CN107912446A - Recycling salt containing glyphosate, Trimethyl phosphite prepares the method and its device of glufosinate-ammonium composite pesticide - Google Patents
Recycling salt containing glyphosate, Trimethyl phosphite prepares the method and its device of glufosinate-ammonium composite pesticide Download PDFInfo
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- CN107912446A CN107912446A CN201711255065.0A CN201711255065A CN107912446A CN 107912446 A CN107912446 A CN 107912446A CN 201711255065 A CN201711255065 A CN 201711255065A CN 107912446 A CN107912446 A CN 107912446A
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- Prior art keywords
- glufosinate
- ammonium
- reaction
- trimethyl phosphite
- recycling
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- 150000003839 salts Chemical class 0.000 title claims abstract description 36
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 28
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 28
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000575 pesticide Substances 0.000 title claims abstract description 20
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- DMXDWFDABLNZKH-UHFFFAOYSA-N CNC(S)=N.COP(C)(O)OC Chemical compound CNC(S)=N.COP(C)(O)OC DMXDWFDABLNZKH-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000005219 aminonitrile group Chemical group 0.000 claims description 2
- 238000004176 ammonification Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- -1 phosphorus trichloride Chloro phosphite ester Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000857 drug effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 241000208841 Ambrosia trifida Species 0.000 description 2
- 235000004385 Conyza canadensis Nutrition 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- RUUYGFRRGLCAIE-UHFFFAOYSA-N chloro dihydrogen phosphite Chemical compound OP(O)OCl RUUYGFRRGLCAIE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical compound C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940127089 cytotoxic agent Drugs 0.000 description 1
- 239000002254 cytotoxic agent Substances 0.000 description 1
- 231100000599 cytotoxic agent Toxicity 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 244000037671 genetically modified crops Species 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate tribasic Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 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 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides it is a kind of containing glyphosate, Trimethyl phosphite recycling salt prepare glufosinate-ammonium composite pesticide method and, using chloromethanes, alchlor and phosphorus trichloride as raw material, react the ternary complexes of generation, at the same time under the catalysis reduction and the decomplexing double action of sodium chloride of aluminium powder, distillation obtains methyl dichloro phosphorus, and then for the synthesis of glufosinate-ammonium composite pesticide.This programme realizes the recycling of the industrial productions such as glyphosate, trimethyl phosphate recycling salt discarded object, and the drug effect of composite pesticide is due to common glufosinate-ammonium.
Description
Technical field
The present invention relates to a kind of improvement of industrial waste salt and the synthetic technology of glufosinate-ammonium pesticide.
Background technology
Substantial amounts of by-product salt can be produced in glyphosate, tripotassium phosphate ester production process, which is chlorine
Change sodium, in addition also containing organic components such as glyphosate, glyphosine and glycine.It is more organic due to containing in by-product Nacl
The presence of nitrogen and organophosphor causes solid abraum salt not apply, and industrial waste salt can only be used as to handle.
Patent announcement number is a kind of processing method of glyphosate by-product Nacl disclosed in the invention of CN104692419A,
Reach ion film caustic soda refined brine standard using technique, the indices such as high-temperature calcination, dissolving dephosphorization, refined, can be direct
Electrolysis process for ion film caustic soda.It need to be calcined in this method at 500 DEG C ~ 600 DEG C of high temperature, then with being passed through after Na2CO3 dephosphorization
Cross resin adsorption and etc. obtain refined brine, the process cycle is long, electrolysis process is more demanding, processing cost is high, and to chlorine
There are security risk for alkali industry.
Disclosure of the invention a kind of industrial by-product salt harmless treatment and the recycling that patent announcement number is CN103267296A
The method utilized, the salt after this method processing can be used as the fields such as building material additives, snow melting agent and raw material salt, but its calcination time
For 4 ~ 10 it is small when, processing cost is high, and production capacity is relatively low.
Pesticide magazine 2002 year the 5th phase of volume 41《The synthetic method of methyl dichloro phosphorus》Method in 1.15 is with chlorine
Methane, alchlor and phosphorus trichloride are raw material, first with aluminium reducing chloromethanes, then carry out complex reaction, then add chlorination
Sodium solution is complexed, and three-step reaction is more complicated, and the reaction time is long.
Glyphosate lifespan in production is grown, and many weeds such as Horseweed Herbs etc. have produced stronger resistance to the medicine at present.
The medicine weeding speed is relatively slow, but its uptake and translocation is very strong, under ground portion can be transmitted to by cauline leaf, in same plant
Different tillers between can also be conducted, weeds can be connected to root kill, to the underground organization destructive power of perennial deep root weeds very
By force, the depth that general agricultural machinery is unable to reach can be reached.Glyphosate bury after quickly with the metal ion such as the iron in soil, aluminium
With reference to and lose activity.
Glufosinate-ammonium is non-selective contact killing type herbicide, is glutamine synthetase inhibitor, has part systemic action.Apply
Ammonium, which is metabolized, after medicine in the short time, in weeds body sinks into disorder, and cytotoxic agent ammonium ion is accumulated in vivo, at the same time photosynthesis
Seriously suppressed, reach weeding purpose.Herbicidal effect is preferable, broad weed-killing spectrum, and the lasting period is up to 1 month, can remove Horseweed Herb etc.
The weeds of stronger resistance have been produced to paraquat, glyphosate.Soil texture is not destroyed, does not hinder crop root.Medicine and soil knot
It can be decomposed after conjunction by edaphon rapidly, various crop safeties are sowed in dispenser after 1 day.Glufosinate-ammonium is gone out as fast-acting type of new generation
Nature herbiciding agent, has obtained highly recognition in production.
《Hangzhou chemical industry》4 phases in 2015 describe the bioactivity and field medicine of glufosinate-ammonium glyphosate mixture aqua
Effect, article are pointed out, with increasingly mature, glyphosate and the glufosinate-ammonium multiple resistance genetically modified crops cultivated area of transgenic technology
Increase rapidly, be on the increase plus glyphosate-resistant weeds, glyphosate and glufosinate-ammonium compound product market potential are huge.It is rationally multiple
With ratio, with ensure product it is efficient, reduce cost, become current research emphasis.
《Pesticide》This special tired Ke Er reaction and close that addition process described in magazine the 9th phase in 2002, using phosphorous acid three
Methyl esters and phosphorus trichloride reaction generation chloro phosphite ester, then carry out reaction and form glufosinate-ammonium.
The content of the invention
Goal of the invention：
Recycling salt can be made full use of by providing one kind, prepared by the recycling salt containing glyphosate, Trimethyl phosphite for preparing high-drug-effect
The method and its preparation facilities of glufosinate-ammonium composite pesticide.
Technical solution：
The method that the recycling salt containing glyphosate, Trimethyl phosphite of this programme prepares glufosinate-ammonium composite pesticide, its preparation have
Following steps：
（1）Commercial recovery salt containing glyphosate, Trimethyl phosphite（Main component sodium chloride）Because wherein containing organic nitrogen and organic
Phosphorus, has caking phenomenon, is first pre-processed, and recycling salt raw material is successively by the pre- place of pre-processing device baking oven and grinding container
Reason.Place it in baking oven and 2 ~ 5h is dried, the sodium chloride powder of 200 ~ 500 mesh is then ground in grinding container, just
It is spare in coming into full contact with reaction with other raw materials；Wherein sodium chloride content can also be analyzed, and carries out purified treatment, works as chlorination
Sodium content is spare when being in the range of 90% ~ 98%, and the impurity in products of so participation subsequent reactions is less, and drug effect is notable.
（2）Closed（It is preferred that corrosion-resistant, compression resistance, heat-resisting Hastelloy）Add in pre-reactor alchlor and
Phosphorus trichloride, vacuum plant and agitating device are connected with reaction kettle, vacuumizes and removes air, heating unit, after stirring evenly
It is passed through chloromethanes.Material in reaction kettle is heated to 85 DEG C, phosphorus trichloride, alchlor and chlorine in the closed reactor
Methane carries out ternary complex reaction.Stop reaction after when reaction progress 6 ~ 12 is small, then reaction solution can be transferred to follow-up anti-
Answer container（It is preferred that the there-necked flask with three material inlets, easy to add reaction solution and two kinds of follow-up reaction raw materials respectively, no
Interfere with each other, avoid any two kinds of materials from being chemically reacted in advance so that intermediate increases in reaction product, the ratio of material
It is that clothing is accurately set, reaction product component is not pure enough）In it is spare.The molar ratio of the phosphorus trichloride and alchlor is 1：（1
~3）, the molar ratio of the phosphorus trichloride and chloromethanes is 1：（1~5）, phosphorus trichloride leaves surplus, easy to step（5）Carry out.
（3）By step（2）The solution system containing ternary complexes is heated to 140 DEG C ~ 160 DEG C of temperature, thereto
Add aluminium powder and step（1）Described in recycle salt, in this method, recycling salt is used as decomplexing agents.Distilled while reaction
Obtain product methyl dichloro phosphorus；The molar ratio of the aluminium powder and the phosphorus trichloride is 1：（0.5~1.5）, it is described recycling salt with
The molar ratio of the aluminium chloride is 1：（1~3）, such ratio ensures that each reaction raw materials fully participate in reacting, has and do not waste,
Finished product yield is higher.
（2）With（3）The chemical equation of middle progress is as follows successively：
（4）The methyl dichloro phosphorus of acquisition further reacts generation glufosinate-ammonium, its structural formula：
The present invention can also have step（5）, reference《Pesticide》Tired Ke Er reactions of this spy described in magazine the 9th phase in 2002 and
That addition process closely, using Trimethyl phosphite and phosphorus trichloride reaction generation chloro phosphite ester, then carries out reaction generation
Methylisothiouronium methylphosphite dimethyl ester, methylisothiouronium methylphosphite dimethyl ester form careless ammonium with aldehyde, Cymag generation amino nitrile, finally hydrolysis-ammonification
Phosphine.
Glyphosate and the glufosinate-ammonium recycled in salt is all phosphorous pesticide, forms that a kind of glyphosate content is relatively low, glufosinate-ammonium contains
The higher mixed insecticide of amount, such as the introduction of background technology, has the drug effect than both highers.
Beneficial effect：
The present invention realizes the recycling of the industrial productions such as glyphosate, Trimethyl phosphite recycling salt discarded object at the same time, subtracts
The discharge of waste is lacked.Drug effect higher is obtained at the same time, discarded object is switched to the NEW TYPE OF COMPOSITE pesticide of active ingredient, is had very high
Economic and social benefit.
Brief description of the drawings
Fig. 1 is a kind of preparation facilities of the present invention and its process flow diagram of the use of time.
Embodiment
Elaborate below to the embodiment of the present invention, the present embodiment is implemented premised on inventive technique scheme, provides
Detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1：
Phosphorus trichloride 277.4g, alchlor 377.4g are added in closed reaction kettle, nitrogen displacement is passed through and goes out air, then lead to
Enter 140g chloromethanes, when reaction 8 is small at 80 DEG C, be transferred to after completion of the reaction spare in three-necked flask.The ternary finished will be reacted
Complex compound is slowly heated to 140 DEG C, adds recycling salt 367.0g and aluminium powder 27.0g, and side border ring distills to obtain 197.0g contents
For 97% methyl dichloro phosphorus, yield 81.7%.
Embodiment 2：
Phosphorus trichloride 277.4g, alchlor 377.4g are added in closed reaction kettle, nitrogen displacement is passed through and goes out air, then lead to
Enter 140g chloromethanes, when reaction 8 is small at 80 DEG C, be transferred to after completion of the reaction spare in three-necked flask.The ternary finished will be reacted
Complex compound is slowly heated to 140 DEG C, adds analysis pure sodium chloride 367.0g and aluminium powder 27.0g, and side border ring distills to obtain
195.0g contents be 98% methyl dichloro phosphorus, yield 81.5%.
Embodiment 3：
Phosphorus trichloride 277.4g, alchlor 377.4g are added in closed reaction kettle, nitrogen displacement is passed through and goes out air, then lead to
Enter 150g chloromethanes, when reaction 6 is small at 80 DEG C, be transferred to after completion of the reaction spare in three-necked flask.The ternary finished will be reacted
Complex compound is slowly heated to 140 DEG C, adds recycling salt 414.1g and aluminium powder 36.0g, and side border ring distills to obtain 190.0g contents
For 99% methyl dichloro phosphorus, yield 80.4%.
In above three embodiment, recycling salt has carried out baking oven baking and milling apparatus grinding pretreatment, phosphorus trichloride, three
Aluminium chloride, chloromethanes are the progress complex reactions in pre-reactor, then in rear reaction vessel together with aluminium powder and recycling salt
Reduction reaction and solution complex reaction are carried out, the methyl dichloro phosphorus of generation further reacts generation glufosinate-ammonium.The glufosinate-ammonium with
Glyphosate one in recycling salt works to form the stronger composite pesticide of drug effect.
Pre-reactor employed in above three embodiment is Hastelloy reaction kettle, and vacuum is connected with pre-reactor
Device, agitating device, heating unit, rear reaction vessel are there-necked flask.
Claims (9)
1. a kind of method that recycling salt containing glyphosate, Trimethyl phosphite prepares glufosinate-ammonium composite pesticide, it is characterised in that：Tool
There is following preparation process：
（1）Commercial recovery salt containing glyphosate, Trimethyl phosphite is first pre-processed, place it in baking oven be dried 2 ~
5h, is then ground to the powder of 200 ~ 500 mesh in grinding container, spare；
（2）Alchlor and phosphorus trichloride are added in closed pre-reactor, chloromethanes is passed through after stirring evenly.
2. the material in reaction kettle is heated to 85 DEG C or so, it is anti-that phosphorus trichloride, alchlor and chloromethanes carry out ternary complexing
Should；Stop reaction after when reaction progress 6 ~ 12 is small, reaction solution is then transferred to subsequent reactions container；
（3）The solution system of ternary complexes in subsequent reactions container is heated to 140 DEG C ~ 160 DEG C of temperature, is added thereto
Aluminium powder and step（1）Described in recycling salt carry out solution complex reaction, reaction while, distills to obtain product methyl dichloro phosphorus；
（4）The methyl dichloro phosphorus of acquisition further reacts generation glufosinate-ammonium.
3. the method that the recycling salt as claimed in claim 1 containing glyphosate, Trimethyl phosphite prepares glufosinate-ammonium composite pesticide,
It is characterized in that：（2）With（3）The chemical equation of middle progress is as follows successively：
。
4. the method that the recycling salt as claimed in claim 1 containing glyphosate, Trimethyl phosphite prepares glufosinate-ammonium composite pesticide,
It is characterized in that：Analytical procedure（1）Middle sodium chloride content, and purified treatment is carried out, in the range of sodium chloride content is 90% ~ 98%
When, it is spare.
5. the method that the recycling salt as claimed in claim 1 containing glyphosate, Trimethyl phosphite prepares glufosinate-ammonium composite pesticide,
It is characterized in that：The step（2）In, the molar ratio of phosphorus trichloride and alchlor is 1：（1~3）, phosphorus trichloride and chloromethanes
Molar ratio be 1：（1~5）；
The step（3）In, the molar ratio of aluminium powder and the phosphorus trichloride is 1：（0.5~1.5）, it is described to recycle salt and the chlorine
The molar ratio for changing aluminium is 1：（1~3）.
6. the method that the recycling salt as claimed in claim 1 containing glyphosate, Trimethyl phosphite prepares glufosinate-ammonium composite pesticide,
It is characterized in that：Also there is preparation process（5）, reacted and generated with the Trimethyl phosphite in recycling salt using a small amount of phosphorus trichloride
Chloro phosphite ester, then carries out reaction generation methylisothiouronium methylphosphite dimethyl ester, and methylisothiouronium methylphosphite dimethyl ester is anti-with aldehyde, Cymag again
Amino nitrile should be generated, finally hydrolysis-ammonification, form glufosinate-ammonium.
7. a kind of recycling salt containing glyphosate, Trimethyl phosphite using described in claim 1 prepares glufosinate-ammonium composite pesticide
Device, it is characterised in that：Vacuum plant, agitating device, heating unit are connected with the pre-reactor.
8. device as claimed in claim 5, it is characterised in that：Pre-reactor is Hastelloy reaction kettle.
9. device as claimed in claim 5, it is characterised in that：Reaction vessel is there-necked flask afterwards.
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