CN108690071A - A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material - Google Patents
A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material Download PDFInfo
- Publication number
- CN108690071A CN108690071A CN201810362616.1A CN201810362616A CN108690071A CN 108690071 A CN108690071 A CN 108690071A CN 201810362616 A CN201810362616 A CN 201810362616A CN 108690071 A CN108690071 A CN 108690071A
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- mixed solution
- raw material
- methanol
- triethylamine
- 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 79
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 79
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000002994 raw material Substances 0.000 title claims abstract description 31
- 230000032050 esterification Effects 0.000 title claims abstract description 25
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 title claims description 22
- 229940106681 chloroacetic acid Drugs 0.000 title claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 180
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 81
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 27
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 25
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 23
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 118
- 239000011259 mixed solution Substances 0.000 claims description 61
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 15
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical class Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000011017 operating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 3
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract description 46
- 239000004471 Glycine Substances 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 13
- 239000000543 intermediate Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- -1 alkyl phosphite Chemical compound 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- WBTIFBJEYFLFFW-UHFFFAOYSA-N 2-(hydroxymethylazaniumyl)acetate Chemical compound OCNCC(O)=O WBTIFBJEYFLFFW-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 6
- 229940071206 hydroxymethylglycinate Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 5
- 235000009508 confectionery Nutrition 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 241000254173 Coleoptera Species 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002373 hemiacetals Chemical class 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- YYPMRNCXTSBAHH-UHFFFAOYSA-N CP(O)(O)(O)C.NCC(=O)O Chemical compound CP(O)(O)(O)C.NCC(=O)O YYPMRNCXTSBAHH-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000002333 glycines Chemical class 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 description 1
- AHHJDIFZRLYOSS-UHFFFAOYSA-N 2-aminoacetic acid;formaldehyde Chemical compound O=C.NCC(O)=O AHHJDIFZRLYOSS-UHFFFAOYSA-N 0.000 description 1
- OQHGAMHDVWVWDJ-UHFFFAOYSA-N P(=O)(OC)(OC)O.NCC(=O)O Chemical compound P(=O)(OC)(OC)O.NCC(=O)O OQHGAMHDVWVWDJ-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- REHUGJYJIZPQAV-UHFFFAOYSA-N formaldehyde;methanol Chemical compound OC.O=C REHUGJYJIZPQAV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000013517 stratification Methods 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
It is a kind of using monoxone as the technique of raw material alkyl esterification method synthesizing glyphosate, belong to glyphosate synthesis technical field.Its feature is:With monoxone, formaldehyde(Paraformaldehyde), methanol, ammonia be raw material glyphosate precursor compound is obtained by the reaction, obtaining solid glyphosate active compound through over-churning, acidolysis, crystallization.The process for synthesizing glyphosate, directly as glyphosate production raw material, need not evade the process that glycine production link generates industrial wastewater using monoxone using glycine as raw material;Glyphosate synthesis flow is simplified, step is few, flow is short, and cost of material and operating cost are low;The yield of glyphosate synthesis byproduct in process object is reduced, and glyphosate yield gets a promotion 0.6%.
Description
Technical field
It is specially a kind of using monoxone as the alkyl esterification method of starting point raw material grass the invention belongs to glyphosate production technical field
Sweet phosphine synthetic method.
Background technology
Glyphosate is a kind of the efficient, less toxic of inner sucting conduction type, wide spectrum, steriland herbicide, and mainstream production method has 2
Kind, first, with the production method that iminodiacetic acid (IDA) is raw material, second is that using glycine, alkyl phosphite as raw material
Production method.Foreign corporation based on Monsanto is substantially all to be produced using iminodiacetic acid (salt) acid system.The glyphosate in China
Production is started in the eighties in last century.1987, it was main former that Shenyang Chemical Engineering Inst, which releases with glycine, dimethylphosphite,
The glycine of material-alkyl esterification method synthesizing glyphosate technique, the method process stabilizing, yield are fine, and solid glyphosate can be made, so
Industrialization is realized quickly, and is quickly grown.But this method is not perfect in every way, it is well known that glycine and glyphosate
Production process waste water yield is big, intractability is big, processing cost is high, it may be said that China is supplying glyphosate products for the world
During paid huge resource and environmentally friendly cost.
China is glyphosate major producing country, and volume of production and marketing accounts for 60% or more the whole world.And glycine-alkyl esterification method in occupation of
Leading position in domestic glyphosate industry, account for about national glyphosate production capacity 75%, actual production 80%.Therefore, constantly improve
Alkyl esterification method glyphosate production technique has extremely strong realistic meaning for China.The present invention also exactly subtracts energy-saving
Row, ecological ideas develop under this background the achievement for carrying out pilot development.
Alkyl esterification method and glycine-dimethylphosphite process introduction:Alkyl esterification method process for synthesizing glyphosate master at present
To be glycine-dimethyl phosphate method, detailed process is:Make catalyst with triethylamine, paraformaldehyde solves in solvent methanol
Consor carries out condensation reaction at hemiacetal, then with glycine, then is esterified with dimethylphosphite, and after through hydrolysis, precipitation
Agent, depickling, crystallization, separation, drying obtain solid glyphosate.The route uses glycine as raw material, has the following disadvantages:1,
The production of raw material glycine(Synthesis, refines separation)Will produce in the process a large amount of ammonium chlorides of a large amount of waste water, especially by-product and
Its mother liquor, about 0.55 ton/ton of quantity, with the big spy of high organic content, ammonia-nitrogen content height, difficult for biological degradation, difficulty of governance
Property.2, catalyst formaldehyde used in glycine production process cannot recycle use.Add formaldehyde in glycine building-up process(Or
Methenamine)As catalyst, in waste liquid and glycine system, the formaldehyde in glycine needs residues of formaldehyde after the completion of reaction
It is removed by refined, wastewater flow rate is big;Formaldehyde in waste liquid needs input great amount of cost to be handled.In addition, the synthesis road
In line, synthesized from glycine again to glyphosate synthesis, entire process route is long, and equipment investment is big, and operating procedure is more, loss of material
Greatly, side reaction is more, and raw material availability is low, and energy consumption is high, and operating cost is high.
CN102898467A discloses a kind of method of monoxone one pot process glyphosate, but there are two for this method
Prodigious disadvantage, first, it generates hydramine using solid polyformaldehyde and methanol, ammonia reaction, due to the use of solid polyformaldehyde
Reaction, slow, the halfway problem of depolymerization that there are depolymerization speed could be participated in after needing first depolymerization, thus changes step and generates alcohol ammonia
The yield of positive reaction is low.Second is that the experimental program in the patent document is in glyphosate precursor hydroxymethylglycinate building-up process,
Addition reaction(The so-called reaction for generating glycine formaldehyde condensation products i.e. in CN102898467A files)After the completion and then
Dimethylphosphite is added and carries out esterification, this operation is the same with traditional glycine method synthesis technology scheme, recognizes in industry
It can not be excessively high for this step addition reaction temperature in alkyl esterification method glyphosate method(Higher than 43 DEG C), otherwise can lead to the sweet ammonia of methylol
Sour intermediate occurs side reaction and so that active principle is reduced and then reduce the yield of glyphosate, thus when reaction finishes cool down rapidly
To 40 DEG C or so add dimethylphosphite or by be slowly directly added into dimethylphosphite control temperature it is not excessively high.
Invention content
This new departure solves problem above by innovation emphasis.In this new departure, subtract first, improving temperature by regulation and control
The small depolymerization time improves depolymerization effect;Solid polyformaldehyde participation is substituted especially with the methanol solution of anhydrous formaldehyde
Reaction, active constituent are hemiacetal and formaldehyde, active feature high, reaction speed is fast, reaction is thorough, therefore the throwing of aldehyde
Enter less, react also more thoroughly, reduces discharge and the wastewater treatment load of formaldehyde.Meanwhile generating the high income of alcohol ammonia, the richness of ammonia
Remaining excess reduces, and realizes and no longer generates ammonium chloride and its mother liquor.Moreover, because of the raising of carbinolamine step reaction yield, grass
The final yield of sweet phosphine also improves.Second is that by the research to reaction mechanism, we thinks traditional glycine method synthesizing glyphosate
Above-mentioned addition temperature control method and unreasonable, the glyphosate yield of this operating method is low.Before this new departure hydroxymethylglycinate
New synthetic schemes is used in body building-up process, based on the new knowledge to reaction mechanism, using new temperature control measure:Reaction 50~
80 minutes to material system by muddy bleach after, be rapidly heated to 50-56 DEG C, stirring, heat preservation 10s-20min, it is then fast again
Speed is cooled to 40 DEG C or so, enters back into and the dimethylphosphite i.e. operation of temperature control is added in next step, and the operation of this temperature control is greatly decreased
The generation of side reaction, it is ensured that the yield of glyphosate improves on year-on-year basis.Third, negative pressure is de- after this new departure obtains mixed solution D
Except partial solvent methanol, then it is aided with cooling, two kinds of measure effects are lower to be precipitated hydrochloric acid triethylammonium salts crystal, then reuses removing
Methanol washing, purifying triethylammonium salts crystal.Hydrochloric acid triethylammonium salts crystal is precipitated fully, and temperature condition is not also harsh.
The present invention provides a kind of using monoxone as the synthetic method of the alkyl esterification method glyphosate of starting material(Abbreviation chloroethene
Acid-dimethyl phosphate method).Present invention solves the technical problem that have at 2 points, when by monoxone synthesize the technique of glycine with
The process integration of glycine and dimethylphosphite synthesizing glyphosate is a technique, does not use glycine and is given birth to as glyphosate
Produce raw material;Second is that according to catalyst in reaction process and the material characteristic of intermediate, is reduced and reacted by specific process
Side reaction in the process improves raw material availability, improves the yield of product glyphosate.
Technical solution
The synthetic method and implementation steps of glyphosate provided by the present invention are as follows:
Using monoxone as raw material, make catalyst with methanol as solvent, with triethylamine, control temperature reacts 8 at 30~65 DEG C~
30 minutes, triethylamine increased chloroethene acid activity, and synthesis obtains using monoxone triethylamine salt and its resets isomers as active ingredient
Mixed solution A.
In above-mentioned steps 1, the molar ratio of material is:Monoxone:Triethylamine:Methanol=1:0.9~1.6:6~8.
0~15min of reaction is carried out at 10~50 DEG C as raw material using paraformaldehyde, methanol, or no water beetle that directly comes into operation
The methanol solution of aldehyde keeps the temperature 0~5min at 10~40 DEG C, then is passed through ammonia, and 20~45min, synthesis are reacted at 0~40 DEG C
It obtains using carbinolamine, dimethanolamine as the mixed solution B of active ingredient.
In above-mentioned steps 2, the molar ratio of material is:Formaldehyde:Methanol:Ammonia=1:1~3:0.45~0.6.
Preferably, in above-mentioned steps 2, formaldehyde source selects the methanol solution of anhydrous formaldehyde.
Preferably, in above-mentioned steps 2, when leading to ammonia reaction, control system pressure is positive pressure, to reduce the volatilization of material, is promoted
It is carried out into positive reaction.
The mixed solution B of above-mentioned steps 2 is added in the mixed solution A of above-mentioned steps 1, reacts 10 at 0~30 DEG C
It~30 minutes, after liquid-phase chromatographic analysis confirms that monoxone peak disappears, maintains the temperature at 0~30 DEG C and is added into system into three second
Amine adjusts pH value between 7.0~9.0.
40~45 DEG C are then heated to, is at the same time gradually added into a small amount of paraformaldehyde several times or continuously(Or nothing
The methanol solution of water beetle aldehyde), react 50~80 minutes, until material system is by muddy bleach, it is hydroxyl first to obtain active ingredient
The intermediates such as base glycine(Glyphosate precursor)Mixed solution C.Then it is rapidly heated to 50-56 DEG C, stirring, heat preservation 10s-
Then 20min is cooled to rapidly 40 DEG C or so again, enter back into and the dimethylphosphite i.e. operation of temperature control is added in next step.
In above-mentioned steps 3, the molar ratio of material is:Monoxone:Triethylamine:Paraformaldehyde:Dimethylphosphite=
1:0.1~1.1:0~1:1~1.4.
Preferably, in above-mentioned steps 3 formaldehyde source select anhydrous formaldehyde methanol solution.
Preferably, in above-mentioned steps 3, when reaction, control system pressure is positive pressure, to reduce the volatilization of material, is promoted just
Reaction carries out.
Preferably, triethylamine is added in step 3 adjusts pH value between 7.5~8.5.
Think that this step addition reaction temperature can not be excessively high in alkyl esterification method glyphosate method, is higher than in this step, in industry
45 DEG C can cause hydroxymethylglycinate intermediate that side reaction occurs and so that active principle is reduced and then reduce the yield of glyphosate, because
And it reacts the when of finishing and takes the rapid operation scheme for being cooled to 40 DEG C or so.And in the present solution, based on recognizing the new of reaction mechanism
Know, using new temperature control measure:Reaction 50~80 minutes to material system by muddy bleach after, be rapidly heated to 50-56 DEG C,
Stirring, heat preservation 10s-20min, promote hemiacetal remaining in elimination system, formaldehyde, are then cooled to 40 DEG C or so rapidly again,
Entering the operation that dimethylphosphite, that is, temperature control is added in next step.
Into the mixed solution C of above-mentioned steps 3, a certain amount of dimethylphosphite is added, is warming up to 50~55 DEG C, heat preservation
A small amount of triethylamine is added after a period of time with regulation system pH value to 7.0~8.8.Then again at 50~55 DEG C reaction 60~
110 minutes, it was the organic phosphines intermediates such as N- dimethyl esters (phosphonomethyl) glycines to obtain main component(Glyphosate precursor)'s
Mixed solution D.
Preferably, in above-mentioned steps 4, the time for adding triethylamine is heat preservation 10min or so, and aforementioned pH value range is 7.2
~8.0.It is further preferred that after adding triethylamine adjusting pH, then add a small amount of dimethylphosphite.
In above-mentioned steps 4, the molar ratio of material is:Monoxone:Triethylamine:Dimethylphosphite=1:0.01-0.1
:1~1.4.
Mixed solution D is squeezed into reactor 4, in 10~65 DEG C and vacuum(Negative pressure)Lower removing partial solvent methanol, control
Time 0-60min processed is subsequently cooled to 0 ~ 20 DEG C, and hydrochloric acid triethylammonium salts crystal is precipitated.
Vacuum(Negative pressure)It is back to use step 1 and step 2 after the condensed device condensation of the methanol of removing, or described for cleaning
Hydrochloric acid triethylammonium salts crystal.
Hydrochloric acid triethylammonium salts crystal will be precipitated using measures such as filtering, centrifugations and supernatant detaches, and using a small amount of
The methanol or triethylamine of fresh methanol or aforementioned condensing recovery wash the hydrochloric acid triethylammonium salts crystal isolated, and obtain three
Ethylamine hydrochloride.Triethylamine hydrochloride is neutralized using liquid caustic soda, triethylamine can be obtained through stratification, is back to use aforementioned step
Rapid 1 and step 4.
When being washed using the methanol or fresh methanol of aforementioned condensing recovery, cleaning solution is merged into isolated
In supernatant, mixed solution E is obtained.When being washed using triethylamine, cleaning solution is subjected to flash separation, flash separation goes out
Gas phase be triethylamine, be back to glyphosate synthesis after condensation;Remaining liquid is phosphorus-containing matter after flash distillation, is merged into
In isolated supernatant, mixed solution E is obtained.
Mixed solution E is refined, dry through acidolysis, crystallization, washing again, obtains solid glyphosate active compound.
In technical solution of the present invention, the various total molar ratios of material are during glyphosate synthesis:Monoxone:Poly first
Aldehyde:Ammonia:Dimethylphosphite:Triethylamine:Methanol=1:2~3.4:1~1.2:1~1.4:1.1~2.25:8~14.
Gained glyphosate technicals are analyzed according to GB 12686-2004, and 95.0% or more glyphosate content, formaldehyde etc. is residual
It stays object qualified, reaches high-class product standard.Glyphosate technicals yield in terms of monoxone reaches 75.2% or more, in active compound and mother liquor
Glyphosate adds up to yield to reach 80% or more, and the yield of year-on-year glycine-dimethylphosphite technique also promotes 0.6% or so.
Technical scheme of the present invention has the advantages that
1, the monoxone-dimethyl phosphate method process for synthesizing glyphosate method is using monoxone as starting material, it is no longer necessary to
Using glycine as raw material, evades glycine production link and has led to the problem of a large amount of industrial wastewaters, reduced the generation of waste water,
Especially production process no longer generates ammonium chloride and its mother liquor.
2, glyphosate synthesis flow has been simplified, low equipment investment reduces cost of material and operating cost, production cost tool
It is advantageous.
3, thrown formaldehyde can further participate in reaction in step 3 in step 2, be fully used, relative to sweet ammonia
Its catalyst formaldehyde in sour production process(Or paraformaldehyde, methenamine)It cannot recycle using for this point, material(Money
Source)Utilization rate is high, and reduces discharge and the wastewater treatment load of formaldehyde.In step 2, it can control formaldehyde relatively excessive, promote
It is reacted completely into the ammonia being passed through, reduces the more than needed of ammonia to the greatest extent, final realize no longer generates ammonium chloride and its mother liquor.
4, micro-adjustment, charging are segmented by the temperature control that heats up after the use of the methanol solution of anhydrous formaldehyde, addition, system pH
Mode such as controls at the concrete technologies scheme, reduces the yield for increasing the byproducts such as sweet phosphorus, methylol glyphosate, and glyphosate yield obtains
Promote 0.6% or so.
Description of the drawings
Fig. 1 is the process flow chart for the alkyl esterification method synthesizing glyphosate that chloroacetic acid of the present invention is raw material.
Fig. 2 is the process flow chart for the alkyl esterification method synthesizing glyphosate that another chloroacetic acid of the invention is raw material.
Specific implementation mode
Embodiment 1
1 bottom of reaction kettle passes through pipeline and 3 top attachment of reaction kettle;1 top of reaction kettle and anhydrous chloroacetic acid, methanol, triethylamine
Measuring tank couples respectively.
2 bottom of reaction kettle passes through pipeline and 3 top attachment of reaction kettle;The top of reaction kettle 2 and methanol, paraformaldehyde or(Nothing
The methanol solution of water beetle aldehyde)Measuring tank couples respectively;2 top of reaction kettle also couples with ammonia pipeline.
3 bottom of reaction kettle passes through pipeline and 4 top attachment of reaction kettle.3 top of reaction kettle and triethylamine, phosphorous acid diformazan
Ester, paraformaldehyde or(The methanol solution of anhydrous formaldehyde)Measuring tank couples respectively.
4 top of reaction kettle couples with vacuum plant, and vacuum plant another port couples with condenser.4 bottom of reaction kettle with
Glyphosate washes material device connection.
As the explanation to attached drawing 1:The function of reaction kettle 3 can also be taken on by reaction kettle 1, i.e.,:Both it can will mix molten
Liquid A, mixed solution B are pumped into reaction kettle 3 and mixed solution C are obtained by the reaction, and can also be pumped into mixed solution B in reaction kettle 1 and mix
It closes solution A and mixed solution C is obtained by the reaction.
The function of reactor 4 can also be taken on by reaction kettle 3.Further, when the function of reaction kettle 3 is carried on a shoulder pole by reaction kettle 1
At that time, the function of reactor 4 was also taken on by reaction kettle 1.
Embodiment 2
1 bottom of reaction kettle passes through pipeline and 3 top attachment of reaction kettle;1 top of reaction kettle and anhydrous chloroacetic acid, methanol, triethylamine
Measuring tank couples respectively.
2 bottom of reaction kettle passes through pipeline and 3 top attachment of reaction kettle;The top of reaction kettle 2 and methanol, paraformaldehyde or(Nothing
The methanol solution of water beetle aldehyde)Measuring tank couples respectively;2 top of reaction kettle also couples with ammonia pipeline.
3 bottom of reaction kettle passes through pipeline and 4 top attachment of reaction kettle.3 top of reaction kettle and triethylamine, phosphorous acid diformazan
Ester, paraformaldehyde or(The methanol solution of anhydrous formaldehyde)Measuring tank couples respectively.
4 top of reaction kettle couples with vacuum plant, and vacuum plant another port couples with condenser.4 bottom of reaction kettle with
The equipment for separating liquid from solid such as filter press, centrifuge, suction strainer slot couple.
The liquid outlet opening of the equipment for separating liquid from solid and 5 top attachment of reaction kettle, the solids exit of equipment for separating liquid from solid
Mouth couples with triethylamine hydrochloride collecting tank.
5 bottom of reaction kettle passes through pipeline and 6 top attachment of reaction kettle;5 top of reaction kettle also couples with hydrochloric acid measuring tank.
6 bottom of reaction kettle is washed material device with glyphosate and is coupled.
Special declaration:
1, the function of reaction kettle 3 can also be taken on by reaction kettle 1, i.e.,:Both mixed solution A, mixed solution B can be pumped into reaction
Mixed solution C is obtained by the reaction in kettle 3, mixed solution B can also be pumped into reaction kettle 1 be obtained by the reaction with mixed solution A mix it is molten
Liquid C.Under such situation, 1 bottom of reaction kettle by pipeline and 3 top attachment of reaction kettle, 1 top of reaction kettle and anhydrous chloroacetic acid,
Methanol, triethylamine, dimethylphosphite, paraformaldehyde or(The methanol solution of anhydrous formaldehyde)Measuring tank couples respectively.
2, the function of reactor 4 can also be taken on by reaction kettle 3.Further, when the function of reaction kettle 3 is by reaction kettle 1
When taking on, the function of reactor 4 is also taken on by reaction kettle 1.
The process route that attached drawing using the present invention carries out is as follows:
Embodiment 3:
3.0mol methanol, 0.6mol triethylamines are added in reaction kettle 1, then add 0.5mol anhydrous chloroacetic acids, temperature control 30~35
It is reacted 20 minutes at DEG C, is then cooled to room temperature, obtains mixed solution A.3.0mol methanol is added in reaction kettle 2, then is added
1.2mol paraformaldehydes react 15min at 30 DEG C, are slowly introducing ammonia, control gauge pressure 100KPa, temperature 15- in reaction kettle
Lead to ammonia 0.55mol at 20 DEG C, has led to reaction 30 minutes, obtained mixed solution B.Mixed solution A and mixed solution B are beaten toward reaction
In kettle 3, in positive pressure(100KPa), react 20 minutes at 10~15 DEG C, the triethylamine that 0.4mol is added into system adjusts pH value
To 8.2,40~43 DEG C are warming up to, is at the same time continuously gradually added into the paraformaldehyde of about 0.25mol, reacts object after sixty minutes
Material system bleach obtains the mixed solution C that main component is the intermediates such as hydroxymethylglycinate.Then it is rapidly heated to 50-
56 DEG C, then stirring, heat preservation 1min are cooled to rapidly 40 DEG C or so again, enter back into addition dimethylphosphite in next step and control
The operation of temperature.The dimethylphosphite of 0.62mol is added, 50~53 DEG C of temperature control adds a small amount of triethylamine after keeping the temperature 5min
With regulation system pH value to 8.0.Then it is reacted 70 minutes at 50~53 DEG C again, it is N- dimethyl esters phosphonos to obtain main component
The mixed solution D of the organic phosphines intermediate such as ylmethyl glycine.Mixed solution D is squeezed into reaction kettle 4, in vacuum degree 60-
Separating methanol 10min at 94KPa and 35-45 DEG C is subsequently cooled to 15 DEG C hereinafter, the hydrochloric acid triethylammonium salts that are precipitated of centrifugation removal are brilliant
Body, successively using the methanol and fresh methanol rinses triethylammonium salts crystal of removing condensation.Cleaning solution is merged into isolated
In supernatant, mixed solution E is obtained.30% hydrochloric acid 1.6mol is added into mixed solution E, through acidolysis, is crystallized, is washed material, drying,
Obtain solid glyphosate active compound, solid glyphosate yield(In terms of monoxone)Yield is 69.2%, and mother liquor glyphosate converts into yield
It is 4.6%, glyphosate total recovery is 74.0%.
Embodiment 4:
3.0mol methanol, 0.6mol triethylamines are added in reaction kettle 1, then add 0.5mol anhydrous chloroacetic acids, temperature control 30~35
It is reacted 20 minutes at DEG C, is then cooled to room temperature, obtains mixed solution A.75g paraformaldehyde depolymerization liquid is added in reaction kettle 2
(That is the methanol solution of anhydrous formaldehyde, content of formaldehyde about 48%, methanol content about 52%, water content are less than 0.5%), add methanol
1.9mol mixes 1min, in positive pressure at 20 DEG C(100KPa), slowly lead to ammonia 0.6mol at 15-20 DEG C of temperature, lead to and reacted 30
Minute, obtain mixed solution B.Mixed solution A and mixed solution B are beaten into reaction kettle 3, in positive pressure(100KPa), at 10 DEG C
Reaction 20 minutes, the triethylamine added into system into 0.43mol adjust pH value to 8.2, are warming up to 40~43 DEG C, at the same time
It is continuously gradually added into the paraformaldehyde of 0.2mol, material system becomes as clear as crystal after reaction 65 minutes, obtains main component
For the mixed solution C of the intermediates such as hydroxymethylglycinate.Then it is rapidly heated to 50-56 DEG C, stirring, heat preservation 15min, then again
40 DEG C or so are cooled to rapidly, enters back into and the dimethylphosphite i.e. operation of temperature control is added in next step.It is added again into reaction kettle 3
The dimethylphosphite of 0.62mol, 50~53 DEG C of temperature control are added a small amount of triethylamine and are arrived with regulation system pH value after keeping the temperature 5min
8.0.Then it is reacted 70 minutes at 50~53 DEG C again, obtain main component has for N dimethyl esters (phosphonomethyl) glycines etc.
The mixed solution D of machine phosphine intermediate.Mixed solution D is squeezed into reaction kettle 4, is taken off at vacuum degree 60-94KPa and 35-45 DEG C
Methanol 10min is subsequently cooled to 15 DEG C hereinafter, the hydrochloric acid triethylammonium salts crystal that centrifugation removal is precipitated, successively uses removing condensation
Methanol and fresh methanol rinses triethylammonium salts crystal.Cleaning solution is merged into isolated supernatant, obtains mixing molten
Liquid E.30% hydrochloric acid 1.60mol is added into mixed solution E, through acidolysis, is crystallized, is washed material, drying, obtains solid glyphosate active compound,
Solid glyphosate yield(In terms of monoxone)Yield is 73.4%, and it is 5.8% that mother liquor glyphosate, which converts into yield, glyphosate total recovery
It is 79.2%.
Embodiment 5:
3mol methanol, 0.6mol triethylamines are added in reaction kettle 1, then add 0.5mol anhydrous chloroacetic acids, 30~35 DEG C of temperature control
Lower reaction 20 minutes, is then cooled to room temperature, obtains mixed solution A.75g paraformaldehyde depolymerization liquid is added in reaction kettle 2(I.e.
The methanol solution of anhydrous formaldehyde, content of formaldehyde about 48%, methanol content about 52%, water content are less than 0.5%), add methanol
1.8mol mixes 1min, in positive pressure at 20 DEG C(100KPa), slowly lead to ammonia 0.6mol at 15-20 DEG C of temperature, lead to and reacted 30
Minute, obtain mixed solution B.Mixed solution B is beaten and is mixed with mixed solution A into reaction kettle 1, in positive pressure
(100KPa), react 20 minutes at 10 DEG C, the triethylamine into 0.45mol is added into system and adjusts pH value to 8.4, temperature control 40~
43 DEG C, 0.2mol paraformaldehydes are at the same time continuously gradually added into, material system is obtained by muddy bleach after reaction 65 minutes
To the mixed solution C that main component is the intermediates such as hydroxymethylglycinate.Then it is rapidly heated to 50-56 DEG C, stirring, heat preservation
Then 10min is cooled to rapidly 40 DEG C or so again, enter back into and the dimethylphosphite i.e. operation of temperature control is added in next step.Again to
In reaction kettle 1 be added 0.65mol dimethylphosphite, 50~53 DEG C of temperature control, keep the temperature 10min after add a small amount of triethylamine with
Regulation system pH value is to 8.0.Then it is reacted 70 minutes at 50~53 DEG C again, it is N- dimethyl esters phosphonos to obtain main component
The mixed solution D of the organic phosphines intermediate such as methylglycine.Reaction kettle 1 is controlled to take off at vacuum degree 60-90KPa and 35-45 DEG C
Except methanol 20min, 15 DEG C are subsequently cooled to hereinafter, the hydrochloric acid triethylammonium salts crystal that centrifugation removal is precipitated, successively cold using removing
Solidifying methanol and fresh methanol rinses triethylammonium salts crystal.Cleaning solution is merged into isolated supernatant, is mixed
Solution E.30% hydrochloric acid 1.6mol is added into mixed solution E, through acidolysis, crystallizes, wash material, drying, obtains solid glyphosate original
Medicine, solid glyphosate yield(In terms of monoxone)Yield is 75.1%, and it is 5.2% that mother liquor glyphosate, which converts into yield, and glyphosate is total
Yield is 80.3%.
Claims (10)
1. a kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that include the following steps:
(1)Using monoxone as raw material, using methanol as solvent, using triethylamine as catalyst, mixed solution A is obtained after reaction;
(2)After using paraformaldehyde, methanol as raw material hybrid reaction, then it is passed through ammonia and mixed solution B is obtained by the reaction;
(3)By above-mentioned steps(2)Mixed solution B and above-mentioned steps(1)Mixed solution A mixed, mended after being stirred to react
Add triethylamine to adjust pH value between 7.0~9.0, while paraformaldehyde is added, mixed solution C is obtained after reaction;
(4)To above-mentioned steps(3)Mixed solution C in, be added dimethylphosphite, triethylamine, regulation system are added after heating
PH value obtains mixed solution D to being reacted after 7.0~8.8;
(5)By above-mentioned steps(4)Mixed solution D remove solvent methanol, cooling, the hydrochloric acid triethylammonium salts crystal of precipitation, washing
Supernatant is isolated, supernatant is refined, dry through acidolysis, crystallization, washing, obtains solid glyphosate active compound.
2. chloroacetic acid described in claim 1 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that step
(1)In, it is reacted 8~30 minutes at 30~65 DEG C of temperature after monoxone, methanol, triethylamine mixing, the molar ratio of material
For:Monoxone:Triethylamine:Methanol=1:0.9~1.6:6~8.
3. chloroacetic acid described in claim 1 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that described
The step of(2)Middle paraformaldehyde can be replaced by the alcoholic solution of anhydrous formaldehyde;The step(2)In, paraformaldehyde or anhydrous
The alcoholic solution of formaldehyde carries out with methanol at 10~50 DEG C reacting 0~15min, then is passed through ammonia, is reacted under the conditions of 0~40 DEG C
20~45min.
4. the chloroacetic acid described in claim 1 or 3 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that
Controlling the mixed molar ratio of each material is:Formaldehyde:Methanol:Ammonia=1:1~3:0.45~0.6.
5. chloroacetic acid described in claim 1 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that described
The step of(3)Middle paraformaldehyde can be replaced by the alcoholic solution of anhydrous formaldehyde;After mixed solution B is mixed with mixed solution A
Reacted 10~30 minutes under the conditions of 0~30 DEG C, then add triethylamine and adjust pH value between 7.0~9.0, then temperature control 40~
45 DEG C, while the methanol solution of paraformaldehyde or anhydrous formaldehyde is added, it reacts 50~80 minutes, obtains mixed solution C.
6. the chloroacetic acid described in claim 1 or 5 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that
The step(3)Middle triethylamine, paraformaldehyde are relative to step(1)The chloroacetic relationship of feeding intake of middle addition is:Material
Molar ratio controls:Monoxone:Triethylamine:Paraformaldehyde=1:0.1~1.1:0~1.
7. the chloroacetic acid described in claim 1 or 5 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that
Mixed solution C is rapidly heated to 50-56 DEG C, 30-40 DEG C is cooled to rapidly after stirring, heat preservation 10s-20min, enters back into next
Step is added in the operating procedure of dimethylphosphite, that is, temperature control.
8. chloroacetic acid described in claim 1 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that step
(4)In, into mixed solution C, dimethylphosphite is added, is warming up to 50~55 DEG C, keep the temperature add after 1-10min triethylamine with
Then regulation system pH value reacts 60~110 minutes at 50~55 DEG C to 7.0~8.8, obtains mixed solution D.
9. the chloroacetic acid described in claim 1 or 8 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that
The step(4)Middle triethylamine, dimethylphosphite are relative to step(1)The chloroacetic relationship of feeding intake of middle addition is:
The molar ratio of material is:Monoxone:Triethylamine:Dimethylphosphite=1:0.01-0.1:1~1.4.
10. chloroacetic acid described in claim 1 is the technique of the alkyl esterification method synthesizing glyphosate of raw material, which is characterized in that step
Suddenly(4)In, mixed solution D is removed into partial solvent methanol, control time 0- under 10~65 DEG C and absolute pressure 0-100KPa
60min is subsequently cooled to 0 ~ 20 DEG C, and hydrochloric acid triethylammonium salts crystal and supernatant is precipitated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810362616.1A CN108690071A (en) | 2018-04-20 | 2018-04-20 | A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810362616.1A CN108690071A (en) | 2018-04-20 | 2018-04-20 | A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108690071A true CN108690071A (en) | 2018-10-23 |
Family
ID=63845780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810362616.1A Pending CN108690071A (en) | 2018-04-20 | 2018-04-20 | A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690071A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891763A (en) * | 2009-05-19 | 2010-11-24 | 李其奎 | Production method of N-(phosphonomethyl)glycine |
| CN102898467A (en) * | 2012-09-14 | 2013-01-30 | 太原理工大学 | One-pot synthesis method for glyphosate from chloroacetic acid |
-
2018
- 2018-04-20 CN CN201810362616.1A patent/CN108690071A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891763A (en) * | 2009-05-19 | 2010-11-24 | 李其奎 | Production method of N-(phosphonomethyl)glycine |
| CN102898467A (en) * | 2012-09-14 | 2013-01-30 | 太原理工大学 | One-pot synthesis method for glyphosate from chloroacetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 高立蕊: "氯乙酸—锅法合成草甘膦新工艺的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100558633C (en) | The method for preparing PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and industrial monoammonium phosphate with phosphoric acid by wet process | |
| CN102963874B (en) | Method for producing industrial-grade potassium dihydrogen phosphate (KH2PO4) by wet method purified phosphoric acid and potassium sulfate | |
| CN105036101A (en) | Semi-hydrated-two-hydrated wet process phosphoric acid production process and system thereof | |
| CN101830946A (en) | Method for synthesizing clindamycin phosphate | |
| CN108383094A (en) | The method for preparing calcium monohydrogen phosphate and ammonium chloride using reverse flotation phosphorus tailing | |
| CN106478715A (en) | A kind of method of synthesizing colourless emtrol polyoxyvinethene phosphate | |
| CN103304423A (en) | Method for recovering triethylamine from glyphosate material | |
| CN101993455A (en) | Glyphosate synthesis process | |
| CN111086977A (en) | Method for preparing MCP and MDCP (Madin-Darby Canine phosphate) by using raffinate acid | |
| CN204873846U (en) | Half water - no. 2 water law phosphoric acid by wet process production system | |
| CN103570760A (en) | Method for producing etidronic acid | |
| CN1939926A (en) | Production of glyphosate by glycine method | |
| CN108690071A (en) | A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material | |
| CN1308336C (en) | Process for treating production mother liquor of glyphosate | |
| CN108329350A (en) | A kind of glyphosate synthesis device | |
| CN1772601A (en) | Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct | |
| CN100396599C (en) | Method for producing phosphorous acid and gypsum using hydrochloric acid method | |
| CN1953986B (en) | Purification of N-(phosphonomethyl)glycine | |
| CN102766160A (en) | Novel process for preparing glyphosate by utilizing glycine method | |
| CN102875401B (en) | Method for producing DL-aspartic acid from waste radix asparagi | |
| CN213141414U (en) | System for producing potassium dihydrogen phosphate by solvent method | |
| CN100500678C (en) | Process of glycine method for preparing glyphosate | |
| CN105503592B (en) | The method that ester-interchange method handles the waste water containing isobutyrate | |
| CN101560210B (en) | Method for synthesizing diprophylline | |
| CN1308634A (en) | Process for prepairng N-phosphonomethyl iminodiacatio acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181023 |
|
| RJ01 | Rejection of invention patent application after publication |