CN107501318A - A kind of synthesis technique of glyphosate intermediate dimethylphosphite - Google Patents
A kind of synthesis technique of glyphosate intermediate dimethylphosphite Download PDFInfo
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- CN107501318A CN107501318A CN201710570152.9A CN201710570152A CN107501318A CN 107501318 A CN107501318 A CN 107501318A CN 201710570152 A CN201710570152 A CN 201710570152A CN 107501318 A CN107501318 A CN 107501318A
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- esterification
- rectifying
- dimethylphosphite
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- methanol
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- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 16
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 16
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 183
- 230000032050 esterification Effects 0.000 claims abstract description 99
- 238000005886 esterification reaction Methods 0.000 claims abstract description 99
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 49
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 27
- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims description 35
- 230000005494 condensation Effects 0.000 claims description 35
- 239000003223 protective agent Substances 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- -1 phosphorous acid diformazan Ester Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 238000007086 side reaction Methods 0.000 description 15
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HCSDJECSMANTCX-UHFFFAOYSA-N dichloro(methoxy)phosphane Chemical compound COP(Cl)Cl HCSDJECSMANTCX-UHFFFAOYSA-N 0.000 description 2
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical compound COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 description 1
- SRXOCFMDUSFFAK-UHFFFAOYSA-N dimethyl peroxide Chemical compound COOC SRXOCFMDUSFFAK-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 229960001952 metrifonate Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of synthesis technique of glyphosate intermediate dimethylphosphite, its step are as follows：Methanol is measured into reaction kettle of the esterification by methanol measuring tank, phosphorus dichloride enters reaction kettle of the esterification after measuring tank, material is entered simultaneously by proportioning, feed liquid after esterification flows into depickling kettle through interior liquid sealing pipe, gas caused by esterification returns to esterifying kettle through being esterified I and II condenser, feed liquid in depickling kettle removes hydrogen chloride under high vacuum and steam heating condition, and feed liquid enters back into rectifying still and carries out rectifying after depickling kettle depickling；The above method of the present invention can make dimethylphosphite realize the production of serialization, lifting for production capacity and operating cost is further greatly lowered provides great development space, and purity is even more to bring up to more than 99.0%.
Description
Technical field
The present invention relates to pesticide processing field, and in particular to a kind of synthesis work of glyphosate intermediate dimethylphosphite
Skill.
Background technology
Dimethylphosphite is a staple product in fine chemistry industry.It is both production glyphosate, metrifonate, rice blast
Only, the intermediate of the agricultural chemicals such as flolimat, it is the raw material of organophosphorus corrosion inhibitor, dye additive, plastic additive and fire retardant again,
Available for water treatment agent is synthesized, the bactericide, antistatic additive, softening agent for synthesizing quaternary ammonium salts can be also used for as methylating reagent
Deng product.
Dimethylphosphite is usually industrially to react to be made as raw material using phosphorus trichloride and methanol：PCl3+3CH3OH→
(CH3O)2POH+2HCl↑+CH3Cl ↑ course of reaction and mechanism are：
PCl3+CH3OH→CH3OPCl2+HCl↑(1)
CH3OPCl2+CH3OH→(CH3O)2PCl+HCl↑(2)
(CH3O)2+CH3OH→(CH3O)3P+HCl↑(3)
(CH3O)3P+HCl→(CH3O)2POH+CH3Cl↑(4)
Trimethyl phosphite in course of reaction in (3) formula is extremely unstable, as long as with the presence of HCl, it is sub- just to react generation
Dimethyl phosphate.And HCl presence, while product dimethylphosphite is continued that following side reaction occurs：
(CH3O)2POH+HCl→CH3OP(OH)2+CH3Cl↑
CH3OP(OH)2+HCl→H3PO3+CH3Temperature in Cl ↑ course of reaction is higher and/or the time is longer, and side reaction is got over
It is more.Because the above-mentioned reaction of phosphorus trichloride and methanol is strongly exothermic transient response, therefore ensure that reaction is smoothed out and completed
Key, be to try to create the condition for making two reactants fully contact, and shorten the reaction time, effectively remove reaction heat, with
And the HCl as much as possible in elimination reaction product, to suppress the generation of side reaction.
The industrial production of dimethylphosphite is continued to use always at present is the batch process of single pot of reaction and one-pot rectifying, its
Reaction mass is sent into via head tank, and measure control difficulty is big, and need to control progress of the reaction below 55 DEG C, frequent operation,
Labor intensity is big, and the production cycle is long, capacity of equipment is low.Meanwhile need to remove reaction with freezing mode during the course of the reaction
Heat, and need to heat material during depickling, the capacity usage ratio in production process is low.
The content of the invention
It is an object of the invention to provide a kind of synthesis technique of glyphosate intermediate dimethylphosphite, product is improved
Purity.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of synthesis technique of glyphosate intermediate dimethylphosphite, it is characterised in that its step is as follows：
1) methanol enters reaction kettle of the esterification by methanol measuring tank, and phosphorus dichloride enters reaction kettle of the esterification after measuring tank,
Material is entered simultaneously by proportioning, then carries out esterification, and stirs 3-10 minutes, and the temperature of reaction kettle of the esterification keeps 20-25
℃；
2) feed liquid after esterification flows into depickling kettle through interior liquid sealing pipe, while gas caused by esterification is through esterification
I and II condenser returns to esterifying kettle；
3) the feed liquid removing hydrogen chloride in depickling kettle；
4) feed liquid enters back into rectifying still progress rectifying and obtains dimethylphosphite after the depickling of depickling kettle.
Further, stirring system is opened during step 1 esterification to be stirred, and mixing time is 15-20 minutes, ester
Heat-conducting oil heating system is opened when changing reaction so that heating-up temperature is kept for 20 DEG C, opens vacuumize process during esterification so that
The pressure of esterification is negative pressure, and the reaction time is 2-6 hours.
Further, gas caused by esterification carries out one-level condensation by one-level esterification condensator in step 2, will be cold
Material after solidifying is transferred to two level esterification condensator and carries out B-grade condensation, and the material after B-grade condensation is transferred into reaction kettle of the esterification
It is interior, carry out esterification.
Further, the hydrogen chloride gas in step 3 is passed through in ammoniacal liquor, and adds protective agent thereto, remove chlorination
The removing condition of hydrogen is that high vacuum pressure and steam heat.
Further, the step 4 distillation first stage keeps the pressure normal pressure of rectifying still, and adjusts rectifying still heat-conducting oil heating
System, rectifying condenser is opened to condensing into material therein, when the temperature on rectifying still kettle top is 63-65 DEG C, the time
For 2-3 hours, steam is distillated；Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still conduction oil and add
Hot systems, rectifying condenser is opened to condensing into material therein, when the temperature on rectifying still kettle top is 100-110 DEG C,
Time is 3-5 hours, distills out methanol；The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still and leads
Heating system of hot oil, rectifying condenser is opened to being condensed into material therein, when the temperature on rectifying still kettle top is 120-
140 DEG C, the time is 30-50 minutes, distills out the steam and methanol of residual.
Further, the mol ratio of methanol and phosphorus dichloride is (2-2.1) in step 1：1.
Further, protective agent is one kind in dichloroethanes, argon gas and nitrogen.
Further, the remaining liquid obtained after step 4 rectifying is condensed to room temperature using rectifying condenser obtains phosphorous acid
Dimethyl ester, survey dimethylphosphite purity.
Further, the methanol that step 4 is distilled is condensed using methanol condenser and first is recovered to by Methanol Recovery pipeline
In alcohol storage tank.
Advantage of the present invention is：Experiment display, aforementioned production method of the invention, phosphorus trichloride is substituted using phosphorus dichloride,
For comparing, the reaction time can be more greatly shortened, the acidolysis side reaction of dimethylphosphite is effectively prevented from, improves original
The conversion efficiency of material, up to more than 90%, the hydrogen chloride removal efficiency in thick ester product is reachable for the yield of dimethylphosphite
98%.And produced in conventional processes is used, the removal efficiency that the yield of dimethylphosphite is generally 80~88%, HCl is left for 90%
The right side, and because the removing to HCl is mainly completed in depickling device, therefore the load of depickling device is big, and HCl removing is too late
When also bring the problem of side reaction is more.In addition, the above method of the present invention can make dimethylphosphite realize serialization
Production, lifting for production capacity and is further greatly lowered operating cost and provides great development space, purity even more raising
To more than 99.0%.
Embodiment
The present invention is described in further details below in conjunction with embodiment.
Embodiment 1
Methanol measures 64Kg by methanol measuring tank and enters reaction kettle of the esterification, and phosphorus dichloride 106Kg after measuring tank enters
Enter reaction kettle of the esterification, expect by proportioning while enter, the feed liquid after esterification flows into depickling kettle, esterification production through interior liquid sealing pipe
Raw gas returns to esterifying kettle through being esterified I and II condenser, and the feed liquid in depickling kettle is under high vacuum and steam heating condition
Hydrogen chloride is removed, feed liquid enters back into rectifying still and carries out the dimethylphosphite that rectifying obtains more than 99% after depickling kettle depickling, by before
The hydrogen chloride gas stated is passed through in ammoniacal liquor, and adds protective agent thereto, and protective agent is dichloroethanes.During foregoing esterification
Open stirring system to be stirred, and mixing time is 15 minutes, opens heat-conducting oil heating system during esterification so that heating
Temperature is kept for 20 DEG C, opens vacuumize process during esterification so that the pressure of esterification be negative pressure, and the reaction time is small for 2
When.Gas caused by esterification carries out one-level condensation by one-level esterification condensator, and condensed material is transferred into two level ester
Change condenser and carry out B-grade condensation, and the material after B-grade condensation is transferred in reaction kettle of the esterification, carry out esterification.
The pressure normal pressure of first stage holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 63 DEG C, the time is 2 hours, distillates steam；
Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still heat-conducting oil heating system, open rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 100 DEG C, the time is 3 hours, distills out methanol；
The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 120 DEG C, the time is 30 minutes, distills out residual
Steam and methanol, the methanol of distillation is recovered in methanol storage tank using methanol condenser condensation by Methanol Recovery pipeline,
The remaining liquid obtained after rectifying is condensed to room temperature using rectifying condenser and obtains dimethylphosphite, and it is pure to survey dimethylphosphite
Degree.And protective agent is argon gas.
Experiment display, aforementioned production method of the invention, using phosphorus dichloride substitute phosphorus trichloride, compare for, more
The reaction time can be greatly shortened by adding, and be effectively prevented from the acidolysis side reaction of dimethylphosphite, improve effective conversion of raw material
Rate, the yield of dimethylphosphite is up to more than 90%, and the hydrogen chloride removal efficiency in thick ester product is up to 98%.And use tradition
Method produces, and the removal efficiency that the yield of dimethylphosphite is generally 80%, HCl is 90% or so, and due to being taken off to HCl
Except mainly completing in depickling device, therefore the load of depickling device is big, and HCl removing is also brought more than side reaction not in time
Problem.In addition, the above method of the present invention can make dimethylphosphite realize the production of serialization, lifting for production capacity and enter
One step is greatly lowered operating cost and provides great development space, and purity is even more to bring up to more than 99.0%.
Embodiment 2
Methanol measures 65.8Kg by methanol measuring tank and enters reaction kettle of the esterification, phosphorus dichloride 106Kg after measuring tank
Into reaction kettle of the esterification, expect by proportioning while enter, the feed liquid after esterification flows into depickling kettle, esterification through interior liquid sealing pipe
Caused gas returns to esterifying kettle through being esterified I and II condenser, and the feed liquid in depickling kettle is in high vacuum and steam heating condition
Lower removing hydrogen chloride, feed liquid enters back into rectifying still and carries out the dimethylphosphite that rectifying obtains more than 99% after depickling kettle depickling, will
Hydrogen chloride gas in foregoing is passed through in ammoniacal liquor, and adds protective agent thereto, and protective agent is dichloroethanes.Foregoing esterification
Shi Kaiqi stirring systems are stirred, and mixing time is 17 minutes, open heat-conducting oil heating system during esterification so that add
Hot temperature is kept for 20 DEG C, opens vacuumize process during esterification so that the pressure of esterification is negative pressure, the reaction time 3
Hour.Gas caused by esterification carries out one-level condensation by one-level esterification condensator, and condensed material is transferred into two level
Esterification condensator carries out B-grade condensation, and the material after B-grade condensation is transferred in reaction kettle of the esterification, carries out esterification.
The pressure normal pressure of first stage holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 64 DEG C, the time is 2.5 hours, distillates steaming
Gas；Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still heat-conducting oil heating system, it is cold to open rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 105 DEG C, the time is 3-5 hours, distills out first
Alcohol；The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, it is cold to open rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 125 DEG C, the time is 35 minutes, is distilled out residual
The steam and methanol stayed, the methanol of distillation is condensed using methanol condenser is recovered to methanol storage tank by Methanol Recovery pipeline
In, the remaining liquid that is obtained after rectifying is condensed to room temperature using rectifying condenser and obtains dimethylphosphite, surveys phosphorous acid diformazan
Ester purity.
And protective agent is dichloroethanes.
Experiment display, aforementioned production method of the invention, using phosphorus dichloride substitute phosphorus trichloride, compare for, more
The reaction time can be greatly shortened by adding, and be effectively prevented from the acidolysis side reaction of dimethylphosphite, improve effective conversion of raw material
Rate, the yield of dimethylphosphite is up to more than 90%, and the hydrogen chloride removal efficiency in thick ester product is up to 98%.And use tradition
Method produces, and the removal efficiency that the yield of dimethylphosphite is generally 82%, HCl is 90% or so, and due to being taken off to HCl
Except mainly completing in depickling device, therefore the load of depickling device is big, and HCl removing is also brought more than side reaction not in time
Problem.In addition, the above method of the present invention can make dimethylphosphite realize the production of serialization, lifting for production capacity and enter
One step is greatly lowered operating cost and provides great development space, and purity is even more to bring up to more than 99.0%.
Embodiment 3
Methanol measures 66.3Kg by methanol measuring tank and enters reaction kettle of the esterification, phosphorus dichloride 106Kg after measuring tank
Into reaction kettle of the esterification, expect by proportioning while enter, the feed liquid after esterification flows into depickling kettle, esterification through interior liquid sealing pipe
Caused gas returns to esterifying kettle through being esterified I and II condenser, and the feed liquid in depickling kettle is in high vacuum and steam heating condition
Lower removing hydrogen chloride, feed liquid enters back into rectifying still and carries out the dimethylphosphite that rectifying obtains more than 99% after depickling kettle depickling, will
Hydrogen chloride gas in foregoing is passed through in ammoniacal liquor, and adds protective agent thereto, and protective agent is dichloroethanes.Foregoing esterification
Shi Kaiqi stirring systems are stirred, and mixing time is 18 minutes, open heat-conducting oil heating system during esterification so that add
Hot temperature is kept for 20 DEG C, opens vacuumize process during esterification so that the pressure of esterification is negative pressure, the reaction time 4
Hour.Gas caused by esterification carries out one-level condensation by one-level esterification condensator, and condensed material is transferred into two level
Esterification condensator carries out B-grade condensation, and the material after B-grade condensation is transferred in reaction kettle of the esterification, carries out esterification.
The pressure normal pressure of first stage holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 65 DEG C, the time is 3 hours, distillates steam；
Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still heat-conducting oil heating system, open rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 108 DEG C, the time is 4 hours, distills out methanol；
The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 130 DEG C, the time is 40 minutes, distills out residual
Steam and methanol, the methanol of distillation is recovered in methanol storage tank using methanol condenser condensation by Methanol Recovery pipeline,
The remaining liquid obtained after rectifying is condensed to room temperature using rectifying condenser and obtains dimethylphosphite, and it is pure to survey dimethylphosphite
Degree.
And protective agent is nitrogen.
Experiment display, aforementioned production method of the invention, using phosphorus dichloride substitute phosphorus trichloride, compare for, more
The reaction time can be greatly shortened by adding, and be effectively prevented from the acidolysis side reaction of dimethylphosphite, improve effective conversion of raw material
Rate, the yield of dimethylphosphite is up to more than 90%, and the hydrogen chloride removal efficiency in thick ester product is up to 98%.And use tradition
Method produces, and the removal efficiency that the yield of dimethylphosphite is generally 84%, HCl is 90% or so, and due to being taken off to HCl
Except mainly completing in depickling device, therefore the load of depickling device is big, and HCl removing is also brought more than side reaction not in time
Problem.In addition, the above method of the present invention can make dimethylphosphite realize the production of serialization, lifting for production capacity and enter
One step is greatly lowered operating cost and provides great development space, and purity is even more to bring up to more than 99.0%.
Embodiment 4
Methanol measures 67.5Kg by methanol measuring tank and enters reaction kettle of the esterification, phosphorus dichloride 106Kg after measuring tank
Into reaction kettle of the esterification, expect by proportioning while enter, the feed liquid after esterification flows into depickling kettle, esterification through interior liquid sealing pipe
Caused gas returns to esterifying kettle through being esterified I and II condenser, and the feed liquid in depickling kettle is in high vacuum and steam heating condition
Lower removing hydrogen chloride, feed liquid enters back into rectifying still and carries out the dimethylphosphite that rectifying obtains more than 99% after depickling kettle depickling, will
Hydrogen chloride gas in foregoing is passed through in ammoniacal liquor, and adds protective agent thereto, and protective agent is dichloroethanes.Foregoing esterification
Shi Kaiqi stirring systems are stirred, and mixing time is 19 minutes, open heat-conducting oil heating system during esterification so that add
Hot temperature is kept for 20 DEG C, opens vacuumize process during esterification so that the pressure of esterification is negative pressure, the reaction time 5
Hour.Gas caused by esterification carries out one-level condensation by one-level esterification condensator, and condensed material is transferred into two level
Esterification condensator carries out B-grade condensation, and the material after B-grade condensation is transferred in reaction kettle of the esterification, carries out esterification.
The pressure normal pressure of first stage holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 63 DEG C, the time is 2 hours, distillates steam；
Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still heat-conducting oil heating system, open rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 110 DEG C, the time is 5 hours, distills out methanol；
The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 140 DEG C, the time is 50 minutes, distills out residual
Steam and methanol, the methanol of distillation is recovered in methanol storage tank using methanol condenser condensation by Methanol Recovery pipeline,
The remaining liquid obtained after rectifying is condensed to room temperature using rectifying condenser and obtains dimethylphosphite, and it is pure to survey dimethylphosphite
Degree.
And protective agent is argon gas.
Experiment display, aforementioned production method of the invention, using phosphorus dichloride substitute phosphorus trichloride, compare for, more
The reaction time can be greatly shortened by adding, and be effectively prevented from the acidolysis side reaction of dimethylphosphite, improve effective conversion of raw material
Rate, the yield of dimethylphosphite is up to more than 90%, and the hydrogen chloride removal efficiency in thick ester product is up to 98%.And use tradition
Method produces, and the removal efficiency that the yield of dimethylphosphite is generally 86%, HCl is 90% or so, and due to being taken off to HCl
Except mainly completing in depickling device, therefore the load of depickling device is big, and HCl removing is also brought more than side reaction not in time
Problem.In addition, the above method of the present invention can make dimethylphosphite realize the production of serialization, lifting for production capacity and enter
One step is greatly lowered operating cost and provides great development space, and purity is even more to bring up to more than 99.0%.
Embodiment 5
Methanol measures 68.2Kg by methanol measuring tank and enters reaction kettle of the esterification, phosphorus dichloride 106Kg after measuring tank
Into reaction kettle of the esterification, expect by proportioning while enter, the feed liquid after esterification flows into depickling kettle, esterification through interior liquid sealing pipe
Caused gas returns to esterifying kettle through being esterified I and II condenser, and the feed liquid in depickling kettle is in high vacuum and steam heating condition
Lower removing hydrogen chloride, feed liquid enters back into rectifying still and carries out the dimethylphosphite that rectifying obtains more than 99% after depickling kettle depickling, will
Hydrogen chloride gas in foregoing is passed through in ammoniacal liquor, and adds protective agent thereto, and protective agent is dichloroethanes.Foregoing esterification
Shi Kaiqi stirring systems are stirred, and mixing time is 20 minutes, open heat-conducting oil heating system during esterification so that add
Hot temperature is kept for 20 DEG C, opens vacuumize process during esterification so that the pressure of esterification is negative pressure, the reaction time 6
Hour.Gas caused by esterification carries out one-level condensation by one-level esterification condensator, and condensed material is transferred into two level
Esterification condensator carries out B-grade condensation, and the material after B-grade condensation is transferred in reaction kettle of the esterification, carries out esterification.
The pressure normal pressure of first stage holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 65 DEG C, the time is 3 hours, distillates steam；
Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still heat-conducting oil heating system, open rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 110 DEG C, the time is 5 hours, distills out methanol；
The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 140 DEG C, the time is 50 minutes, distills out residual
Steam and methanol, the methanol of distillation is recovered in methanol storage tank using methanol condenser condensation by Methanol Recovery pipeline,
The remaining liquid obtained after rectifying is condensed to room temperature using rectifying condenser and obtains dimethylphosphite, and it is pure to survey dimethylphosphite
Degree.
And protective agent is dichloroethanes.
Experiment display, aforementioned production method of the invention, using phosphorus dichloride substitute phosphorus trichloride, compare for, more
The reaction time can be greatly shortened by adding, and be effectively prevented from the acidolysis side reaction of dimethylphosphite, improve effective conversion of raw material
Rate, the yield of dimethylphosphite is up to more than 90%, and the hydrogen chloride removal efficiency in thick ester product is up to 98%.And use tradition
Method produces, and the removal efficiency that the yield of dimethylphosphite is 88%, HCl is 90% or so, and due to the removing master to HCl
If completed in depickling device, therefore the load of depickling device is big, and HCl removing also brings asking more than side reaction not in time
Topic.In addition, the above method of the present invention can make dimethylphosphite realize the production of serialization, lifting for production capacity and enter one
Step is greatly lowered operating cost and provides great development space, and purity is even more to bring up to more than 99.0%.
Claims (9)
1. a kind of synthesis technique of glyphosate intermediate dimethylphosphite, it is characterised in that its step is as follows：
1) methanol enters reaction kettle of the esterification by methanol measuring tank, and phosphorus dichloride enters reaction kettle of the esterification after measuring tank, and material is pressed
Proportioning enters simultaneously, then carries out esterification, and stirs 3-10 minutes, and the temperature of reaction kettle of the esterification is kept for 20-25 DEG C；
2) feed liquid after esterification flows into depickling kettle through interior liquid sealing pipe, while gas caused by esterification is through esterification one, two
Level condenser returns to esterifying kettle；
3) the feed liquid removing hydrogen chloride in depickling kettle；
4) feed liquid enters back into rectifying still progress rectifying and obtains dimethylphosphite after the depickling of depickling kettle.
A kind of 2. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Step
Stirring system is opened during rapid 1 esterification to be stirred, and mixing time is 15-20 minutes, open conduction oil during esterification
Heating system so that heating-up temperature is kept for 20 DEG C, opens vacuumize process during esterification so that the pressure of esterification is negative
Pressure, the reaction time is 2-6 hours.
A kind of 3. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Step
Gas caused by esterification carries out one-level condensation by one-level esterification condensator in rapid 2, and condensed material is transferred into two level
Esterification condensator carries out B-grade condensation, and the material after B-grade condensation is transferred in reaction kettle of the esterification, carries out esterification.
A kind of 4. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Will
Hydrogen chloride gas in step 3 is passed through in ammoniacal liquor, and adds protective agent thereto, and removing removing hydrogen chloride condition is high vacuum
Pressure and steam heating.
A kind of 5. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Step
The rapid 4 distillation first stage keeps the pressure normal pressure of rectifying still, and adjusts rectifying still heat-conducting oil heating system, opens rectifying condenser
To being condensed into material therein, when the temperature on rectifying still kettle top is 63-65 DEG C, the time is 2-3 hours, distillates steam；
Distill second stage and keep the vacuum pressure normal pressure of rectifying still, and adjust rectifying still heat-conducting oil heating system, open rectifying condensation
Device into material therein to condensing, and when the temperature on rectifying still kettle top is 100-110 DEG C, the time is 3-5 hours, is distilled out
Methanol；The vacuum pressure normal pressure of phase III holding rectifying still is distilled, and adjusts rectifying still heat-conducting oil heating system, opens rectifying
Condenser into material therein to condensing, and when the temperature on rectifying still kettle top is 120-140 DEG C, the time is 30-50 minutes,
Distill out the steam and methanol of residual.
A kind of 6. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Step
The mol ratio of methanol and phosphorus dichloride is (2-2.1) in rapid 1：1.
A kind of 7. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Protect
Shield agent is one kind in dichloroethanes, argon gas and nitrogen.
A kind of 8. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 1, it is characterised in that：Step
The remaining liquid obtained after rapid 4 rectifying is condensed to room temperature using rectifying condenser and obtains dimethylphosphite, surveys phosphorous acid diformazan
Ester purity.
A kind of 9. synthesis technique of glyphosate intermediate dimethylphosphite according to claim 5, it is characterised in that：Will
The methanol that step 4 is distilled is recovered in methanol storage tank using methanol condenser condensation by Methanol Recovery pipeline.
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