CN108017671A - The method of phosphorous acid glycine synthesizing glyphosate - Google Patents
The method of phosphorous acid glycine synthesizing glyphosate Download PDFInfo
- Publication number
- CN108017671A CN108017671A CN201610991827.2A CN201610991827A CN108017671A CN 108017671 A CN108017671 A CN 108017671A CN 201610991827 A CN201610991827 A CN 201610991827A CN 108017671 A CN108017671 A CN 108017671A
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- calculation amount
- formaldehyde
- glycine
- phosphorous acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 88
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 88
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 70
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004471 Glycine Substances 0.000 title claims abstract description 35
- 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 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 98
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000543 intermediate Substances 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 43
- 238000004364 calculation method Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 5
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- ZEKANFGSDXODPD-UHFFFAOYSA-N glyphosate-isopropylammonium Chemical compound CC(C)N.OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 15
- 239000012267 brine Substances 0.000 abstract description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 10
- 239000011780 sodium chloride Substances 0.000 abstract description 8
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 abstract description 4
- -1 methylol glyphosate Chemical class 0.000 abstract description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- 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
- C07F9/38—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
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a kind of method or technique route for combining three kinds of Material synthesis glyphosates of phosphorous acid and glycine and formaldehyde.Compared with traditional IDA production glyphosate methods, it is not necessary to iminodiacetonitrile raw material, it is not necessary to prepare pmida intermediate or raw material；Compared with traditional glycine production glyphosate method, it is not necessary to triethylamine raw material, it is not necessary to dimethylphosphite raw material, it is not necessary to methanol feedstock.Prepared by this method is N methylol glyphosate intermediates or raw material, and the intermediate or raw material then are converted into glyphosate by the approach of oxydrolysis.Whole production process does not produce sodium chloride effluent brine, and production cost declines 20% or so compared to existing glyphosate production technique.
Description
First, technical field
The present invention relates to a kind of method or technique for combining three kinds of Material synthesis glyphosates of phosphorous acid and glycine and formaldehyde
Route.Compared with traditional IDA production glyphosate methods, it is not necessary to iminodiacetonitrile raw material, it is not necessary to prepare in pmida
Mesosome or raw material；Compared with traditional glycine production glyphosate method, it is not necessary to triethylamine raw material, it is not necessary to phosphorous acid diformazan
Ester raw material, it is not necessary to methanol feedstock.Prepared by this method is N- methylol glyphosate intermediates or raw material, then by the intermediate
Or raw material is converted into glyphosate by the approach of oxydrolysis.Whole production process does not produce sodium chloride effluent brine, production cost
Decline 20% or so compared to existing glyphosate production technique.
2nd, background technology
The method for combining three kinds of Material synthesis glyphosates of phosphorous acid and glycine and formaldehyde or dimethoxym ethane, is one unknown
The technology path of synthesizing glyphosate, yet there are no the open report of any data and document so far.Existing glyphosate work
Industry production line is two：1st, three kinds of Material synthesis glyphosates of glycine and dimethylphosphite and paraformaldehyde are combined, are prepared
Be N- methylol glyphosate dimethyl ester triethylamine salt intermediates, it is necessary to add substantial amounts of triethylamine and absolute methanol, it is therefore necessary
Auxiliary construction triethylamine retracting device and Methanol Recovery rectifying column are wanted, thereby increases the throwing of production cost and fixed assets
Money.Especially thus produce 1 ton of glyphosate and necessarily lead to more than 10 tons high concentration sodium chloride effluent brines, not only largely consume hydrochloric acid
With two kinds of raw materials of sodium hydroxide, cost of material is added, and be substantially increased because of the processing up to standard of waste water and abraum salt
Environmentally friendly cost, so as to significantly add the production cost of glyphosate.2nd, iminodiacetic acid and phosphorous acid and formaldehyde three are combined
Kind Material synthesis glyphosate, preparation is pmida intermediate or raw material, and pmida then is passed through oxygen or air or dioxygen
Water oxygen hydrolysis is glyphosate.Have to the production dress that auxiliary construction iminodiacetonitrile is hydrolyzed to iminodiacetic acid
Put, thereby increase production cost.Especially thus produce 1 ton of pmida intermediate or raw material necessarily lead to more than 10 tons it is highly concentrated
Sodium chloride effluent brine is spent, hydrochloric acid and sodium hydroxide raw material is not only largely consumed, adds cost of material, and because of waste water and abraum salt
Processing up to standard and be substantially increased environmentally friendly cost, so as to significantly add the production cost of glyphosate.
The technology path of method using the present invention or the present invention production glyphosate, it is not necessary to sodium hydroxide, triethylamine, first
The raw materials such as alcohol, iminodiacetonitrile, it is impossible to produce sodium chloride effluent brine, fundamentally thoroughly solve traditional glyphosate production
Technique largely produces high concentration sodium chloride effluent brine problem to be treated.Combine phosphorous acid and glycine and formaldehyde prepares N- hydroxyls
Methyl glyphosate intermediate or raw material, it is not necessary to consume the raw materials such as sodium hydroxide, it is also not possible to produce effluent brine, cost of material phase
To minimum, environment protection treating cost is also relatively minimum.And with glycine, synthesize N- methylol glyphosate intermediates or raw material
Yield is up to more than 90%.Therefore, have dropped compared to the cost (including wastewater treatment) for preparing pmida intermediate or raw material
30% or so.By N- methylol glyphosates be converted into glyphosate process and process units with pmida air oxidation is converted into
The process and process units of glyphosate are essentially identical, which does not produce effluent brine, only produce and can be directly used for preparing glyphosate
The mother liquor of aqua.And the two (N- methylols glyphosate is each converted into the reaction of glyphosate with pmida) all by-product formic acid,
The accessory substance and transforming principle of the two are essentially identical, and the conversion ratio of the two is also essentially identical with yield.The main distinction of the two exists
Sodium chloride effluent brine is not produced in production N- methylols glyphosate, and substantial amounts of sodium chloride effluent brine must be produced by producing pmida.
Therefore, method or technique route using the present invention prepares glyphosate, and whole production process does not produce the effluent brine for needing to administer.
To sum up, no matter being adjusted using which kind of standard, this method compares all traditional glyphosate production techniques, production cost
Decline 20% or so.
3rd, the content of the invention
The object of the present invention is to provide one kind to combine three kinds of Material synthesis glyphosate technicals of phosphorous acid and glycine and formaldehyde
And its one of the method or technique route of aqua, its feature be mainly generated in preparation process N- methylol glyphosate intermediates or
Raw material；The two of its feature are the reaction bottom together as synthesizing glyphosate three kinds of material combinations of phosphorous acid and glycine and formaldehyde
The purposes of thing；A kind of method for combining three kinds of Material synthesis N- methylol glyphosates of phosphorous acid and glycine and formaldehyde is provided, its
It is characterized in three kinds of material combinations of phosphorous acid and glycine and formaldehyde together as the reaction substrate for preparing N- methylol glyphosates
Purposes；A kind of method that glyphosate is prepared using glyphosine or N- methylols glyphosate as raw material is provided, it is characterized in that passing through oxygen
Change the approach of hydrolysis, add hydrogen peroxide in aqueous or add oxygen or air to glyphosine or N- methylols glyphosate into
Row oxydrolysis, generation glyphosate and by-product formic acid；If being converted into glyphosate by intermediate or raw material of glyphosine, it is special
Levy the methylphosphonic acid that accessory substance is coproduction.
A, it is a kind of three kinds of material combinations of phosphorous acid and glycine and formaldehyde together synthesizing glyphosate active compound and its aqua
Method, includes several steps of following sequence：
1st, the preparation of N- methylols glyphosate
The phosphorous acid and glycine of calculation amount are added into stirring reactor, or adds the glycine and first of calculation amount
Aldehyde, while the technical hydrochloric acid of calculation amount is added, start stirring, be slowly ramped to reflux temperature, the formaldehyde of calculation amount is slowly added dropwise
Aqueous solution, or the liquid phosphorous acid of calculation amount is slowly added dropwise, time for adding and insulated and stirred reaction time totally 6 it is small when；Cooling,
Under conditions of high vacuum and no more than 70 DEG C, hydrogen chloride and water are steamed as best one can, distillation substrate is N- methylol glyphosates
Product；
2nd, the preparation of glyphosate
The water that calculation amount is added into above-mentioned distillation substrate is dissolved, and the material of dissolving is sent into stirring-type autoclave pressure
In, the iron-molybdic catalyst of the activated carbon catalyst for adding calculation amount or the prepn. of formaldehyde by oxidation of methanol for adding calculation amount, is warming up to 106
More than DEG C, the hydrogen peroxide of calculation amount is slowly added dropwise or continuously adds oxygen or air, time for adding and be stirred at reflux anti-
When common 4-6 is small between seasonable；Cooling, crystallization, filtering, filter cake is glyphosate technicals and activated carbon catalyst or iron-molybdic catalyst
Mixture, filtrated stock can be directly as the solvents for preparing gyphosate solution product；Mixed with the isopropylamine of calculation amount with filter cake
Glyphosate technicals in thing carry out neutralization reaction, and are filtered, and the filter cake of the secondary filter is the activated carbon catalyst added
Or iron-molybdic catalyst, recyclable to apply mechanically, which is 40% glyphosate isopropylamine salt water solution product.
B, a kind of method that three kinds of material combinations of phosphorous acid and glycine and formaldehyde are synthesized N- methylol glyphosates together,
Several steps including following sequence：
The glycine and formaldehyde and hydrochloric acid solution of calculation amount are added into stirring reactor, is slowly ramped to 60 DEG C,
When stirring reaction 2 is small, more than 106 DEG C are continuously heating to, the liquid phosphorous acid of calculation amount is slowly added dropwise at reflux, is added dropwise
Time and insulated and stirred reaction time totally 6 it is small when；Cooling, under conditions of high vacuum and no more than 70 DEG C, is evaporated net anti-as far as possible
The hydrogen chloride and water in device are answered, distillation substrate is N- methylol glyphosate products.
As long as combination three kinds of raw materials of phosphorous acid and glycine and formaldehyde prepare the technology path of N- methylol glyphosates, must
Right by-product glyphosine.Therefore, industrial production needs to develop the new process that glyphosine is converted into glyphosate, sweet for reducing grass
The production cost of phosphine has great importance.
C, a kind of method for glyphosine being converted into glyphosate, includes several steps of following sequence：
Into stirring-type autoclave pressure put into calculation amount glyphosine and water, while put into calculation amount activated carbon catalyst or
The iron-molybdic catalyst of the prepn. of formaldehyde by oxidation of methanol of calculation amount is put into, is slowly ramped to more than 106 DEG C, the double of calculation amount are slowly added dropwise
Oxygen water, or when continuously addition oxygen or air, time for adding and the common 4-6 of insulated and stirred reaction small；Cooling, crystallization, mistake
Filter, filter cake are glyphosate technicals and activated carbon catalyst or the mixture of iron-molybdic catalyst, with isopropylamine and water by the mixture
In glyphosate technicals gyphosate solution product is made, while be separated by filtration recycling activated carbon catalyst or iron-molybdic catalyst, mistake
The methylphosphonic acid containing coproduction in mother liquor is filtered, can be directly as the solvent for preparing gyphosate solution.
4th, specific embodiment
Embodiment 1
Acidproof electric stirring reactor is selected, configures condenser pipe and thermometer, throws the glycine that mass content is 99%
30 grams, 32.8 grams of the phosphorous acid that mass content is 99% is thrown, 228 grams of the hydrochloric acid that mass content is 30% is thrown, starts stirring, slowly
106 DEG C of reflux are warming up to, start that 64 grams of the formaldehyde that mass content is 37% is added dropwise, 5 drip off when small, continue insulated and stirred reaction 1
Hour；Then 50 DEG C or so are cooled to, opens high vacuum, controls below temperature 70 C, steams the hydrogen chloride in reactor as far as possible
And water, distillation substrate is N- methylol glyphosates, containing 9% or so glyphosine；Again plus bottom is distilled in 20-40 grams of pure water, dissolving
The aqueous solution is sent into stirring-type autoclave pressure by thing to measure transparent aqueous solution clearly, adds 30 grams or so of activated carbon catalyst, or
Person adds 15 grams or so of the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol, is slowly ramped to more than 106 DEG C, control temperature is at 118 DEG C
Hereinafter, start that 64 grams -91 grams of the hydrogen peroxide that content is 30% is added dropwise, or continuously add oxygen or air, when 4-5 is small
Drip off, when continuation insulated and stirred reaction 1-2 is small, then cools down, crystallize, filtering, filter cake is that glyphosate technicals and activated carbon are urged
The mixture of agent or iron-molybdic catalyst, glyphosate technicals content separated with catalyst is 97%, with glycine, glyphosate
The yield of active compound is more than 80%；Glyphosine in N- methylol glyphosates has been converted into glyphosate, and glyphosine conversion ratio is
98%.
Embodiment 2
Acidproof electric stirring reactor is selected, by the glyphosate technicals and activated carbon catalyst of 1 output of above-described embodiment
Mixture is put into the reactor, adds 109 grams of pure water, starts stirring, and the isopropylamine that mass content is 99% is added dropwise at normal temperatures
18.9 grams, continue after dripping off stirring measured clearly to solution it is transparent, filtering, filter cake for add activated carbon catalyst, recovery, mistake
Filter the glyphosate isopropylamine salt water solution product that mother liquor is 40%.
Embodiment 3
Acidproof stirring-type autoclave pressure, supporting installation condenser and the measuring tank and high vacuum system that are added dropwise are selected,
Under conditions of open normal pressure, 30 kilograms of the glycine that mass concentration is 99% is added, adds the phosphorous acid that mass concentration is 99%
32.8 kilograms, add 30% 228 kilograms of technical hydrochloric acid；Start stirring, be slowly ramped to 106 DEG C of reflux, start that quality is added dropwise
Concentration is 37% 64 kilograms of formalin, and 5 drip off when small, continue to keep the temperature back flow reaction 1 it is small when, be then cooled to 50 DEG C, close
Blow valve is closed, opens vacuum valve, controls below temperature 70 C, steams hydrogen chloride and water as far as possible；High vacuum distillation finishes, and unlatching is put
Empty valve, closes vacuum valve, adds 20-40 kilograms of pure water, dissolving distillation substrate is limpid transparent solution, adds activated carbon catalysis
30 kilograms of agent, or 15 kilograms of the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol is added, more than 106 DEG C are slowly ramped to, is controlled
Less than 118 DEG C, blow valve is closed, starts that 64-91 kilograms of the hydrogen peroxide that mass concentration is 30% is added dropwise, or continuously add
Enter oxygen or air, dripped off when 3-4 is small, when continuation insulated and stirred reaction 2-3 is small, is cooled to 60 DEG C or so, opens blow valve, after
It is continuous to be cooled to less than 10 DEG C, crystallize two hours, filtering, filter cake is glyphosate technicals and activated carbon catalyst or iron-molybdic catalyst
Mixture, the glyphosate technicals content after being separated with catalyst are 97%, yield 87%.
Embodiment 4
Acidproof electric stirring reactor is selected, 30 grams of the glycine that input mass concentration is 99%, puts into mass concentration
For 37% 64 grams of formaldehyde, 228 grams of the technical hydrochloric acid that input mass concentration is 31%, starts stirring, is slowly warming up to 106 DEG C and returns
Stream, starts that 37 grams of the liquid phosphorous acid that mass concentration is 90% is added dropwise, and 5 drip off when small, when continuation insulated and stirred reaction 1 is small, so
After be cooled to 50 DEG C or so, open high vacuum distillation, control vapo(u)rizing temperature is no more than 70 DEG C, is evaporated as far as possible in the net reactor
Hydrogen chloride and water, distillation substrate is N- methylol glyphosates, content 84%, containing 7% or so glyphosine, with glycine
Meter, the yield of N- methylol glyphosates is 90% or so, and the yield of by-product glyphosine is 5% or so.
Embodiment 5
The N- methylols glyphosate of 4 output of above-described embodiment is dissolved as limpid transparent solution with 20 grams of water, is added resistance to
In the stirring-type autoclave pressure reactor of acid, it is 2 or so with alkali tune solution Ph values, adds 0.27 gram of sodium tungstate, be slowly warming up to 106
DEG C, blow valve is closed, 64-91 grams of the hydrogen peroxide that mass concentration is 30% is added dropwise, control 4 drips off when small, and it is anti-to continue insulated and stirred
When answering 1-2 small, 40 DEG C are then cooled to, opens blow valve, the ferrous sulfate aqueous solution that mass concentration is 10% is added dropwise at 40 DEG C
15.5 grams, control 4 drips off when small, continue to stir insulation reaction 2 it is small when, cooling, is cooled to less than 10 DEG C, crystallize 2 it is small when, mistake
Filter, filter cake is glyphosate technicals, drying, and glyphosate content is 95%, and with glycine, glyphosate technicals yield is 76%,
Filtrated stock can be directly as the solvent for preparing gyphosate solution.
Embodiment 6
Choose an acidproof stirring-type autoclave pressure reactor, the glyphosine aqueous solution 300 that input mass concentration is 20%
Gram, 30 grams of activated carbon catalyst, or 15 grams of the iron-molybdic catalyst of input prepn. of formaldehyde by oxidation of methanol are put into, starts stirring, slowly
106 DEG C are warming up to, closes blow valve, mass concentration is added dropwise and is 30% 31 grams of hydrogen peroxide, or continually adds oxygen or sky
Gas, control time for adding for 4 it is small when, continue to stir insulation reaction 1-2 it is small when, be then turned on blow valve, be cooled to less than 10 DEG C,
Crystallize 2 it is small when, filtering, filter cake be glyphosate technicals and the mixture of activated carbon catalyst or iron-molybdic catalyst, is divided with activated carbon
From glyphosate technicals content be 97%, the yields of glyphosate technicals is more than 90%, and it is female that the methylphosphonic acid of coproduction is dissolved in filtering
In liquid, the recyclable raw material as methylphosphonic acid diester product.
Embodiment 7,
Select acidproof stirring-type autoclave pressure reactor, the N- methylol glyphosate aqueous solutions that input mass concentration is 50%
80 grams, 30 grams of the activated carbon catalyst of input KOH activation, or 15 grams of the iron-molybdic catalyst of input prepn. of formaldehyde by oxidation of methanol, open
Dynamic stirring, is slowly warming up to more than 130 DEG C, and control temperature is no more than 150 DEG C, starts that the hydrogen peroxide that mass concentration is 30% is added dropwise
64-91 grams, or oxygen or air are continuously added, when control time for adding 5 is small, when continuation insulated and stirred reaction 1 is small；
Room temperature is cooled to, crystallization, filtering, filter cake is glyphosate technicals and activated carbon catalyst or the mixture of iron-molybdic catalyst, with urging
The content of the separated glyphosate technicals of agent is 95%, and the yield of glyphosate technicals is 80%.
Embodiment 8,
Acidproof electric stirring reactor is selected, throws 100 grams of the N- methylols glyphosate that mass concentration is 50%, with alkali tune
Ph values are 2, add 0.17 gram of sodium tungstate, control temperature 60 C, and 34 grams of the hydrogen peroxide that mass concentration is 30%, time for adding is added dropwise
3 it is small when, when the insulated and stirred reaction time 3 is small, adds the iron-molybdic catalyst of 5 grams of prepn. of formaldehyde by oxidation of methanol, then slowly heat up
To 106 DEG C -118 DEG C, continue to be stirred at reflux reaction 3 it is small when；40 DEG C are cooled to, 10% 4 grams of ferrous sulfate aqueous solution is added dropwise, is dripped
Add time 2 h, insulation reaction time 2 h；Less than 10 DEG C, when crystallization 2 is small are cooled to, is filtered, is separated, drying, obtains careless sweet
35.7 grams of phosphine active compound, content 95%.
Claims (7)
1. a kind of combination phosphorous acid and the method or technique of three kinds of Material synthesis glyphosate technicals of glycine and formaldehyde and its aqua
One of route, its feature is that N- methylol glyphosate intermediates or raw material are mainly generated in preparation process；The two of its feature are handles
Purposes of the three kinds of material combinations of phosphorous acid and glycine and formaldehyde together as the reaction substrate of synthesizing glyphosate.
A kind of 2. method using three kinds of Material synthesis N- methylol glyphosates of phosphorous acid and glycine and formaldehyde, it is characterized in that handle
Purposes of the three kinds of material combinations of phosphorous acid and glycine and formaldehyde together as the reaction substrate for preparing N- methylol glyphosates.
A kind of 3. method that glyphosate is prepared as intermediate or raw material using glyphosine or N- methylols glyphosate, it is characterized in that in water
Hydrogen peroxide or addition oxygen are added in solution or air carries out oxydrolysis and is converted into glyphosate；Using glyphosine as intermediate
Or raw material prepares glyphosate, its feature accessory substance is the methylphosphonic acid of coproduction.
4. it is a kind of three kinds of material combinations of phosphorous acid and glycine and formaldehyde together synthesizing glyphosate active compound and its method for aqua,
Several steps including following sequence：
1st, the preparation of N- methylols glyphosate
The phosphorous acid and glycine of calculation amount are added into stirring reactor, or adds the glycine and formaldehyde of calculation amount,
The technical hydrochloric acid of calculation amount is added at the same time, starts stirring, is slowly ramped to reflux temperature, and the formaldehyde that calculation amount is slowly added dropwise is water-soluble
Liquid, or the liquid phosphorous acid of calculation amount is slowly added dropwise, time for adding and insulated and stirred reaction time totally 6 it is small when；Cooling, in height
Vacuum and no more than 70 DEG C under conditions of, steam hydrogen chloride and water as best one can, distillation substrate is N- methylol glyphosate products；
2nd, the preparation of glyphosate
The water that calculation amount is added into above-mentioned distillation substrate is dissolved, and the material of dissolving is sent into stirring-type autoclave pressure, is added
Enter calculation amount activated carbon catalyst or add calculation amount prepn. of formaldehyde by oxidation of methanol iron-molybdic catalyst, be warming up to 106 DEG C with
On, the hydrogen peroxide of calculation amount is slowly added dropwise or continuously adds oxygen or air, time for adding and when being stirred at reflux reaction
Between common 4-6 it is small when；Cooling, crystallization, filtering, filter cake are the mixing of glyphosate technicals and activated carbon catalyst or iron-molybdic catalyst
Thing, filtrated stock can be directly as the solvents for preparing gyphosate solution product；With in the isopropylamine and filter cake mixture of calculation amount
Glyphosate technicals carry out neutralization reaction, and filtered, the filter cake of the secondary filter is the activated carbon catalyst or iron that add
Molybdenum catalyst, recyclable to apply mechanically, which is 40% glyphosate isopropylamine salt water solution product.
5. a kind of method that three kinds of material combinations of phosphorous acid and glycine and formaldehyde are synthesized N- methylol glyphosates together, including
Several steps of following sequence：
The glycine and formaldehyde and hydrochloric acid solution of calculation amount are added into stirring reactor, is slowly ramped to 60 DEG C, stirring
React 2 it is small when, be continuously heating to more than 106 DEG C, at reflux slowly be added dropwise calculation amount liquid phosphorous acid, time for adding
With the insulated and stirred reaction time totally 6 it is small when；Cooling, under conditions of high vacuum and no more than 70 DEG C, is evaporated net reactor as far as possible
In hydrogen chloride and water, distillation substrate be N- methylol glyphosate products.
6. a kind of method for glyphosine being converted into glyphosate, includes several steps of following sequence：
The glyphosine and water of calculation amount are put into stirring-type autoclave pressure, while puts into the activated carbon catalyst or input of calculation amount
The iron-molybdic catalyst of the prepn. of formaldehyde by oxidation of methanol of calculation amount, is slowly ramped to more than 106 DEG C, and the dioxygen of calculation amount is slowly added dropwise
Water, or when continuously addition oxygen or air, time for adding and the common 4-6 of insulated and stirred reaction small；Cooling, crystallization, filtering,
Filter cake is glyphosate technicals and activated carbon catalyst or the mixture of iron-molybdic catalyst, with isopropylamine and water by the mixture
Gyphosate solution product is made in glyphosate technicals, while is separated by filtration recycling activated carbon catalyst or iron-molybdic catalyst, and filtering is female
Methylphosphonic acid containing coproduction in liquid, can be directly as the solvent for preparing gyphosate solution.
7.N- methylols glyphosate prepares glyphosate as a kind of intermediate for preparing glyphosate technicals and its aqua or conduct
The purposes of the raw material of active compound and its aqua.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610991827.2A CN108017671A (en) | 2016-11-04 | 2016-11-04 | The method of phosphorous acid glycine synthesizing glyphosate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610991827.2A CN108017671A (en) | 2016-11-04 | 2016-11-04 | The method of phosphorous acid glycine synthesizing glyphosate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108017671A true CN108017671A (en) | 2018-05-11 |
Family
ID=62084791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610991827.2A Pending CN108017671A (en) | 2016-11-04 | 2016-11-04 | The method of phosphorous acid glycine synthesizing glyphosate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108017671A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333519A (en) * | 2020-03-11 | 2020-06-26 | 陈兴华 | Comprehensive treatment and resource recycling method for glyphosate mother liquor |
-
2016
- 2016-11-04 CN CN201610991827.2A patent/CN108017671A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333519A (en) * | 2020-03-11 | 2020-06-26 | 陈兴华 | Comprehensive treatment and resource recycling method for glyphosate mother liquor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262394B (en) | The environment friendly clean producing method of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid and device | |
| CN102875594B (en) | Continuous synthesis technique of hydroxyethylidenediphosphonic acid | |
| CN101709064A (en) | Process for synthesizing glyphosate | |
| CN104177250A (en) | Process for producing glycollic acid from methyl glycolate | |
| CN114085244B (en) | Preparation method of 4- (hydroxymethyl phosphono) -2-carbonyl butyric acid | |
| CN109438182A (en) | A kind of production system and its production technology of 99 grades of pentaerythrites | |
| CN104944398B (en) | Glyphosate mother solution recoverying and utilizing method | |
| CN100577670C (en) | Method for producing phosphorus compound having phosphate-phosphonate bond | |
| CN101824051B (en) | Lycopene intermediate 1,3,6,10-4-pentadienyl phosphonate as well as preparation method and application thereof | |
| CN105753899A (en) | Recovery method of rectification residual liquid of dimethyl phosphite | |
| CN108017671A (en) | The method of phosphorous acid glycine synthesizing glyphosate | |
| CN106397481A (en) | Synthesis method of triethyl phosphonoacetate | |
| CN103374028A (en) | Preparation method of triethyl phosphate | |
| CN101157046A (en) | A technique for preparing cobalt manganese bromine catalyst | |
| CN101462943B (en) | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate | |
| CN103554180B (en) | The preparation method of glyphosate | |
| CN103819505B (en) | A kind of method improving PMIDA yield | |
| CN101824049A (en) | Application of phosphine or hypophosphite or phosphate in preparation of glyphosate | |
| CN103554182B (en) | Prepare the method for glyphosate | |
| CN114853808A (en) | Method and device for producing glyphosate by glycine method | |
| CN109942626A (en) | A kind of synthetic method of glyphosate | |
| CN110862413A (en) | Glyphosate synthesis process and device | |
| CN104098602B (en) | A kind of energy-saving clean production method of PMIDA | |
| CN106632470B (en) | The synthesis of N- methylol glyphosate or its ester and its method for preparing glyphosate | |
| CN102766160A (en) | Novel process for preparing glyphosate by utilizing glycine method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180511 |