CN110407870B - Preparation method of glyphosate and microchannel reactor thereof - Google Patents
Preparation method of glyphosate and microchannel reactor thereof Download PDFInfo
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- CN110407870B CN110407870B CN201910746193.8A CN201910746193A CN110407870B CN 110407870 B CN110407870 B CN 110407870B CN 201910746193 A CN201910746193 A CN 201910746193A CN 110407870 B CN110407870 B CN 110407870B
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 28
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000007259 addition reaction Methods 0.000 claims abstract description 37
- 230000020477 pH reduction Effects 0.000 claims abstract description 34
- 238000006482 condensation reaction Methods 0.000 claims abstract description 33
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 29
- 239000004471 Glycine Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000009833 condensation Methods 0.000 claims description 19
- 230000005494 condensation Effects 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 229940087646 methanolamine Drugs 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000013529 heat transfer fluid Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004009 herbicide Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- SGVDYFNFBJGOHB-UHFFFAOYSA-N 2-[methyl(phosphonomethyl)amino]acetic acid Chemical compound OC(=O)CN(C)CP(O)(O)=O SGVDYFNFBJGOHB-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002373 hemiacetals Chemical class 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- -1 CN100567311C Chemical compound 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000003321 amplification Effects 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
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method of glyphosate, which comprises the following reaction steps: a preheating step, an addition reaction step, a condensation reaction step and an acidification reaction step; in the addition reaction, formaldehyde is gradually added into the whole slurry; in the condensation reaction, the addition reaction liquid is gradually added to the entire dimethyl phosphite. The reaction device is a micro-channel reactor, and is provided with a preheating module, an addition reaction module, a condensation reaction module and an acidification reaction module which are connected in series according to the reaction sequence. The invention has the advantages of high mass and heat transfer efficiency, accurate control of reaction time, short reaction period, less side reaction products, high purity of the obtained glyphosate product, and the like.
Description
Technical Field
The invention relates to a synthesis technology of glyphosate herbicide.
Background
Glyphosate (N-phosphonomethyl glycine) is a high-efficiency, broad-spectrum, low-toxicity and biocidal post-emergence herbicide, is very effective in preventing and controlling perennial deep-rooted malignant weeds, has good biological activity, belongs to systemic conductivity herbicide, and is one of the most widely applied herbicides at present. The production process of glyphosate mainly comprises glycine method and iminodiacetic acid method (IDA method). The process mainly comprises the steps of taking paraformaldehyde, glycine, dimethyl phosphite, methanol and triethylamine as raw materials, carrying out catalytic depolymerization on the paraformaldehyde in a methanol solvent to form depolymerization liquid, reacting the depolymerization liquid with glycine and triethylamine in the methanol solvent to generate addition liquid, carrying out condensation reaction on the addition liquid with dimethyl phosphite to generate condensation liquid, and carrying out acidolysis, dealcoholization and deacidification, crystallization, centrifugation and other procedures to obtain glyphosate solid.
In the conventional process, in order to make glycine react completely, an excessive amount of formaldehyde (the molar ratio of glycine to formaldehyde is about 1:2) is required to react with the glycine, the molar ratio of paraformaldehyde to glycine in the raw material is 2:1, and after glycine is added, hemiacetals (an intermediate combining methanol and formaldehyde, unstable and interconverting with formaldehyde) in the system react with glycine to form a monosubstituted intermediate and a disubstituted intermediate, the proportions of which are about 40% and 60% respectively, and the remaining hemiacetals [2- (0.4+0.6×2) ]/2=20%.
In the condensation stage, the dimethyl phosphite also needs to be excessive (the molar ratio of glycine to dimethyl phosphite is about 1:1.2), and the excessive dimethyl phosphite can be hydrolyzed to generate phosphorous acid, and excessive phosphorus-containing substances enter the mother liquor, so that the total phosphorus content in the wastewater is increased.
However, excessive formaldehyde brings about side reactions during the subsequent reaction.
In recent years, there has been an increase in reports of continuous production of glyphosate, such as CN100567311C, reporting continuous acidolysis. Reported in patent number CN101704840B is a method for continuous desolventizing to produce glyphosate. The patent No. CN102775441B describes a continuous depolymerization, addition and condensation method, wherein the continuous process is realized by combining a kettle type reactor and a pipeline reactor, the reaction period can be shortened by 20-30 minutes, and the production cost can be reduced to a certain extent.
In the process, part of patents only realize the continuity of acidification or desolventizing stages, and the steps of synthesis of glyphosate are not involved, and part of patents realize the continuity of synthesis, so that the reaction period is shortened, the cost is reduced, and the requirements on equipment and safety are still higher. In addition, since excessive formaldehyde is added during the synthesis process, a series of side reactions are caused in the subsequent reaction, and no mention is made of how to avoid by-products generated in the partial reaction.
Disclosure of Invention
The invention aims to:
overcomes the defects of large flow, multiple side reactions and the like of the prior art, and provides a preparation method of glyphosate and a microchannel reactor thereof, which can accurately control the dosage of various raw materials, the adding time and the purity of the product.
The technical scheme is as follows:
the preparation method of the glyphosate comprises the following steps of preheating, addition reaction, condensation reaction and acidification reaction in sequence.
(1) Preheating: glycine, methanol and triethylamine are mixed to form slurry, and the glycine content in the slurry is 5% -20% (w/w), and more preferably 8% -10%. Preheating is carried out at a lower temperature (avoiding methanol volatilization). Preheating to 40-65 ℃, preferably 40-55 ℃.
(2) The addition reaction step: adding formaldehyde into the preheated slurry (preferably adding formaldehyde gradually into the whole slurry to avoid excessive formaldehyde in the initial stage of the reaction, reduce the formation rate of disubstituted intermediates, reduce complex side reaction products in the subsequent reaction process, reduce the heating time of the formaldehyde, avoid the volatilization of the formaldehyde caused by heating before the unreacted reaction, and improve the conversion rate of a semi-finished product, so that depolymerization liquid is formed, and the temperature is maintained for 60-90 s for carrying out addition reaction.
In this step, the molar ratio of formaldehyde to glycine in (1) is 1.0 to 2.0:1, preferably 1.4 to 1.8:1. The content of formaldehyde in the depolymerization liquid is 20% -55% (w/w), preferably 30% -50%.
(3) Condensation reaction step: mixing the addition reaction liquid formed in the step (2) with dimethyl phosphite, and performing condensation reaction to form a condensation liquid. (preferably, all dimethyl phosphite is prepared and heated, then the addition reaction liquid is gradually added into the reaction liquid, because the boiling point of the dimethyl phosphite is higher, the dimethyl phosphite is not easy to volatilize and lose, meanwhile, the excessive dimethyl phosphite is ensured in the initial stage of the reaction, the reaction liquid is acidic at the initial stage, the residual formaldehyde is discharged from the solution, the formaldehyde is easy to polymerize in the aqueous solution to form acetic acid, the polymerization reaction is basically not carried out in an acidic environment, and the generation of side reaction products, namely methyl glyphosate and glyphosate is avoided in the subsequent reaction. The condensation reaction temperature is 40-65 ℃, preferably 55-65 ℃, and the total residence time of the materials in the first step is 50-80 s.
In the step (3), the molar ratio of the dimethyl phosphite to the glycine is 1.0-1.2:1, and more preferably 1.02-1.05:1. The dosage of the dimethyl phosphite is less than that of the traditional process, the probability of generating phosphorous acid by hydrolysis is reduced, and the total phosphorus content in the wastewater is prevented from being increased.
(4) An acidification reaction step: mixing the condensation liquid formed in the step (3) with 28-32% hydrochloric acid solution, performing acidification reaction at a certain temperature, and discharging to obtain an acidified liquid. The reaction temperature is 10-50 ℃, preferably 20-40 ℃, and the total residence time of the materials in the third reaction module is 40-60 s.
In the step (4), the molar ratio of the hydrochloric acid to the glycine is 3.2-3.5.
Reaction equipment:
the reaction device adopted by the invention is a micro-channel reactor, and is provided with a preheating module, an addition reaction module, a condensation reaction module and an acidification reaction module which are connected in series according to the reaction sequence.
The preheating module is provided with a first inlet and a first outlet, wherein the first inlet is used for entering three initial raw materials, and the first outlet is used for flowing out slurry. The addition reaction module is provided with a second inlet, an addition material inlet and a second outlet, wherein the second inlet is communicated with the first outlet, the addition material inlet is used for allowing formaldehyde to enter, and the second outlet is used for allowing an addition reaction liquid to flow out. The condensation reaction module is provided with a third inlet, a condensation material inlet and a third outlet, wherein the third inlet is communicated with the second outlet, the condensation material inlet is used for allowing dimethyl phosphite to enter, and the third outlet is used for allowing condensation reaction liquid to flow out. The acidification reaction module is provided with a fourth inlet, an acidification material inlet and a fourth outlet, wherein the fourth inlet is communicated with the third outlet, the acidification material inlet is used for allowing hydrochloric acid to enter, and the fourth outlet is used for allowing a final reaction product to flow out.
The addition material inlet, the condensation material inlet and the acidification material inlet are respectively provided with a control valve capable of controlling respective materials to enter, each control valve is connected with the same controller, and the controller can send out instructions of opening and closing time (time and duration for calculating and controlling each valve to be opened and closed in sequence according to data such as flow rate of reaction materials, length and volume of each module, consumption of the reaction materials and the like). The control valve of the addition reaction inlet is opened at the moment that the slurry in the preheating step firstly enters the dosage required by the addition reaction module, and then the slurry is opened and put into formaldehyde. The control valve of the condensation reaction inlet is opened at the moment that the needed amount of dimethyl phosphite is firstly put into the condensation reaction module, and then the addition reaction liquid flows in.
In a preferred embodiment of the invention, the metering and feeding of the materials are carried out by a metering pump, the addition reaction module preferably completes the feeding by a diaphragm pump, and the accurate metering is completed by matching with a balance, and the condensation reaction and acidification reaction module preferably completes the metering and feeding by a plunger pump.
The module has a three-layer sandwich mechanism, the outer two layers being used for recirculation of the heat transfer fluid and the middle layer being used for flow of the reaction fluid. Wherein the preheating module and the addition reaction module are controlled by the same oil bath heating device, so as to ensure the basically same temperature; the condensation reaction module is controlled by a separate oil bath heating device, the acidification reaction module is controlled by a water bath device, and the respective required reaction temperatures are respectively controlled.
In the scheme of the invention, the pH value of the mixed fluid in the previous 1-3 modules is 7.0-8.3, and finally the reaction of the module 4 is carried out in an acidic environment and is within the normal working range of the reactor. The module is made of glass or ceramic material, and the intermediate layer can adapt to the reaction conditions of within 1.8Mpa and minus 60-200 ℃, and has better chemical corrosiveness.
The beneficial effects are that:
compared with the traditional kettle type production, the reactor has the advantages of high mass and heat transfer efficiency, convenient operation, capability of accurately controlling the reaction time, small occupied area, no amplification effect and the like. Because the amount of the reaction materials in the unit volume is small, the heat release is controllable, and the environment is protected and safe. Because of the special structure in the micro-channel, the mass and heat transfer efficiency is high, the reaction period is shortened, the number of side reaction products is small, and the purity and the yield of the obtained product are high.
The generation of the byproducts of methyl glyphosate and glyphosate in the background technology is that the product of glyphosate reacts with excessive formaldehyde or phosphorous acid. The microchannel reactor for synthesizing glyphosate provided by the invention can realize multi-section feeding and accurately control the entering time and the reaction temperature of various raw materials. Most importantly, the reactor has no back mixing in the mixing process of materials, and controls the entering mode, the time and the reaction technological parameters of the respective raw materials, so that the problem of excessive byproducts caused by the series reaction can be well solved.
Drawings
FIG. 1 is a schematic perspective view of a microchannel reactor according to the present invention;
in the figure, a 1-preheating module; a 2-addition reaction module; a 3-condensation reaction module; 4-acidification reaction module; 5-an upper heating layer; 6-an intermediate reaction layer; 7-a lower heating layer; 8-a fourth outlet; 9-acidizing material inlet; 10-condensate inlet; 11-an addition inlet; 12-first inlet.
Detailed Description
Example 1:
the microchannel reactor shown in fig. 1 is provided with a preheating module, an addition reaction module, a condensation reaction module and an acidification reaction module which are connected in series according to the reaction sequence.
The preheating module is provided with a first inlet and a first outlet, wherein the first inlet is used for entering three initial raw materials; the addition reaction module is provided with a second inlet and an addition material inlet, and formaldehyde enters the addition material inlet. The condensation reaction module is provided with a third inlet and a condensation material inlet, wherein the condensation material inlet is used for allowing dimethyl phosphite to enter. The acidification reaction module is provided with a fourth inlet, an acidification material inlet and a fourth outlet, wherein the acidification material inlet is used for allowing hydrochloric acid to enter, and the fourth outlet is used for allowing glyphosate solution which is a final reaction product to flow out.
The addition material inlet, the condensation material inlet and the acidification material inlet are respectively provided with a control valve, so that the entering time of the respective materials can be manually or automatically controlled.
Weighing 30.6g of powdery glycine, 36g of triethylamine and 239.4g of methanol, fully stirring to prepare glycine slurry, preheating the glycine slurry by a preheating module heated at 50-60 ℃ through a diaphragm pump, entering an addition reaction module, starting a depolymerization liquid pump while feeding the slurry into the reaction module, adding 30.6g of depolymerization liquid containing 55% of formaldehyde into the addition reaction module to perform addition reaction with the glycine slurry to generate addition liquid, starting a dimethyl phosphite feeding pump while feeding the addition liquid into a condensation reaction module, and adding 45.4g of dimethyl phosphite into the condensation module, wherein the heating temperature is controlled to be 50-60 ℃, so as to complete the condensation reaction. And (3) starting a hydrochloric acid feeding pump while feeding the condensation liquid into an acidification reaction module, adding 155.7g of 30% hydrochloric acid solution into the module, controlling the reaction temperature to 20-40 ℃ in a water bath, and reacting to obtain the acidification liquid.
The obtained acidified liquid is subjected to dealcoholization, deacidification, neutralization and crystallization, and is filtered to obtain 56.5g of glyphosate solid, the content is 96.3%, and the yield of the solid glyphosate is 80.45%.
Example 2:
the same microchannel reactor as in example 1 above was used.
Weighing 30.6g of powdery glycine, 36g of triethylamine and 315.9g of methanol, fully stirring to prepare glycine slurry, preheating the glycine slurry by a diaphragm pump in a preheating module heated at 50-60 ℃, then entering an addition reaction module, starting a depolymerization liquid pump while feeding the slurry into the reaction module, adding 108.1g of depolymerization liquid containing 22% formaldehyde into the addition reaction module to perform addition reaction with the glycine slurry to generate addition liquid, starting a dimethyl phosphite feeding pump while feeding the addition liquid into a condensation reaction module, and adding 46.8g of dimethyl phosphite into the module, wherein the heating temperature is controlled at 50-60 ℃, thereby completing the condensation reaction. And (3) starting a hydrochloric acid feeding pump while feeding the condensation liquid into an acidification reaction module, adding 170.3g of 30% hydrochloric acid solution into the module, controlling the reaction temperature to 20-40 ℃ in a water bath, and reacting to obtain the acidification liquid.
The obtained acidified liquid is subjected to dealcoholization, deacidification, neutralization and crystallization, and is filtered to obtain 56.7g of glyphosate solid, the content is 96.0%, and the yield of the solid glyphosate is 80.49%.
Claims (6)
1. A preparation method of glyphosate, which comprises a preheating step, an addition reaction step, a condensation reaction step and an acidification reaction step which are continuously carried out in the following sequence, and is characterized in that:
(1) Preheating: mixing glycine, methanol and triethylamine to form slurry, and preheating to 40-65 ℃; (2) an addition reaction step: adding formaldehyde into the preheated slurry to form depolymerization liquid, maintaining the temperature for 60-90 s, and carrying out addition reaction;
(3) Condensation reaction step: mixing the addition reaction liquid formed in the step (2) with dimethyl phosphite to perform condensation reaction to form a condensation liquid; the condensation reaction temperature is 40-65 ℃, and the total residence time of the materials in the step is 50-80 s;
(4) An acidification reaction step: mixing the condensation liquid formed in the step (3) with 25-32% hydrochloric acid solution, performing an acidification reaction, and discharging to obtain an acidification liquid; the reaction temperature is 10-50 ℃, and the total residence time of the materials in the third reaction module is 40-60 s;
in the addition reaction step, formaldehyde is gradually added into the whole slurry;
in the condensation reaction, all dimethyl phosphite is prepared and heated, then an addition reaction liquid is gradually added into the dimethyl phosphite, and the dimethyl phosphite and the addition reaction liquid are mixed for condensation reaction; the condensation reaction temperature is 50-60 ℃;
the preparation method adopts a micro-channel reactor, wherein the micro-channel reactor is provided with a preheating module, an addition reaction module, a condensation reaction module and an acidification reaction module which are connected in series according to a reaction sequence;
the preheating module is provided with a first inlet and a first outlet, wherein the first inlet is used for entering three initial raw materials; the addition reaction module is provided with a second inlet, an addition material inlet and a second outlet, the second inlet is communicated with the first outlet, and the addition material inlet is used for formaldehyde to enter;
the condensation reaction module is provided with a third inlet, a condensation material inlet and a third outlet, the third inlet is communicated with the second outlet, and the condensation material inlet is used for allowing dimethyl phosphite to enter; the acidification reaction module is provided with a fourth inlet, an acidification material inlet and a fourth outlet, the fourth inlet is communicated with the third outlet, the acidification material inlet is used for entering hydrochloric acid, and the fourth outlet is used for flowing out acidification liquid of a final reaction product;
the addition material inlet, the condensation material inlet and the acidification material inlet are respectively provided with a control valve, so that the entering time of the respective materials can be manually or automatically controlled.
2. A process for the preparation of glyphosate as claimed in claim 1, wherein: in the addition reaction step, the molar ratio of the added formaldehyde to the glycine in the step (1) is 1.4-1.8:1.
3. A process for the preparation of glyphosate as claimed in claim 1, wherein: in the condensation reaction, the molar ratio of the dimethyl phosphite to the glycine is 1.02-1.05:1.
4. A process for the preparation of glyphosate as claimed in claim 1, wherein: in the acidification reaction, the molar ratio of hydrochloric acid to glycine is 3.2-3.5.
5. A process for the preparation of glyphosate as claimed in claim 1, wherein: the modules all have a three-layer sandwich structure, the outer two layers are used for recycling heat transfer fluid, and the middle layer is used for flowing reaction fluid.
6. A process for the preparation of glyphosate as claimed in claim 1, wherein: the preheating module and the addition reaction module are controlled by the same oil bath heating device, the condensation reaction module is controlled by an independent oil bath heating device, and the acidification reaction module is controlled by a water bath device.
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| CN110922426B (en) * | 2019-11-22 | 2022-04-22 | 湖北泰盛化工有限公司 | Alkyl ester method glyphosate continuous production system and process |
| CN111804252A (en) * | 2020-07-01 | 2020-10-23 | 南通江山农药化工股份有限公司 | Dimethyl phosphite byproduct hydrolysis process and microchannel reactor thereof |
| CN112940033A (en) * | 2021-02-09 | 2021-06-11 | 利尔化学股份有限公司 | Continuous preparation method of glufosinate-ammonium intermediate |
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