CN110407870A - The preparation method and its micro passage reaction of glyphosate - Google Patents
The preparation method and its micro passage reaction of glyphosate Download PDFInfo
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- CN110407870A CN110407870A CN201910746193.8A CN201910746193A CN110407870A CN 110407870 A CN110407870 A CN 110407870A CN 201910746193 A CN201910746193 A CN 201910746193A CN 110407870 A CN110407870 A CN 110407870A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 71
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 30
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000007259 addition reaction Methods 0.000 claims abstract description 36
- 230000020477 pH reduction Effects 0.000 claims abstract description 32
- 238000006482 condensation reaction Methods 0.000 claims abstract description 26
- 238000009833 condensation Methods 0.000 claims abstract description 22
- 230000005494 condensation Effects 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical class COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000004471 Glycine Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- USPDYHQWWULKMD-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(O)(O)O USPDYHQWWULKMD-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000002363 herbicidal effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 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 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
- 239000006227 byproduct Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 2
- 150000002373 hemiacetals Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000012257 stirred material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 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
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of glyphosate, have the reaction step carried out in the following order: preheating step, addition reaction step, step of condensation, acidification reaction step；In addition reaction, formaldehyde is gradually added in whole slurries；In condensation reaction, addition reaction liquid is gradually added in whole dimethylphosphites.Used reaction unit is micro passage reaction, has the warm-up block and addition reaction module, condensation reaction module, acidification reaction module being cascaded by reaction sequence.The advantages that present invention has mass-and heat-transfer high-efficient, accurately controls the reaction time, and reaction time is short, and side reaction product is few, and obtained glyphosate products are with high purity.
Description
Technical field
The present invention relates to a kind of synthetic technologys of glyphosate herbicidal.
Background technique
Glyphosate (N- (phosphonomethyl) glycine) is the herbicide after seedling of efficient one kind, wide spectrum, low toxicity, natural disposition of going out, right
The prevention and treatment of perennial depth root malignant weed is very effective, has good bioactivity, belongs to uptake and translocation herbicide, be mesh
Before one of the herbicide that is most widely used.Glyphosate production technique mainly has glycine method and iminodiacetic acid (salt) acid system (IDA
Method).Wherein glycine method mainly produces at home, the technique mainly with paraformaldehyde, glycine, dimethylphosphite, methanol,
Triethylamine is raw material, and wherein paraformaldehyde forms depolymerization liquid through triethylamine catalytic degradation in methanol solvate, with glycine, three second
Amine reacted in methanol solvate generate addition liquid, then with dimethylphosphite carry out condensation reaction generate condensation liquid, by acidolysis,
The processes such as dealcoholysis depickling, crystallization, centrifugation obtain glyphosate.
In traditional handicraft, to keep glycine reactant complete, needing excessive formaldehyde, (molar ratio of glycine and formaldehyde is about
It being reacted for 1:2), the molar ratio of paraformaldehyde and glycine is 2:1 in raw material, after throwing glycine, the hemiacetal in system
(intermediate of the methanol in conjunction with formaldehyde, unstable, with the mutual inversion of phases of formaldehyde) and glycine reactant generate monosubstituted intermediate and
Disubstituted intermediate, ratio respectively may be about 40%, 60%, remaining hemiacetal [2- (0.4+0.6*2)]/2=20%.
Condensation the stage, dimethylphosphite be also required to excess (molar ratio of glycine and dimethylphosphite is about 1:
1.2), excessive dimethylphosphite may hydrolyze generation phosphorous acid, and extra phosphorus containg substances enter mother liquor, increase waste water
In total phosphorus content.
But excessive formaldehyde can bring side reaction during subsequent reactions.
The report about continuous production glyphosate increased in recent years, special such as Patent No. CN100567311C
Benefit, report be hydrolysis step serialization.The patent report of Patent No. CN101704840B is the production of serialization precipitation
The method of glyphosate.The patent of Patent No. CN102775441B describes a kind of serialization and carries out depolymerization, addition and condensation
Method, the continuous process introduced in the patent is implemented in combination with by using autoclave and pipeline reactor, and reaction time can
Shorten 20 ~ 30 minutes, production cost can be reduced to a certain extent.
In process above, partial monopoly is the serialization for realizing acidification or precipitation stage, to the step of glyphosate synthesis
Suddenly without reference to partial monopoly realizes the serialization of synthesis, only shortens reaction time, departmental cost is reduced, to setting
Standby and safe requirement is still higher.In addition, making it in subsequent reactions since excessive formaldehyde is added in the synthesis process
Cause a series of side reaction, the by-product for how avoiding part reaction from generating all does not refer in the above patent.
Summary of the invention
Goal of the invention:
The disadvantages of prior art process is big, side reaction is more is overcome, when various raw material dosages, addition can accurately be controlled by providing one kind
The preparation method and its micro passage reaction of the high glyphosate of machine, product purity.
Technical solution:
Glyphosate preparation method of the invention has the preheating step being carried out continuously in the following order, addition reaction step, condensation
Reaction step, acidification reaction step.
(1) preheating step: glycine and methanol, triethylamine these three raw materials are mixed into slurry, glycine contains in slurry
Amount is 5% ~ 20%(w/w), more preferable 8% ~ 10%.It is preheated by lower temperature (methanol is avoided to volatilize).Being preheated to temperature is
40 ~ 65 DEG C, preferably 40 ~ 55 DEG C.
(2) addition reaction step: in the slurry after preheating, formaldehyde is added and (preferably in whole slurries, is gradually added first
Aldehyde avoids formaldehyde initial reaction stage excessive, reduces the formation rate of disubstituted intermediate, brings complexity during reducing subsequent reactions
Side reaction product；The heated time for reducing formaldehyde simultaneously avoids heated volatilization before its unreacted, it is difficult to accurately control its ratio
Example, improves the conversion ratio of semi-finished product), depolymerization liquid is formed, temperature 60s ~ 90s is maintained, carries out addition reaction.
In the step, the molar ratio of the glycine in the formaldehyde that is added and (1) is 1.0 ~ 2.0:1, preferably 1.4 ~ 1.8:
1.The content of formaldehyde is 20% ~ 55%(w/w in depolymerization liquid), preferably 30 ~ 50%.
(3) step of condensation: the addition reaction liquid formed in (2) is mixed with dimethylphosphite, is carried out
Condensation reaction forms condensation liquid.It (preferably first gets and heats whole dimethylphosphites ready, be then gradually added addition wherein
Reaction solution is not easy volatilization loss because dimethylphosphite boiling point is higher；Meanwhile initial reaction stage guarantees dimethylphosphite mistake
Amount, but temperature is higher, so that reaction solution initial stage in acidity, promotes remaining formaldehyde to emit from solution-exist because of formaldehyde
It is easy to polymerize in aqueous solution and forms acetic acid, acidic environment can be carried out its polymerization reaction not substantially；To avoid subsequent reaction
The middle generation for reducing side reaction product methyl glyphosate and glyphosine).Setting-up point be 40 ~ 65 DEG C, preferably 55 ~ 65 DEG C,
Material total residence time in the step is 50s ~ 80s.
In the step (3), the molar ratio of dimethylphosphite and glycine is 1.0 ~ 1.2:1, more preferable 1.02 ~ 1.05:
1.Dimethylphosphite dosage is less than traditional handicraft, reduces the probability that hydrolysis generates phosphorous acid, avoids increasing total in waste water
Phosphorus amount.
(4) acidification reaction step: by (3) formed condensation liquid mixed with the hydrochloric acid solution of 28-32%, under certain temperature into
Row acidification reaction obtains acidifying solution after discharging.Reaction temperature is 10 ~ 50 DEG C, and preferably 20 ~ 40 degrees Celsius, material is anti-in third
Answering the total residence time in module is 40s ~ 60s.
In above-mentioned steps (4), the mol ratio of hydrochloric acid and glycine is 3.2 ~ 3.5.
Consersion unit:
The reaction unit that the present invention uses has the warm-up block being connected in series by reaction sequence for micro passage reaction
With addition reaction module, condensation reaction module, acidification reaction module.
Warm-up block has first entrance and first outlet, and first entrance enters for three kinds of raw materials of initial stage, and first outlet supplies
Slurry outflow.Addition reaction module has second entrance, addition material entrance and second outlet, and second entrance and first outlet join
Logical, addition material enters the entrance of confession formaldehyde, and second outlet goes out for addition reaction liquid stream.Condensation reaction module has third entrance, contracting
Material entrance and third outlet, third entrance and second outlet connection are closed, condensation expects to enter into confession dimethylphosphite, and third goes out
The outflow of confession condensation reaction solution.Acidification reaction module has the 4th entrance, acidification material entrance and the 4th outlet, the 4th entrance and the
Three outlet connection, acidification expect to enter into confession hydrochloric acid, and the 4th outlet is flowed out for final reacting product.
Addition material entrance, condensation material entrance, acidification material entrance are respectively provided with the control valve that can control respective material entrance,
Each control valve connects the same controller, and controller can issue each control valve folding opportunity (according to the stream of reaction mass
Speed, the data such as dosage of the length volume of modules, reaction mass calculate and control time that each valve successively opens and closes and
Duration) instruction.The control valve of addition reaction entrance, which is opened the slurry that opportunity is preheating step and is introduced into, reaches addition reaction mould
After the dosage needed in block, then opens and be put into formaldehyde.The control valve of condensation reaction entrance opens opportunity to be first put into phosphorous acid two
The amount that methyl esters needs is into condensation reaction module, then flows into addition reaction liquid.
In preferred embodiment of the invention, the metering and charging of material are carried out by metering pump, and above-mentioned addition reaction module is excellent
Choosing completes input by diaphragm pump, and completes accurate measurement with the use of balance, and condensation reaction and acidification reaction module are preferably by column
Plug pump completes metering and charging.
The module has three-layer sandwich mechanism, and two outside layers are recycled for heat transfer oil, and middle layer is for reacting
Fluid flowing.Wherein warm-up block and addition reaction module are controlled by the same oil bath heating device, guarantee essentially identical temperature
Degree；Condensation reaction module is controlled by individual oil bath heating device, and acidification reaction module is controlled by water bath device, and control is each respectively
From the reaction temperature of needs.
In scheme of the present invention, before in 1-3 module fluid-mixing pH between 7.0 ~ 8.3, last module 4
Reaction carried out in acidic environment, in the normal range of operation of reactor.The module is by glass or ceramic material system
It is suitable within 1.8Mpa at middle layer, -60 ~ 200 DEG C of reaction condition, while there is preferable chemical corrosivity.
The utility model has the advantages that
Reactor of the invention and traditional autoclave comparision of production, have mass-and heat-transfer it is high-efficient, it is easy to operate, accurately control
The advantages that reaction time, occupied area small, without enlarge-effect.Since reaction mass is few in unit volume, keep heat release controllable, environmentally friendly
Safety.Due to the special construction in microchannel, keep mass-and heat-transfer high-efficient, can make shorten reaction time, side reaction product is few, obtains
The product purity that arrives is high, high income.
The generation of by-product methyl glyphosate in background technique and glyphosine is all product glyphosate and excessive formaldehyde
Or phosphorous acid reaction generates.The micro passage reaction that synthesizing glyphosate provided by the invention uses can be realized multistage feeding, essence
Really control various raw material entry time and reaction temperature.Most of all, the reactor is in the mixed process of material both without returning
It is mixed, and mode of entrance and the opportunity, reaction process parameter of respective raw material are controlled respectively, above-mentioned tandem reaction can be well solved
Lead to the problem that by-product is excessive.
Detailed description of the invention
Fig. 1 is a kind of schematic perspective view of micro passage reaction of the invention；
In figure, 1- warm-up block；2- addition reaction module；3- condensation reaction module；4- acidification reaction module；The upper heating layer of 5-；
6- intermediate reaction layer；Heating layer under 7-；8- the 4th is exported；9- acidification material entrance；10- condensation material entrance；11- addition material entrance；
12- first entrance.
Specific embodiment
Embodiment 1:
Micro passage reaction as shown in Figure 1 has the warm-up block and addition reaction being connected in series by reaction sequence
Module, condensation reaction module, acidification reaction module.
Warm-up block has first entrance and first outlet, and first entrance enters for three kinds of raw materials of initial stage；Addition reaction mould
Block has second entrance, addition material entrance, and addition material enters the entrance of confession formaldehyde.Condensation reaction module has third entrance, condensation
Expect entrance, condensation expects to enter into confession dimethylphosphite.Acidification reaction module has the 4th entrance, acidification material entrance and the 4th
Outlet, acidification expect to enter into confession hydrochloric acid, and the 4th outlet is flowed out for final reacting product glyphosate solution.
Addition material entrance, condensation material entrance, acidification material entrance are respectively provided with control valve, can manually or automatically control each
From the material entry time.
Powdered glycine 30.6g, triethylamine 36g, methanol 239.4g are weighed, glycine slurry is prepared into after being sufficiently stirred
Material, the warm-up block for entering 50 ~ 60 DEG C of heating through diaphragm pump preheat, and enter back into addition reaction module, and slurry is into reaction module
Meanwhile open depolymerization liquid pump, by be 55% containing formaldehyde depolymerization liquid 30.6g be added to addition reaction module and glycine slurry into
Row addition reaction generates addition liquid, while addition liquid enters condensation reaction module, opens dimethylphosphite feed pump, will
45.4g dimethylphosphite is added in condensation module, controls 50 ~ 60 DEG C of heating temperature, completes condensation reaction.Condensation liquid is into acidification
While reaction module, hydrochloric acid feed pump is opened, 30% hydrochloric acid solution 155.7g is added in module, water-bath control reaction
20 ~ 40 degrees Celsius of temperature, reaction obtains acidifying solution.
Glyphosate 56.5g is obtained by filtration through dealcoholysis depickling, neutralization, crystallization in obtained acidifying solution, content 96.3%, Gu
Body glyphosate yield 80.45%.
Embodiment 2:
Using identical micro passage reaction in above-described embodiment 1.
Powdered glycine 30.6g, triethylamine 36g, methanol 315.9g are weighed, glycine slurry is prepared into after being sufficiently stirred
Material, the warm-up block for entering 50 ~ 60 DEG C of heating through diaphragm pump preheat, and enter back into addition reaction module, and slurry is into reaction module
Meanwhile open depolymerization liquid pump, by be 22% containing formaldehyde depolymerization liquid 108.1g be added to addition reaction module and glycine slurry into
Row addition reaction generates addition liquid, while addition liquid enters condensation reaction module, opens dimethylphosphite feed pump, will
46.8g dimethylphosphite is added in module, controls 50 ~ 60 DEG C of heating temperature, completes condensation reaction.Condensation liquid is into acidification reaction
While module, hydrochloric acid feed pump is opened, 30% hydrochloric acid solution 170.3g is added in module, water-bath controls reaction temperature
20 ~ 40 degrees Celsius, reaction obtains acidifying solution.
Glyphosate 56.7g is obtained by filtration through dealcoholysis depickling, neutralization, crystallization in obtained acidifying solution, content 96.0%, Gu
Body glyphosate yield 80.49%.
Claims (10)
1. a kind of preparation method of glyphosate has the preheating step being carried out continuously in the following order, addition reaction step, condensation
Reaction step, acidification reaction step, it is characterised in that:
(1) preheating step: glycine and methanol, triethylamine these three raw materials are mixed into slurry, being preheated to temperature is 40 ~ 65
℃；
(2) addition reaction step: in the slurry after preheating, being added formaldehyde, form depolymerization liquid, maintain above-mentioned temperature 60s ~ 90s, into
Row addition reaction；
(3) step of condensation: the addition reaction liquid formed in (2) is mixed with dimethylphosphite, is condensed
Reaction forms condensation liquid；Setting-up point is 40 ~ 65 DEG C, and total residence time is 50s ~ 80s to material in this step；
(4) acidification reaction step: the condensation liquid that (3) are formed is mixed with the hydrochloric acid solution of 25-32%, carries out acidification reaction, discharging
After obtain acidifying solution；Reaction temperature is 10 ~ 50 DEG C, and total residence time of the material in third reaction module is 40s ~ 60s.
2. the preparation method of glyphosate as claimed in claim 1, it is characterised in that: in addition reaction step, in whole
Formaldehyde is gradually added in slurry.
3. the preparation method of the glyphosate as described in claims 1 or 3, it is characterised in that: in addition reaction step, be added
Formaldehyde and (1) in glycine molar ratio be 1.4 ~ 1.8:1.
4. the preparation method of glyphosate as claimed in claim 1, it is characterised in that: in condensation reaction, first get ready and heat
Then whole dimethylphosphites are gradually added addition reaction liquid wherein, mix with addition reaction liquid and carry out condensation reaction；Contracting
Closing reaction temperature is 55 ~ 65 DEG C.
5. the preparation method of the glyphosate as described in claims 1 or 4, it is characterised in that: in condensation reaction, phosphorous acid diformazan
The molar ratio of ester and glycine is 1.02 ~ 1.05:1.
6. the preparation method of glyphosate as claimed in claim 1, it is characterised in that: in acidification reaction, hydrochloric acid and glycine
Mol ratio be 3.2 ~ 3.5.
7. a kind of micro passage reaction for being prepared glyphosate using method described in claim 1 is had and is connected by reaction sequence
Warm-up block, addition reaction module, condensation reaction module and the acidification reaction module to link together；
Warm-up block has first entrance and first outlet, and first entrance enters for three kinds of raw materials of initial stage；Addition reaction module tool
There are second entrance, addition material entrance and second outlet, second entrance and first outlet connection, addition material enters the entrance of confession formaldehyde；
Condensation reaction module has third entrance, condensation material entrance and a third outlet, third entrance and second outlet connection, condensation expect into
Confession dimethylphosphite enters；Acidification reaction module have the 4th entrance, acidification material entrance and the 4th outlet, the 4th entrance with
Third exports connection, and acidification expects to enter into confession hydrochloric acid, and the 4th outlet is flowed out for the acidifying solution of final reacting product.
8. the preparation micro passage reaction of glyphosate as claimed in claim 7, it is characterised in that: addition material entrance, condensation
Material entrance, acidification material entrance are respectively provided with control valve, can manually or automatically control the respective material entry time.
9. the preparation micro passage reaction of glyphosate as claimed in claim 7 or 8, it is characterised in that: the module is equal
With three-layer sandwich mechanism, two outside layers are recycled for heat transfer oil, and middle layer is flowed for reacting fluid.
10. the preparation micro passage reaction of glyphosate as claimed in claim 9, it is characterised in that: warm-up block and addition
Reaction module is controlled by the same oil bath heating device, and condensation reaction module is controlled by individual oil bath heating device, and acidification is anti-
Module is answered to be controlled by water bath device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922426A (en) * | 2019-11-22 | 2020-03-27 | 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 by-product hydrolysis process and its microchannel reactor |
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