde based on formaldehyde monomer in paraformaldehyde.
The molar ratio of dimethyl phosphite to glycine in the present invention is 1 (0.88-1.17), and may be, for example, 1:0.88, 1:0.9, 1:0.92, 1:0.94, 1:0.95, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.05, 1:1.08, 1:1.1, 1:1.12, 1:1.15, 1:1.16 or 1:1.17, but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and preferably (0.95-1.05).
Preferably, the depolymerization reaction in step (1) is carried out at a temperature of 40-50 deg.C, such as 40 deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C, 49 deg.C or 50 deg.C, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the depolymerization reaction in step (1) is carried out for 20-40min, for example, 20min, 22min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the temperature of the addition reaction in step (2) is 37-47 ℃, for example 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃ or 47 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 40-42 ℃.
Preferably, the time of the addition reaction in step (2) is 50-60min, such as 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60min, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the condensation reaction in step (3) is carried out at a temperature of 50-60 deg.C, such as 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C, 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C or 60 deg.C, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the condensation reaction time in step (3) is 60-80min, such as 60min, 65min, 70min, 75min or 80min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the acidification in step (4) comprises adding a strong acid comprising hydrochloric acid and/or sulfuric acid and water to the product after the condensation reaction.
The acidification of the invention comprises adding strong acid and water into the product after the condensation reaction, wherein the strong acid and the water can be respectively added or a mixture of the strong acid and the water, and the total addition amount of the strong acid and the water can be controlled. According to the invention, by controlling the addition amount of the strong acid and the water, enamine compounds and hydroxymethyl glycine which are not completely reflected in the condensation reaction are completely decomposed and reduced into glycine, and the glycine is recovered by subsequent alcohol precipitation for reuse, so that the product yield is ensured.
Preferably, the ratio of the molar amount of hydrogen ions in the strong acid to the molar amount of glycine in step (2) is (0.3-0.6):1, and may be, for example, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1 or 0.6:1, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
If the addition amount of the hydrogen ions is small, the hydrogen ions cannot be effectively acidized, decomposed and reduced into glycine; however, if the amount of hydrogen ions added is large, glycine is an amphoteric substance, and glycine hydrochloride which is difficult to precipitate is generated.
Preferably, the ratio of the molar amount of water to the molar amount of glycine in step (2) is (0.8-1.8):1, and may be, for example, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1 or 1.8:1, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
If the water content is too high, the solubility of glycine in the reaction solution increases, and the recovery rate decreases, while if the water content is too low, the decomposition of hydroxymethyl glycine into glycine methyl ester hydrochloride is incomplete.
Preferably, the acidification temperature is from 30 to 50 ℃, for example 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, but not limited to the values listed, and other values within the range of values not listed are equally applicable, preferably from 40 to 50 ℃.
Preferably, the acidification time is 30-120min, for example 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the alcohol precipitation in step (4) is carried out by adding methanol to the acidified product, wherein the ratio of the molar amount of methanol to the molar amount of glycine in step (2) is (0.1: 1 to 10:1, for example 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably (4-8: 1).
Preferably, the temperature of the alcohol precipitation in step (4) is 10 to 30 ℃, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 24 ℃, 25 ℃, 27 ℃, 28 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the alcohol precipitation time in the step (4) is 30-120 min.
Preferably, the glyphosate synthesis method further comprises a step of washing glycine after solid-liquid separation, and the washing liquid and the reaction liquid obtained by solid-liquid separation are combined for hydrolysis reaction.
Preferably, the glycine obtained by the solid-liquid separation in the step (4) is reused for the addition reaction in the step (2) to replace part of the glycine raw material, so that the total glycine charge amount meets the proportion requirement.
The post-treatment in step (5) of the present invention is a step of performing liquid caustic soda neutralization, cooling, crystallization, centrifugal separation, washing and drying on the acid mother liquor obtained by the hydrolysis reaction, which is conventional in the art, and the present invention is not particularly limited.
As a preferred technical scheme of the glyphosate synthesis method, the glyphosate synthesis method comprises the following steps:
(1) mixing paraformaldehyde, triethylamine and methanol, and performing depolymerization reaction at 40-50 deg.C for 20-40 min;
(2) mixing glycine with the product obtained after the depolymerization reaction in the step (1), and carrying out addition reaction at 37-47 ℃ for 50-60 min;
(3) mixing the product obtained after the addition reaction in the step (2) with dimethyl phosphite, and carrying out condensation reaction for 60-80min at 50-60 ℃;
(4) sequentially carrying out acidification, alcohol precipitation and solid-liquid separation on the product obtained after the condensation reaction in the step (3), and reusing glycine obtained by the solid-liquid separation in the addition reaction in the step (2); the acidification comprises adding a strong acid and water to the product after the condensation reaction, wherein the strong acid comprises hydrochloric acid or sulfuric acid; the ratio of the molar weight of hydrogen ions in the strong acid to the molar weight of the glycine in the step (2) is (0.3-0.6): 1; the ratio of the molar amount of water to the molar amount of glycine in the step (2) is (0.8-1.8): 1; acidifying at 30-50 deg.C for 30-120 min;
the alcohol precipitation is to add methanol into the acidification product, and the ratio of the molar quantity of the methanol to the molar quantity of the glycine in the step (2) is (0.1-10): 1; the temperature of alcohol precipitation is 10-30 deg.C, and the time is 30-120 min;
(5) washing glycine after solid-liquid separation in the step (4), combining the washing liquid and the reaction liquid obtained by solid-liquid separation, performing hydrolysis reaction, and performing aftertreatment to obtain a glyphosate finished product;
the glycine obtained by the solid-liquid separation in the step (4) is circularly sleeved in the addition reaction in the step (2) to replace part of glycine raw materials, so that the total feed amount of the glycine meets the proportion requirement;
the molar ratio of the dimethyl phosphite to the triethylamine, the paraformaldehyde and the glycine is 1 (0:82-0.99) to 1.60-1.80 to 0.88-1.17.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, by increasing the use amount of glycine and triethylamine, the proportion of the mono-substituted hydroxymethyl glycine intermediate is improved, and the amount of free formaldehyde and dimethylol glycine is reduced, so that the side reaction of dimethyl phosphite is reduced, and the utilization rate of dimethyl phosphite is improved;
(2) according to the reversible property of the reaction of the enamine compound and the hydroxymethyl glycine, after the condensation reaction is finished, the enamine compound and the hydroxymethyl glycine intermediate which are not completely reacted are adjusted and controlled to be completely decomposed into the glycine by adding the amount of strong acid and water, and a part of glycine added during feeding is recovered by adding a certain amount of methanol, so that the overall raw material consumption of the glyphosate is reduced, and the production cost is reduced.
Drawings
FIG. 1 is a process flow diagram of the glyphosate synthesis method for improving the utilization rate of dimethyl phosphite provided by the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The process flow diagram of the glycine glyphosate synthesis method provided in the following example is shown in fig. 1.
In the following examples, the mass fraction of glyphosate dry powder was obtained by a liquid chromatography method in which a sample was dissolved in a mobile phase, and glyphosate in the sample was separated and measured by high performance liquid chromatography using a stainless steel column (strong anion exchange column) packed with Agilent ZORBAX SAX and an ultraviolet detector (195nm) with an aqueous potassium dihydrogen phosphate solution having a pH of 1.9 and methanol as mobile phases. The mass fraction calculation formula of the glyphosate dry powder is as follows:
ω2＝(A2×m1×ω1)/(A1×m2)
wherein ω is2Is the mass fraction of glyphosate in the sample, expressed as wt%; a. the1The average value of the glyphosate peak area in the standard sample solution is shown; a. the2The average value of the glyphosate peak area in the sample solution is obtained; m is1The unit is the mass of the glyphosate standard sample and is g; m is2Is the mass of the sample in g; omega1Is the mass fraction of glyphosate in the standard sample and is expressed by wt%.
The method for calculating the effective utilization rate of the dimethyl phosphite comprises the following steps: the molar weight of the glyphosate dry powder is divided by the molar weight of glyphosate theoretically generated by the feeding amount of dimethyl phosphite.
The method for calculating the yield of the glyphosate dry powder comprises the following steps: the molar weight of the glyphosate dry powder is divided by the molar weight of glyphosate theoretically generated by the glycine feeding amount.
Comparative example 1
This comparative example provides a general synthesis of glyphosate comprising the steps of:
(1) adding 38g of paraformaldehyde with the content of 96 wt%, 208g of methanol and 60g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 45 ℃, stirring for 30 minutes, cooling to 37 ℃, and finishing depolymerization reaction;
(2) adding 47.6g of glycine into the depolymerization reaction product, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) adding 240g of 30% hydrochloric acid into the reaction solution for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; the glyphosate powder with the mass fraction of 95 percent is obtained by washing, filtering and drying, the yield of the glyphosate powder is 75 percent based on the glycine, and the effective utilization rate of the dimethyl phosphite is 64.5 percent.
Example 1
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 67.6g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, cooling to 37 ℃, and finishing depolymerization reaction;
(2) adding 57.6g of glycine into the depolymerization reaction product, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 15g of hydrogen chloride gas into a product after the condensation reaction, adding 18g of water, controlling the temperature to be 40 ℃, stirring for 60 minutes, adding 100g of methanol for alcohol precipitation, controlling the temperature to be 30 ℃, crystallizing for 60 minutes, and filtering to obtain 10g of glycine with the mass fraction of 75%;
(5) adding 195g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 88.6g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 76% in terms of glycine, and the effective utilization rate of dimethyl phosphite is 68.6%.
Example 2
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 67.6g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, cooling to 37 ℃, and finishing depolymerization reaction;
(2) adding 49.2g of glycine into the depolymerization reaction product, adding 8g of the glycine recovered in the embodiment 1, controlling the temperature at 42 ℃, and stirring for 50 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) adding 27.8g of 36% hydrochloric acid into a product after the condensation reaction, controlling the temperature to be 45 ℃, stirring for 30 minutes, adding 100g of methanol for alcohol precipitation, controlling the temperature to be 20 ℃, crystallizing for 120 minutes, and filtering to obtain 8g of glycine with the mass fraction of 73%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 88g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 76.4% and the effective utilization rate of dimethyl phosphite is 68.1% in terms of glycine.
Example 3
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 68.6g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 47.6g of glycine into the depolymerization reaction product, adding 5g of the glycine recovered in the embodiment 2, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) adding 18g of 36% hydrochloric acid into a product obtained after the condensation reaction, controlling the temperature at 40 ℃, stirring for 30 minutes, adding 50g of methanol for alcohol precipitation, controlling the temperature at 20 ℃, crystallizing for 60 minutes, and filtering to obtain 5g of glycine with the mass fraction of 75%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 86.1g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 77.7% and the effective utilization rate of dimethyl phosphite is 66.7% in terms of glycine.
Example 4
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 69.6g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, cooling to 37 ℃, and finishing depolymerization reaction;
(2) adding 55.6g of glycine into the depolymerization reaction product, adding 5g of the glycine recovered in the embodiment 3, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) adding 36g of 36% hydrochloric acid into a product after the condensation reaction, controlling the temperature at 45 ℃, stirring for 120 minutes, adding 200g of methanol for alcohol precipitation, controlling the temperature at 30 ℃, crystallizing for 120 minutes, and filtering to obtain 11.2g of glycine with the mass fraction of 77%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; and (3) washing, filtering and drying to obtain 89.0g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 75.3% and the effective utilization rate of dimethyl phosphite is 68.9% in terms of glycine.
Example 5
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 70g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, cooling to 37 ℃, and finishing depolymerization reaction;
(2) adding 49.2g of glycine into the depolymerization reaction product, adding 8g of the glycine recovered in the embodiment 4, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 10g of hydrogen chloride gas into a product after the condensation reaction, adding 13.5g of water, controlling the temperature at 40 ℃, stirring for 60 minutes, adding 50g of methanol for alcohol precipitation, controlling the temperature at 30 ℃, crystallizing for 120 minutes, and filtering to obtain 9.2g of glycine with the mass fraction of 70%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, adding 72g of water when the temperature reaches 120 ℃, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH to 1, continuously stirring for 1 hour, and standing for crystallization; washing, filtering and drying to obtain 87g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 76.2% and the effective utilization rate of dimethyl phosphite is 67.4% in terms of glycine.
Example 6
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 71g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 49.2g of glycine into the depolymerization reaction product, adding 8g of the glycine recovered in the embodiment 5, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 15g of hydrogen chloride gas into a product after the condensation reaction, adding 11g of water, controlling the temperature to be 40 ℃, stirring for 60 minutes, adding 100g of methanol for alcohol precipitation, controlling the temperature to be 20 ℃, crystallizing for 120 minutes, and filtering to obtain 8.2g of glycine with the mass fraction of 73%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; and (3) washing, filtering and drying to obtain 89g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 78.2% and the effective utilization rate of dimethyl phosphite is 68.9% in terms of glycine.
Example 7
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 72g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 49.2g of glycine into the depolymerization reaction product, adding 8g of the glycine recovered in the embodiment 6, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 15.5g of sulfuric acid with the mass fraction of 98% into a product after the condensation reaction, adding 20.5g of water, controlling the temperature at 40 ℃, stirring for 60 minutes, adding 100g of methanol for alcohol precipitation, controlling the temperature at 20 ℃, crystallizing for 120 minutes, and filtering to obtain 7.6g of glycine with the mass fraction of 73%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 87.5g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 75.8% and the effective utilization rate of dimethyl phosphite is 67.8% in terms of glycine.
Example 8
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 73g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 49.2g of glycine into the depolymerization reaction product, adding 7.6g of the glycine recovered in the embodiment 7, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 12.4g of sulfuric acid with the mass fraction of 98% into a product after the condensation reaction, adding 11g of water, controlling the temperature at 40 ℃, stirring for 60 minutes, cooling to 20 ℃, crystallizing for 120 minutes, and filtering to obtain 7.2g of glycine with the mass fraction of 65%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 88g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 75.3% and the effective utilization rate of dimethyl phosphite is 68.1% in terms of glycine.
Example 9
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 70g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 47 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 49.2g of glycine into the depolymerization reaction product, adding 5.7g of the glycine recovered in the embodiment 8, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 15.5g of sulfuric acid with the mass fraction of 98% into a product after the condensation reaction, controlling the temperature at 40 ℃, stirring for 60 minutes, then cooling to 30 ℃, crystallizing for 120 minutes, and filtering to obtain 6.2g of glycine with the mass fraction of 42%;
(5) adding 210g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; and (3) washing, filtering and drying to obtain 85g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 72.4% and the effective utilization rate of dimethyl phosphite is 65.8% in terms of glycine.
Example 10
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 74g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 40 ℃, stirring for 40 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 62.2g of glycine into the depolymerization reaction product, adding 6g of the glycine recovered in the example 9, controlling the temperature at 37 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature at 50 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) introducing 15g of hydrogen chloride gas into a product after the condensation reaction, adding 18g of water, controlling the temperature to be 40 ℃, stirring for 60 minutes, adding 100g of methanol for alcohol precipitation, controlling the temperature to be 30 ℃, crystallizing for 60 minutes, and filtering to obtain 18.5g of glycine with the mass fraction of 75%;
(5) adding 195g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; and (3) washing, filtering and drying to obtain 89.2g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 75.4% in terms of glycine, and the effective utilization rate of dimethyl phosphite is 69.1%.
Example 11
The embodiment provides a glyphosate synthesis method for improving the utilization rate of dimethyl phosphite as shown in fig. 1, and the glyphosate synthesis method comprises the following steps:
(1) adding 38g of paraformaldehyde, 208g of methanol and 74g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 50 ℃, stirring for 20 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 57.9g of glycine into the depolymerization reaction product, adding 9g of the glycine recovered in the embodiment 10, controlling the temperature at 47 ℃, and stirring for 50 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature at 60 ℃, and stirring for 60 minutes to complete the condensation reaction;
(4) introducing 15g of hydrogen chloride gas into a product after the condensation reaction, adding 18g of water, controlling the temperature to be 40 ℃, stirring for 60 minutes, adding 100g of methanol for alcohol precipitation, controlling the temperature to be 30 ℃, crystallizing for 60 minutes, and filtering to obtain 19.6g of glycine with the mass fraction of 70%;
(5) adding 195g of hydrochloric acid into the reaction solution continuously for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 87.8g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 74.0% and the effective utilization rate of dimethyl phosphite is 68.0% in terms of glycine.
Comparative example 2
The present comparative example provides a method of synthesizing glyphosate, comprising the steps of:
(1) adding 38g of paraformaldehyde, 208g of methanol and 65g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 45 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 47.6g of glycine into the depolymerization reaction product, controlling the temperature at 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) adding 240g of 30% hydrochloric acid into the reaction solution for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; the glyphosate powder with the mass fraction of 95 percent is obtained by washing, filtering and drying, the yield of the glyphosate powder is 75.2 percent and the effective utilization rate of dimethyl phosphite is 64.7 percent based on glycine.
Comparative example 3
The present comparative example provides a method of synthesizing glyphosate, comprising the steps of:
(1) adding 38g of paraformaldehyde, 208g of methanol and 60g of triethylamine into a 1000mL four-mouth reaction bottle, heating to 45 ℃, stirring for 30 minutes, and cooling to 37 ℃ to complete depolymerization reaction;
(2) adding 57.6g of glycine into the depolymerization reaction product, controlling the temperature to be 42 ℃, and stirring for 60 minutes to complete the addition reaction;
(3) adding 82.4g of dimethyl phosphite into the addition reaction product, controlling the temperature to be 52 ℃, and stirring for 80 minutes to complete the condensation reaction;
(4) adding 240g of 30% hydrochloric acid into the reaction solution for acidification, desolventizing and hydrolyzing for 3 hours, wherein the temperature reaches 120 ℃; adding 72g of water, cooling to below 100 ℃, dropwise adding liquid alkali to adjust the pH value to 1, continuously stirring for 1 hour, standing and crystallizing; washing, filtering and drying to obtain 88.2g of glyphosate dry powder with the mass fraction of 95%, wherein the yield of the glyphosate dry powder is 65.6% and the effective utilization rate of dimethyl phosphite is 68.3% in terms of glycine.
For ease of data comparison, the dry glyphosate yields and the effective utilization of dimethyl phosphite for comparative example 1 and examples 1-9 are shown in table 1.
TABLE 1
In conclusion, the invention improves the proportion of the mono-substituted hydroxymethyl glycine intermediate by increasing the dosage of the glycine and the triethylamine, and reduces the dosage of free formaldehyde and dihydroxymethyl glycine, thereby reducing the side reaction of dimethyl phosphite and improving the utilization rate of dimethyl phosphite; according to the reversible property of the reaction of the enamine compound and the hydroxymethyl glycine, after the condensation reaction is finished, the enamine compound and the hydroxymethyl glycine intermediate which are not completely reacted are adjusted and controlled to be completely decomposed into the glycine by adding the amount of strong acid and water, and a part of glycine added during feeding is recovered by adding a certain amount of methanol, so that the overall raw material consumption of the glyphosate is reduced, and the production cost is reduced.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A glyphosate synthesis method for improving the utilization rate of dimethyl phosphite is characterized by comprising the following steps:
(1) mixing paraformaldehyde, triethylamine and methanol to carry out depolymerization reaction;
(2) mixing glycine with the product obtained after the depolymerization reaction in the step (1) to perform an addition reaction;
(3) mixing the product obtained after the addition reaction in the step (2) with dimethyl phosphite for condensation reaction;
(4) sequentially carrying out acidification, alcohol precipitation and solid-liquid separation on the product obtained after the condensation reaction in the step (3), and reusing glycine obtained by the solid-liquid separation in the addition reaction in the step (2);
(5) carrying out hydrolysis reaction on the reaction liquid obtained by the solid-liquid separation in the step (4), and carrying out post-treatment to obtain a glyphosate finished product;
the molar ratio of the dimethyl phosphite, the triethylamine, the paraformaldehyde and the glycine in the step (1) is 1 (0.82-0.99): (1.6-1.8): 0.88-1.17).
2. The method for synthesizing glyphosate according to claim 1, wherein the molar ratio of the dimethyl phosphite to the triethylamine, the paraformaldehyde and the glycine is 1 (0.85-0.9): 1.6-1.7): 0.95-1.05.
3. The glyphosate synthesis process of claim 1 or 2, wherein the temperature of the depolymerization reaction of step (1) is 40-50 ℃;
preferably, the time of the depolymerization reaction in step (1) is 20-40 min.
4. The process for the synthesis of glyphosate according to any of claims 1-3, characterized in that the temperature of the addition reaction of step (2) is 37-47 ℃, preferably 40-42 ℃;
preferably, the time of the addition reaction in the step (2) is 50-60 min.
5. The method for synthesizing glyphosate according to any one of claims 1-4, wherein the temperature of the condensation reaction in step (3) is 50-60 ℃;
preferably, the time of the condensation reaction in the step (3) is 60-80 min.
6. The process for synthesizing glyphosate according to any one of claims 1-5, wherein the acidification in step (4) comprises adding a strong acid comprising hydrochloric acid and/or sulfuric acid and water to the product after the condensation reaction;
preferably, the ratio of the molar amount of hydrogen ions in the strong acid to the molar amount of glycine in the step (2) is (0.3-0.6): 1;
preferably, the ratio of the molar amount of water to the molar amount of glycine in step (2) is (0.8-1.8): 1';
preferably, the acidification temperature is 30-50 ℃, preferably 40-50 ℃;
preferably, the acidification time is 30-120 min.
7. The glyphosate synthesis method of any one of claims 1-6, wherein the alcohol precipitation in step (4) is the addition of methanol to the acidified product, and the ratio of the molar amount of methanol to the molar amount of glycine in step (2) is (0.1-10):1, preferably (4-8): 1;
preferably, the temperature of alcohol precipitation in the step (4) is 10-30 ℃;
preferably, the alcohol precipitation time in the step (4) is 30-120 min.
8. The method for synthesizing glyphosate according to any one of claims 1 to 7, further comprising a step of washing glycine after solid-liquid separation, wherein the washing solution is combined with the reaction solution obtained by solid-liquid separation and then subjected to hydrolysis reaction.
9. The method for synthesizing glyphosate according to any one of claims 1-8, wherein glycine obtained by the solid-liquid separation in the step (4) is reused for the addition reaction in the step (2) to replace part of glycine raw material, so that the total glycine charge amount meets the proportion requirement.
10. The method for synthesizing glyphosate according to any one of claims 1-9, wherein the method for synthesizing glyphosate comprises the following steps:
(1) mixing paraformaldehyde, triethylamine and methanol, and performing depolymerization reaction at 40-50 deg.C for 20-40 min;
(2) mixing glycine with the product obtained after the depolymerization reaction in the step (1), and carrying out addition reaction at 37-47 ℃ for 50-60 min;
(3) mixing the product obtained after the addition reaction in the step (2) with dimethyl phosphite, and carrying out condensation reaction for 60-80min at 50-60 ℃;
(4) sequentially carrying out acidification, alcohol precipitation and solid-liquid separation on the product obtained after the condensation reaction in the step (3), and reusing glycine obtained by the solid-liquid separation in the addition reaction in the step (2); the acidification comprises adding a strong acid and water to the product after the condensation reaction, wherein the strong acid comprises hydrochloric acid or sulfuric acid; the ratio of the molar weight of hydrogen ions in the strong acid to the molar weight of the glycine in the step (2) is (0.3-0.6): 1; the ratio of the molar amount of water to the molar amount of glycine in the step (2) is (0.8-1.8): 1; acidifying at 30-50 deg.C for 30-120 min;
the alcohol precipitation is to add methanol into the acidification product, and the ratio of the molar quantity of the methanol to the molar quantity of the glycine in the step (2) is (0.1-10): 1; the temperature of alcohol precipitation is 10-30 deg.C, and the time is 30-120 min;
(5) washing glycine after solid-liquid separation in the step (4), combining the washing liquid and the reaction liquid obtained by solid-liquid separation, performing hydrolysis reaction, and performing aftertreatment to obtain a glyphosate finished product;
the glycine obtained by the solid-liquid separation in the step (4) is circularly sleeved in the addition reaction in the step (2) to replace part of glycine raw materials, so that the total feed amount of the glycine meets the proportion requirement;
the molar ratio of the dimethyl phosphite to the triethylamine, the paraformaldehyde and the glycine is 1 (0:82-0.99) to 1.60-1.80 to 0.88-1.17.
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