CN106632470A - Synthesis of N-hydroxymethyl glyphosate or ester thereof and method for preparing glyphosate - Google Patents
Synthesis of N-hydroxymethyl glyphosate or ester thereof and method for preparing glyphosate Download PDFInfo
- Publication number
- CN106632470A CN106632470A CN201611184168.8A CN201611184168A CN106632470A CN 106632470 A CN106632470 A CN 106632470A CN 201611184168 A CN201611184168 A CN 201611184168A CN 106632470 A CN106632470 A CN 106632470A
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- Prior art keywords
- glyphosate
- glycine
- calculation
- methylol
- amount
- Prior art date
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- Granted
Links
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 207
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 207
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 60
- 230000015572 biosynthetic process Effects 0.000 title claims description 23
- 238000003786 synthesis reaction Methods 0.000 title claims description 23
- 150000002148 esters Chemical class 0.000 title claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 145
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000004471 Glycine Substances 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 36
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 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 claims abstract description 19
- 239000012267 brine Substances 0.000 claims abstract description 17
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 17
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 146
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 229960002449 glycine Drugs 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 49
- 238000004364 calculation method Methods 0.000 claims description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 47
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 235000009508 confectionery Nutrition 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 24
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 24
- 235000019253 formic acid Nutrition 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 19
- 235000013877 carbamide Nutrition 0.000 claims description 19
- -1 ester hydrochlorides Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 15
- 239000003337 fertilizer Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229960001269 glycine hydrochloride Drugs 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- YWICANUUQPYHOW-UHFFFAOYSA-M sodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].OP(O)(=O)CNCC([O-])=O YWICANUUQPYHOW-UHFFFAOYSA-M 0.000 claims description 11
- ZEKANFGSDXODPD-UHFFFAOYSA-N glyphosate-isopropylammonium Chemical compound CC(C)N.OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 8
- DSKJXGYAJJHDOE-UHFFFAOYSA-N methylideneurea Chemical compound NC(=O)N=C DSKJXGYAJJHDOE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 238000013459 approach Methods 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- LIOPHZNMBKHGAV-UHFFFAOYSA-M potassium;2-(phosphonomethylamino)acetate Chemical compound [K+].OC(=O)CNCP(O)([O-])=O LIOPHZNMBKHGAV-UHFFFAOYSA-M 0.000 claims description 5
- SGVDYFNFBJGOHB-UHFFFAOYSA-N 2-[methyl(phosphonomethyl)amino]acetic acid Chemical compound OC(=O)CN(C)CP(O)(O)=O SGVDYFNFBJGOHB-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 3
- 210000002700 urine Anatomy 0.000 claims description 3
- DCPKPRMFZRJEMG-UHFFFAOYSA-N 2-aminoacetate;triethylazanium Chemical compound NCC(O)=O.CCN(CC)CC DCPKPRMFZRJEMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000000524 functional group Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- USPDYHQWWULKMD-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(O)(O)O USPDYHQWWULKMD-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000010931 ester hydrolysis Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 abstract description 15
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 abstract description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- WBZVQGYKIVWFGQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetic acid Chemical compound NC(=O)COCC(O)=O WBZVQGYKIVWFGQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006400 oxidative hydrolysis reaction Methods 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 50
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 22
- 239000000543 intermediate Substances 0.000 description 22
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 238000001816 cooling Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003570 air Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JTPUMZTWMWIVPA-UHFFFAOYSA-O Isopropamide Chemical compound C=1C=CC=CC=1C(C(N)=O)(CC[N+](C)(C(C)C)C(C)C)C1=CC=CC=C1 JTPUMZTWMWIVPA-UHFFFAOYSA-O 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
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- RBEVVLXUECGFTL-UHFFFAOYSA-N dimethyl hydrogen phosphite methanol Chemical compound OC.COP(O)OC RBEVVLXUECGFTL-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229960001737 isopropamide Drugs 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/02—Fertilisers containing urea or urea compounds containing urea-formaldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- 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)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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Abstract
The invention relates to a method for synthesizing N-hydroxymethyl glyphosate from three raw materials including combined glycine, phosphorus trichloride or dimethyl phosphite or phosphorous acid, and formaldehyde, and a method or a technical route for preparing glyphosate raw powder and a glyphosate aqueous solution by adopting N-hydroxymethyl glyphosate as an intermediate or a raw material. Compared with a conventional technical route for producing glyphosate by virtue of an IDA method, raw materials including iminodiacetonitrile and diglycolamidic acid are not needed, and the preparation of a PMIDA intermediate or raw material is not needed; and compared with a conventional technical route for producing glyphosate by virtue of a glycine method, the raw materials including triethylamine, dimethyl phosphite and formaldehyde are not needed. According to the method provided by the invention, N-hydroxymethyl glyphosate or an N-hydroxymethyl glyphosate hydrochloride intermediate or raw material is prepared, and then the intermediate or raw material is converted into glyphosate and an aqueous solution thereof by virtue of oxidative hydrolysis. Sodium chloride effluent brine is not generated, and the production cost is reduced by 15% or above compared with an existing glyphosate production process.
Description
Technical field
The present invention relates to one kind combines glycine and Phosphorous chloride. or dimethylphosphite or phosphorous acid and three kinds of formaldehyde is former
The method of material synthesis N- methylol glyphosates, and adopt N- methylols glyphosate the former powder of glyphosate is prepared for intermediate or raw material
And its method or technique route of gyphosate solution.Compared with the technology path of traditional IDA methods production glyphosate, it is not necessary to
Iminodiacetonitrile 1,1'-Imidodiacetonitrile and iminodiacetic acid (salt) acid starting material, it is not necessary to prepare PMIDA intermediate or raw material；With traditional glycine method
The technology path of production glyphosate compares, it is not necessary to triethylamine raw material, it is not necessary to triethylamine recovery process.The inventive method system
Standby is N- methylols glyphosate and its hydrochlorate or N- methylol glyphosate dimethyl esters and its hydrochloride intermediate or raw material, so
The intermediate or raw material are converted into into glyphosate and its water preparation by the approach of oxydrolysises afterwards.Whole production process does not produce chlorine
Change sodium effluent brine, production cost is compared existing glyphosate production technique and declines more than 15%.
Background technology
Combine glycine and Phosphorous chloride. and these three raw materials of formaldehyde or these three reaction substrates synthesis N- methylol grass are sweet
Phosphine (the sweet phosphine of abbreviation hydroxyl) or synthesis N- methylol glyphosate dimethyl esters (the sweet phosphine ester of abbreviation hydroxyl), or combination glycine and phosphorous
Acid and these three raw materials of formaldehyde or these three reaction substrates synthesize N- methylol glyphosates, or combination glycine and phosphorous acid two
Methyl ester and these three raw materials of formaldehyde or these three reaction substrates synthesize N- methylol glyphosate dimethyl esters, and will be N- methylol grass sweet
Phosphine (the sweet phosphine of hydroxyl) or N- methylol glyphosate dimethyl esters (the sweet phosphine ester of hydroxyl) are further converted to the side of glyphosate original powder and its water preparation
Method, yet there are no the open report of documents and materials, and more loseing has corresponding industrial production device.Existing glyphosate industry is raw
Production. art route has two：First, glycine and three kinds of raw materials of dimethylphosphite and formaldehyde or three kinds of reaction substrate synthesis are combined
Glyphosate, preparation is N- methylol glyphosate dimethyl ester triethylamine salt intermediate, needs to add substantial amounts of triethylamine, therefore necessary
Auxiliary construction triethylamine retracting device is wanted, the investment of production cost and fixed assets is thereby increased.Especially for recovery three
Ethamine, causes 1 ton of glyphosate of production to necessarily lead to more than 5 tons high concentration Sodium Chloride effluent brines, not only consumes hydrochloric acid and hydrogen in a large number
Sodium oxide this two kinds of raw materials, increased cost of material, and are substantially increased environmental protection because of the process up to standard of the strong brine that gives up
Cost, so as to increased the production cost of glyphosate.2nd, iminodiacetic acid and three kinds of raw materials of phosphorous acid and formaldehyde or anti-are combined
Substrate synthesizing glyphosate is answered, preparation is PMIDA intermediate or raw material, then by oxygen or air or hydrogen peroxide or dense sulfur
PMIDA oxydrolysises are converted into glyphosate by acid etc..But in order to prepare iminodiacetic acid, it is necessary to auxiliary construction imino group
Diacetonitrile is hydrolyzed to the process units of iminodiacetic acid, thereby increases production cost.In particular by sodium hydroxide water
Solution Iminodiacetonitrile 1,1'-Imidodiacetonitrile, therefore 1 ton of PMIDA intermediate of production or raw material necessarily lead to more than 5 tons high concentration Sodium Chloride abraum salts
Water, not only needs to consume hydrochloric acid and this two kinds of raw materials of sodium hydroxide in a large number, increased cost of material, and reaching because of the strong brine that gives up
Mark is processed and is substantially increased environmentally friendly cost, so as to increased the production cost of glyphosate.
Using the process route production glyphosate of the method for the present invention or the present invention, sodium hydroxide, triethylamine, Asia are eliminated
Be present the neutralization reaction process of sodium hydroxide and hydrochloric acid in the raw materials such as aminoacetaldehyde diethyl nitrile, whole production process, therefore will not produce
Sodium Chloride effluent brine, fundamentally thoroughly solves traditional glyphosate production technique and produces high concentration Sodium Chloride effluent brine need in a large number
A difficult problem to be processed.Combination glycine and Phosphorous chloride. or dimethylphosphite or phosphorous acid and formaldehyde these three reaction substrate systems
Standby N- methylol glyphosate intermediate or raw material, or N- methylols glyphosate dimethyl ester intermediate or raw material are prepared, it is whole to make
Standby process need not use sodium hydroxide, and by-product hydrochloric acid, therefore not consume sodium hydroxide and hydrochloric acid this two kinds of raw materials, raw material into
This relatively all traditional glyphosate production technique is minimum, due to not producing Sodium Chloride effluent brine, therefore environment protection treating cost also phase
Should be minimum.Compared with traditional IDA methods production glyphosate technique, eliminate Iminodiacetonitrile 1,1'-Imidodiacetonitrile alkaline hydrolysis and prepare iminodiacetic acid (salt)
The operation of acid；Compared with traditional preparing glyphosate by glycin method technique, triethylamine recovery process is eliminated.Thus it is also larger
The workshop cost of glyphosate production is reduced to amplitude, the investment of fixed assets is reduced again.With glycine, synthesize N- hydroxyl first
The yield of base glyphosate intermediate or raw material or synthesis N- methylols glyphosate dimethyl ester intermediate or raw material up to 90% with
On.Therefore, the cost for preparing " the sweet phosphine of hydroxyl " (N- methylol glyphosates) compares the cost of preparation " PMIDA " (including at effluent brine
Reason) have dropped more than 20%.And " the sweet phosphine of hydroxyl " oxidation is converted into the process and process units and " PMIDA " oxygen of glyphosate
The process and process units that change is converted into glyphosate is substantially identical.And, the process of PMIDA oxidation conversion is not produced
Sodium Chloride effluent brine, only produces the mother solution that can be directly used for preparing gyphosate solution.The two (the sweet phosphine of hydroxyl and PMIDA) conversion is anti-
The essence answered has identical point：As the sweet phosphine of hydroxyl and PMIDA belong to the similar tertiary amine compounds of molecular structural formula,
They can occur oxydrolysises reaction in water and generate glyphosate secondary amine and formaldehyde, or turn under the catalysis of ferrous ion
Turn to secondary amine and formaldehyde.Therefore this method can utilize traditional PMIDA oxidation conversion to prepare a whole set of production of glyphosate completely
Equipment produces glyphosate.But the maximum difference of the two is that production " the sweet phosphine of hydroxyl " does not produce Sodium Chloride effluent brine, and produce " double
Sweet phosphine " necessarily leads to substantial amounts of concentrated sodium chloride effluent brine.It is therefore evident that：Prepared using the method for the present invention or technology path
Glyphosate, whole production process do not produce the effluent brine for needing governance for reaching standard, and not producing needs useless solid sodium chloride salt to be processed.
Sum it up, no matter being adjusted using which kind of standard, this method compares all traditional glyphosate production techniques, production cost
Decline more than 15%.
The present invention the most typical feature of technology path have to be by synthesize N- methylol glyphosates (the sweet phosphine of hydroxyl) or
Go to prepare glyphosate and its water preparation by the approach for synthesizing N- methylol glyphosate diester intermediates or raw material.As long as N- hydroxyl first
Methylol functional groups in base glyphosate structural formula hydrolyze, and are also converted to for glyphosate and formaldehyde.It is former with glyphosate
The reaction of powder and formaldehyde is easy to prepare N- methylol glyphosates, thus the N- hydroxymethylations of glyphosate be one kind can be converse
Should, therefore in the aqueous solution of N- methylol glyphosates, there is a certain amount of free formaldehyde, as long as constantly this free formaldehyde
The other materials such as formic acid or ureaformaldehyde slow release fertilizer are converted into, just necessarily can be the methylol functional groups in hydroxyl sweet phosphine thoroughly
Pull down from nitrogen, so as to hydroxyl sweet phosphine is irreversibly converted into glyphosate.So, a kind of method of the present invention is with urine
Free formaldehyde reaction in element and aqueous solution, constantly generate more stable methylolurea and its condensation polymer (urea-formaldehyde fertilizer or
Oligomeric methylene urea), so as to constantly in N- methylol glyphosates methylol functional groups hydrolysis cut-out draw in aqueous solution into
For free formaldehyde, methylolurea and oligomeric methylene urea are constantly generated；Shifting is balanced constantly from there through this reversible reaction
Dynamic mode, is converted into glyphosate and urea-formaldehyde fertilizer N- methylol glyphosates (the sweet phosphine of hydroxyl), and the sweet phosphine conversion ratio of hydroxyl is close to
100%；Another kind of method of the present invention is the production equipment that glyphosate is produced using traditional PMIDA catalysis oxidation, uses oxygen
Or air or hydrogen peroxide are constantly oxidized into formic acid the free formaldehyde in aqueous solution, so as to constantly N- methylol grass sweet
Methylol functional groups' oxydrolysises cut-out in phosphine (the sweet phosphine of hydroxyl) becomes free formaldehyde in drawing in aqueous solution, constantly generates first
Acid, from there through the mode of this reversible reaction constantly balanced sequence, just N- methylol glyphosates be converted into glyphosate and
Formic acid, the sweet phosphine conversion ratio of hydroxyl are close to 100%.Because both approaches produce glyphosate while can coproduction urea-formaldehyde fertilizer or
Person's formate product, the atom utilization of raw material is more than 95%.Thus the technology path of preparing glyphosate from N-phosphonomethyl aminodiacetic acid is compared, this
The technology path of invention can reach " three wastes " zero-emission.
The content of the invention
It is an object of the invention to provide a kind of combination glycine and Phosphorous chloride. and formaldehyde these three Material synthesis glyphosates
And its method for gyphosate solution, or a kind of combination glycine and phosphorous acid and formaldehyde these three Material synthesis glyphosates are provided
And its method for gyphosate solution, or a kind of combination glycine and dimethylphosphite and formaldehyde these three Material synthesis are provided
The method of glyphosate and its gyphosate solution, it is characterised in that glycine and Phosphorous chloride. and formaldehyde these three material combinations one
Rise in synthesis N- methylols glyphosate and its hydrochloride intermediate or synthesis N- methylol glyphosate dimethyl esters and its hydrochlorate
Mesosome, or a kind of glycine and phosphorous acid and formaldehyde these three material combinations are synthesized N- methylols glyphosate and its salt together
Hydrochlorate intermediate, or a kind of glycine and dimethylphosphite and formaldehyde these three material combinations are synthesized N- methylols together
Glyphosate dimethyl ester and its hydrochloride intermediate, and this intermediate or raw material are disappeared by the approach of reversible reaction balanced sequence
Except this functional group of methylol, so as to be converted into glyphosate original powder and its gyphosate solution；As whole preparation process will not be produced
Raw Sodium Chloride effluent brine, therefore the package unit that traditional processing technology processes glyphosate effluent brine is also just eliminated, including it is current
The sodium chloride salt incinerator that manufacturing enterprise is currently in use；A kind of combination glycine and Phosphorous chloride. and formaldehyde these three raw materials are provided
The method of synthesis N- methylols glyphosate and its hydrochlorate or synthesis N- methylol glyphosate dimethyl esters and its hydrochlorate, or
A kind of method that combination glycine and phosphorous acid and these three Material synthesis of formaldehyde N- methylols glyphosate and its hydrochlorate are provided,
Or a kind of combination glycine and dimethylphosphite and formaldehyde these three Material synthesis N- methylol glyphosate dimethyl esters are provided
And its method for hydrochlorate, it is characterised in that glycine and Phosphorous chloride. and formaldehyde these three material combinations together as preparation
The purposes of the reaction substrate of N- methylols glyphosate and its hydrochlorate or N- methylol glyphosate dimethyl esters and its hydrochlorate, or
It is together as preparing N- methylols (N- dimethyl phosphonates glycine and dimethylphosphite and these three material combinations of formaldehyde
Ylmethyl) glycine and its hydrochlorate reaction substrate purposes, or these three are former glycine and phosphorous acid and formaldehyde
Material combination prepares the purposes of the reaction substrate of N- methylols (N- phosphonic acids ylmethyls) glycine and its hydrochlorate together；There is provided a kind of
Carbamide and N- methylols glyphosate application and method as the raw material for preparing glyphosate, it is characterised in that carbamide and N- hydroxyl first
Base glyphosate or its hydrochlorate this two kinds of material combinations prepare together glyphosate original powder and its oligomeric methylene urea of water preparation co-production or
Ureaformaldehyde；Or the purposes that formic acid prepares the catalyst of glyphosate as a kind of catalysis oxidation N- methylol glyphosate is provided, with
And the purposes of the catalyst of glyphosate is prepared as a kind of catalysis oxidation PMIDA and glyphosine；There is provided with N- methylols (N- phosphines
Acidic group methyl) glycine and its hydrochlorate be application that raw material or intermediate prepare glyphosate original powder and its water preparation；There is provided with N-
Methylol (N- dimethyl phosphonate ylmethyls) glycine and its hydrochlorate are that raw material or intermediate prepare glyphosate original powder and its water
The application of agent；A kind of method for adopting glycine and dimethylphosphite that glyphosate is prepared for raw material is provided, be it is characterized in that whole
The alkaline reagents such as triethylamine or potassium hydroxide or sodium hydroxide need not be added in individual preparation process, N- methylol (N- are not produced
Dimethyl phosphonate ylmethyl) glycine triethylamine salt intermediate, or do not produce triethylamine hydrochloride or potassium chloride or Sodium Chloride
Deng salts substances, it is not necessary to the device such as triethylamine removal process and its Sodium Chloride incinerator, Sodium Chloride effluent brine is not produced.
Add a formaldehyde molecule in the nitrogen that so-called N- methylols glyphosate refers in glyphosate molecular structure
Compound, its another name is for N- methylols (N- phosphonic acids ylmethyls) glycine, or referred to as N- methylols (N- methylphosphine acidic groups) amino
Acetic acid, molecular formula are C4H10NO6P, molecular weight are 199, are the adduction of glyphosate molecular weight and formaldehyde molecule amount, its hydrochlorate
Molecular weight is 233.5, can prepare the standard sample of N- methylol glyphosates with glyphosate original powder and two kinds of raw material reactions of formaldehyde；Institute
Meaning N- methylol glyphosate dimethyl esters are referred to《The side reaction research caused by formaldehyde in glycine method synthesizing glyphosate》(author is
Huang Ming, Yin Yingwu, look into just bright) " compound 10 " in paper deduct triethylamine molecule, and its another name is N- methylols (N- phosphonic acids two
Methyl ester ylmethyl) glycine, or referred to as N- methylols (N- dimethyl methyl phosphonate bases) glycine, its molecular formula is
C6H14NO6P, molecular weight are 227, and its hydrochlorate molecular weight is 263.5, conventionally produced N- methylols (N- phosphonic acids two
Methyl ester ylmethyl) glycine triethylamine salt hydrochloric acid is neutralized reaction, can prepare the standard of N- methylol glyphosate dimethyl esters
Sample.
It is a kind of three kinds of material combinations of glycine and Phosphorous chloride. and formaldehyde together synthesizing glyphosate original powder and its water preparation
Method, including several steps of following sequence：
Step 1, N, the preparation of N- dihydroxymethyls glycine and its hydrochlorate
The glycine and formalin of amount of calculation are added in stirring reactor, while adding the Nacl of amount of calculation
Acid, starts stirring, is slowly ramped to 60 DEG C；Then in fine vacuum and less than under conditions of 60 DEG C, distillation 3-5 hours or so,
Distillation substrate is N, N- dihydroxymethyl glycine hydrochloride liquid crystal；
The preparation of step 2, N- methylols glyphosate or N- methylol glyphosate dimethyl esters and its hydrochlorate
2.1 N, N- dihydroxymethyl glycine hydrochloride liquid crystal is cooled to subzero 5 degrees Celsius (- 5 DEG C) below, slowly Deca
The temperature of amount of calculation is -8 DEG C of Phosphorous chloride., probably the Phosphorous chloride. of the 70% of Deca amount of calculation when stop stirring, continue slow
Slow addition does not drip remaining Phosphorous chloride., below 4 DEG C stands 24 hours, and it is unnecessary in net reactor then to be drained with vacuum
Phosphorous chloride., the pure water of Deca amount of calculation below 2 DEG C, or the absolute methanol of Deca amount of calculation opened after standing 10 hours
Dynamic stirring, in 20 DEG C of -30 DEG C of insulated and stirred reaction 2-3 hours；High vacuum distillation, control temperature are less than 70 DEG C, steam as far as possible
Hydrogen chloride and water, distill the mixture that substrate is N- methylols glyphosate and N- methylol glyphosate salt hydrochlorates, or distillation
Substrate is the mixture of N- methylol glyphosate dimethyl esters and N- methylol glyphosate diformazan ester hydrochlorides；
2.2 select acidproof electric stirring reactor, put into the Phosphorous chloride. of the amount of calculation that temperature is -8 DEG C, and starting is stirred
Mix, control temperature less than 10 DEG C, slowly Deca above-mentioned steps 1 preparation amount of calculation N, N- dihydroxymethyl glycine hydrochlorides
Liquid crystal, time for adding and insulation reaction time common 5-7 hours, then less than 10 DEG C and under conditions of isolation air, filter
Go out remaining Phosphorous chloride., filter cake is N- methylols (N- phosphonyl dichloride ylmethyls) glycine intermediate；Then by the middle of this
In body input reactor, slowly dropping temperature is the amount of calculation that the pure water or dropping temperature of 2 DEG C of amount of calculation are 2 DEG C without water beetle
Alcohol, in 20-30 DEG C of insulated and stirred reaction 2-3 hour；High vacuum distillation, control temperature are less than 70 DEG C, steam hydrogen chloride as far as possible
And water, the mixture that substrate is N- methylols glyphosate and N- methylol glyphosate salt hydrochlorates is distilled, or distillation substrate is
For N- methylol glyphosate diformazan ester products；
2.3rd, acidproof electric stirring reactor is selected, puts into the N of the amount of calculation prepared by above-mentioned steps 1, N- dihydroxy first
Base glycine hydrochloride liquid crystal, is warming up to 60-105 DEG C, under conditions of decompression or normal pressure, is slowly added into the phosphorous acid of amount of calculation
The phosphorous acid of dimethyl ester or addition amount of calculation, stirring reaction 4-8 hour, reaction mass become N- methylol glyphosate dimethyl ester salt
Hydrochlorate or N- methylol glyphosate salt hydrochlorates.
The preparation of step 3, glyphosate original powder and its water preparation
3.1st, acidproof stirring-type autoclave pressure reactor is selected, puts into the N- hydroxyl of the mass concentration for 20-40 ﹪ of amount of calculation
Methyl glyphosate and its hydrochloric acid saline solution, or the N- methylol glyphosate diformazans that the mass concentration of input amount of calculation is 20 ﹪
Ester methanol aqueous solution, starts stirring, and it is 2 to adjust solution ph with alkali, adds the sodium tungstate of amount of calculation, in 60 DEG C or so slowly Deca
The mass concentration of amount of calculation is 30% hydrogen peroxide, time for adding and insulated and stirred response time common 10-12 hours；Then add
The carbamide of amount of calculation or without carbamide, or the formic acid of input amount of calculation, are slowly warming up to 78-104 DEG C, start Deca amount of calculation
Mass concentration be 10 ﹪ ferrous sulfate aqueous solution, time for adding and insulated and stirred response time common 5-7 hours；It is cooled to 10
Below DEG C, crystallize 2 hours, filter, drying obtains glyphosate original powder, and content is more than 95%.
3.2nd, acidproof stirring-type autoclave pressure reactor is selected, puts into the N- hydroxyl of the mass concentration for 20-40% of amount of calculation
Methyl glyphosate and its HCI solution, or the N- methylol glyphosate dimethyl esters that the mass concentration of input amount of calculation is 20%
And its HCI solution, while the activated carbon or iron-molybdic catalyst and carbamide of amount of calculation is put into, or the activated carbon of input amount of calculation
Or iron-molybdic catalyst and formic acid；Start stirring, it is 4.5- the pH value of solution to be adjusted with 2-aminopropane. or potassium hydroxide or sodium hydroxide
8.5, or without adjusting PH with base value, temperature is controlled for 78-104 DEG C, control pressure is 0.15-0.4MPa, starts Deca amount of calculation
Mass concentration be 30% hydrogen peroxide, or add the oxygen of certain pressure, or continuously add excess air, drip
With insulated and stirred response time common 4-8 hours between the added-time, until N- methylols glyphosate or N- methylol glyphosate dimethyl ester water
Solution reaction is complete, is cooled to room temperature, filters out activated carbon and glyphosate original powder；Under vacuum filtrated stock is distilled to molten
Melting state, temperature being controlled for 78-104 DEG C, then insulation reaction 2 hours carries out secondary filter, and filter cake is urea-formaldehyde fertilizer,
Secondary filter mother solution is glyphosate isopropylamine salt water solution or sylvine aqua with glyphosate or sodium glyphosate water preparation, by the water preparation
Water be evaporated only, drying, as glyphosate isopropyl amine salt original powder or glyphosate potassium original powder or sodium glyphosate original powder.
Specific embodiment
Embodiment 1
Acidproof electric stirring reactor is selected, 30 grams of the glycine that mass concentration is 99% is thrown, throwing mass concentration is
64 grams of 37% formaldehyde, throws 98 grams of the technical hydrochloric acid that mass concentration is 30%, starts stirring, be slowly ramped to 60 DEG C, and stirring is anti-
Answer 2 hours, lower the temperature, start high vacuum distillation, control high vacuum distillation temperature is less than 60 DEG C, and distillation time is 5 hours；Distillation
Substrate is N, N- dihydroxymethyl glycine hydrochloride liquid crystal；Be then shut off vacuum valve, open atmospheric valve, be cooled to -5 DEG C with
Under, starting 56-180 gram of the Phosphorous chloride. that dropping temperature is -8 DEG C and mass concentration is 98%, control time for adding 4 hours is left
It is right；Probably 39-126 gram of Deca Phosphorous chloride. when stop stirring, below 0 DEG C, continue to drip three that remaining temperature is -8 DEG C
Phosphorus chloride, after dripping off, stands 24 hours below 4 DEG C, and reaction mass has become monoblock solid, as N- methylols (N- phosphonos
Dichloro ylmethyl) glycine intermediate；Unnecessary Phosphorous chloride. is extracted out with vacuum, then dropping temperature is 2 DEG C of pure water 150
Gram, or 150 grams of the absolute methanol that dropping temperature is 2 DEG C, control time for adding 4 hours, slowly start stirring, after dripping off, at 4 DEG C
Hereinafter continue stirring reaction 1-2 hour, then start vacuum distilling, control vapo(u)rizing temperature is less than 70 DEG C, is evaporated net chlorine as far as possible
Change hydrogen and water or methanol, distill the mixture product that substrate is N- methylols glyphosate and N- methylol glyphosate salt hydrochlorates,
Or the mixture product that distillation substrate is N- methylol glyphosate dimethyl esters and its hydrochlorate, with glycine, product yield
For more than 90%.
Embodiment 2
Product prepared by above-described embodiment 1 prepare become N- methylols glyphosate that mass concentration is 20-40% and its
100 grams of HCI solution, or prepare become 100 grams of the N- methylol glyphosate diformazans ester solution that mass concentration is 20%, throw
Enter in acidproof stirring-type autoclave pressure reactor, start stirring, with potassium hydroxide or or sodium hydroxide or ammonia adjust the pH of solution
Being worth for 2, adding 0.07-0.13 gram of the sodium tungstate that mass concentration is 99%, temperature is controlled for 60 DEG C, Deca mass concentration is
13-27 gram of 30% hydrogen peroxide, time for adding and insulated and stirred response time common 10-12 hours, are examined with potassium iodide starch test paper
Reaction mass is surveyed, reagent paper is reaction end for white；Then add mass concentration be 99% 6-12 gram of carbamide or without
Carbamide, or 25 grams of activated-carbon catalysts of addition, or the iron-molybdic catalyst of 15 grams of prepn. of formaldehyde by oxidation of methanol of addition, slowly heat up
To 78-104 DEG C, start Deca mass concentration be 10% 3.8-7.7 gram of ferrous sulfate aqueous solution, time for adding about 4-5 hours,
After dripping off, continue insulated and stirred reaction about 1-2 hours, middle control analysis are carried out with glyphosate GB liquid chromatography, until reaction
The mass concentration of N- methylols glyphosate or N- methylol glyphosate dimethyl esters in material is reaction end when being less than 1%；
Less than 10 DEG C are cooled to, atmospheric valve is opened, in 10 DEG C of crystallization below 2 hours, are filtered, drying, obtain glyphosate original powder 13.9-27.8
Gram, mass concentration is 97%.
Embodiment 3
Acidproof stirring-type autoclave pressure reactor is selected, the N- methylol glyphosate solutions that mass concentration is 30% are put into
100 grams, or 100 grams of the N- methylol glyphosate diformazans ester solution that input mass concentration is 20%, start stirring, use 2-aminopropane.
Or the pH value of solution is adjusted to 4.5-8.5 by potassium hydroxide or sodium hydroxide, or without adjusting PH with base value, while adding activated carbon
10-15 gram of catalyst, or 2-4 gram of the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol is added, add the urine that mass concentration is 99%
Plain 4.5-9 gram, or 3.5-6.9 gram of the formic acid that addition mass concentration is 99%；78-104 DEG C is slowly warming up to, starts Deca matter
Amount concentration is 30% 20-40 gram of hydrogen peroxide, or continuously adds oxygen or air, controls reactor pressure for 0.15-
0.4MPa, it is 4-5 hours to control time for adding, after dripping off, continues insulated and stirred reaction 1-2 hours, is then cooled to room temperature, opens
Atmospheric valve is opened, the glyphosate original powder of the activated carbon catalyst or iron-molybdic catalyst and output of addition is recovered by filtration, by filtrated stock
Under conditions of fine vacuum, stop distillation after being distilled into molten condition, contain formic acid by-product in the aqueous solution for steaming, can return
Receive；Atmospheric valve is opened, continues 1-2 hours are stirred under conditions of 78-104 DEG C, plus 30 grams of dissolvings of pure water, cooling, secondary filter,
Filter cake is ureaformaldehyde slow release fertilizer, and secondary filter mother solution is glyphosate isopropylamine salt water solution, or is sylvine aqua with glyphosate, or
Person is sodium glyphosate water preparation, and with glycine, the total recovery of gyphosate solution is 82%.
Embodiment 4
Acidproof stirring-type autoclave pressure reactor is selected, the N- methylol glyphosate aqueous solutions that mass concentration is 20% are put into
100 grams, or 100 grams of the N- methylol glyphosate dimethyl esters methanol aqueous solution that input mass concentration is 20%, start stirring, use
The pH value of solution is adjusted to 4.5-8.5 by 2-aminopropane. or potassium hydroxide or sodium hydroxide, adds the carbamide 6 that mass concentration is 99%
Gram or so, or 4.8 grams -15 grams of the formic acid that addition mass concentration is 99%；78-118 DEG C is warming up to slowly, addition pressure is
The oxygen of 0.15-0.4MPa, or excess air is continuously added, the pressure of control pressure kettle reactor is 0.15-
0.4Mpa or so, continues insulated and stirred reaction 5-7 hours, then lowers the temperature, under conditions of fine vacuum, be distilled into molten condition
Stop distillation afterwards, it is containing by-product and the formic acid for adding in the aqueous solution for steaming, recyclable to apply mechanically；Atmospheric valve is opened, is continued in 78-
Stirring reaction 1-2 hour under conditions of 104 DEG C, plus 30 grams of dissolvings of pure water, cooling are filtered, ureaformaldehyde slow release of the filter cake for coproduction
Fertilizer, filtrated stock are glyphosate isopropylamine salt water solution, or are sylvine aqua with glyphosate, or are sodium glyphosate water preparation,
With glycine, the total recovery of gyphosate solution is 84%.
Embodiment 5
Acidproof electric stirring reactor is selected, 80-180 gram of the Phosphorous chloride. that temperature is -8 DEG C is put into, is started stirring, delay
38 grams of the N that slow Deca is prepared by above-described embodiment 1, N- dihydroxymethyl glycine hydrochloride liquid crystal, time for adding 4-5 is little for control
When, 10 DEG C of dropping temperature of control is following, drips off follow-up continuous insulation reaction 1-2 hour, then using temperature below 10 DEG C and energy
The filter of isolation air is filtered, and leaches remaining Phosphorous chloride., recovery, and filter cake is N- methylols (N- phosphonos two
Chloro methyl) glycine solidss, the solidss are pulverized below 10 DEG C with the machine of designed, designed, input electric stirring is anti-
In answering device, less than 10 DEG C, dropping temperature is 2 DEG C or so of pure water to control temperature of reactor, or dropping temperature is 2 DEG C or so
Absolute methanol, time for adding 5-7 hours, in 20-30 DEG C of insulation reaction 1-2 hour, then under a high vacuum, control temperature is not
More than 70 DEG C, the hydrogen chloride being evaporated in net reactor as far as possible and water, distillation substrate are N- methylols glyphosate and its N- methylols
The mixture product of glyphosate salt hydrochlorate, or for N- methylols glyphosate diformazan ester products and its mixing produce of hydrochlorate
Thing, with glycine, product yield is more than 90%.
Embodiment 6
Acidproof stirring-type autoclave pressure reactor is selected, the N- methylol glyphosate aqueous solutions that mass concentration is 20% are put into
100 grams, or 100 grams of the N- methylol glyphosate dimethyl esters methanol aqueous solution that input mass concentration is 20%, while input 12
Gram mass concentration is 50% carbamide and 10 grams of activated carbon catalysts or iron-molybdic catalyst, or while puts into 20 gram mass concentration
For 50% formic acid, start stirring, the pH value of aqueous solution or methanol solution is adjusted with 2-aminopropane. or potassium hydroxide or sodium hydroxide
For 4.8-8.5, or without adjusting PH with base value, oxygen is subsequently adding, the pressure for controlling oxygen in reactor is 0.15-0.4MPa,
Controlling reaction temperature is 90-118 DEG C, response time 4-8 hour, and cooling is filtered, leaches activated carbon catalyst or iron-molybdic catalyst
With the glyphosate original powder of output, recovery distills filtrated stock to molten condition, containing by-product in the aqueous solution for steaming
Formic acid and the formic acid for adding, recyclable to apply mechanically, under conditions of 50-80 DEG C, insulation reaction 2-4 hour is cooled to room temperature, plus pure
The dissolving of 25 grams of water, secondary filter, filter cake is ureaformaldehyde slow-release fertilizer, and filtrated stock is glyphosate isopropylamine salt water solution or glyphosate
Sylvine aqua or sodium glyphosate water preparation, in terms of N- methylol glyphosates, gyphosate solution yield is more than 90%.
Embodiment 7
Acidproof stirring-type autoclave pressure reactor is selected, the N- methylol glyphosate solutions that mass concentration is 20% are put into
100 grams, or 100 grams of the N- methylol glyphosate diformazans ester solution that input mass concentration is 20%, while putting into mass concentration
For 50% 12-24 gram of carbamide, or 18-36 gram of the formic acid that input mass concentration is 50%, start stirring, with 2-aminopropane. or hydrogen
The pH value of potassium oxide or sodium hydrate regulator solution is 4.8-8.5, or without adjusting PH with base value, is then continuously added excessive
Air or oxygen or hydrogen peroxide, it is 0.15-0.4MPa to control the pressure in reactor, and controlling reaction temperature is 78-118 DEG C, instead
4-8 hours between seasonable；Under conditions of less than 104 DEG C, the water being evaporated in net reactor contains coproduction in the aqueous solution for steaming
Formic acid and add formic acid, it is recyclable to apply mechanically；Under conditions of 78-118 DEG C, insulation reaction 1-2 hour is cooled to room temperature,
Plus 30 grams of dissolvings of pure water, filtering, filter cake is ureaformaldehyde slow-release fertilizer and the mixture of glyphosate original powder, and filtrated stock is glyphosate
Isopropamide AS or sylvine aqua with glyphosate or sodium glyphosate water preparation, in terms of the sweet phosphine of hydroxyl, gyphosate solution yield is 87%
More than.
Embodiment 8
The reactor of immobilized activated carbon catalyst or immobilized iron-molybdic catalyst is selected, N- of the mass concentration for 40-60% is thrown
100 grams of methylol glyphosate aqueous solution, or the N- methylol glyphosate dimethyl ester methanol aqueous solutions that input mass concentration is 20%
100 grams, while 30-72 gram of the carbamide that mass concentration is 50% is added, or the formic acid 28-55 that input mass concentration is 50%
Gram, start stirring or reaction mass circulating pump, be 4.8- with 2-aminopropane. or potassium hydroxide or sodium hydrate regulator solution pH value
8.5,78-118 DEG C is warming up to, excess air or oxygen or hydrogen peroxide is continuously added, is controlled reactor pressure 0-
0.15MPa, insulation reaction time 4-8 hours, then distills, and water in reactor is evaporated only, containing connection in the aqueous solution for steaming
The formic acid of product and the formic acid for adding, it is recyclable to apply mechanically, under conditions of 78-104 DEG C, insulation reaction 1-2 hour, cooling, filtration,
Filter cake is ureaformaldehyde slow-release fertilizer, and filtrated stock is glyphosate isopropyl amine salt aqueous solution or glyphosate potassium saline solution or glyphosate sodium
The water of these aqueous solutions is steamed 80% by saline solution, and then cooling, crystallization, filtration, drying, obtain glyphosate isopropyl amine salt
Former powder or glyphosate potassium original powder or sodium glyphosate original powder, former powder content is 97%, in terms of N- methylol glyphosates, glyphosate
The yield of salt original powder is 89%.
Embodiment 9
Acidproof stirring-type autoclave pressure reactor is selected, the N- methylol glyphosate aqueous solutions that mass concentration is 40% are put into
100 grams, or 100 grams of PMIDA or the glyphosine aqueous solution that input mass concentration is 20%, while put into mass concentration being
10-20 gram of 50% carbamide, or 10-20 gram of the formic acid that mass concentration is 50% is added, start stirring, temperature is controlled for 78-118
DEG C, add oxygen or add 24 grams of the hydrogen peroxide that mass concentration is 30%, or continuously add excess air；Control is anti-
Pressure in device is answered to be 0.15-0.4MPa, insulated and stirred reaction 4-8 hours carry out middle control analysis with glyphosate GB chromatography,
Reaction end is when Zhi amount Nong Du≤1% of N- methylols glyphosate or PMIDA in reaction mass, normal pressure is depressurized to,
Less than 10 DEG C are cooled to, are crystallized 2 hours, filtered, dry, obtain glyphosate 30 grams of powder of original, mass concentration is 97% or so；Add
Carbamide or formic acid are all dissolved in filtrated stock, recyclable to apply mechanically
Embodiment 10
Acidproof electric stirring reactor is selected, the sweet phosphine of hydroxyl (the i.e. N- methylols glyphosate) water that mass concentration is 30% is thrown
100 grams of solution, or the sweet phosphine ester of hydroxyl (the i.e. N- methylols glyphosate dimethyl ester) methanol aqueous solution 100 that input mass concentration is 20%
Gram, while adding 12-24 gram of the carbamide that mass concentration is 50%, start stirring, be warming up to 78-118 DEG C, when insulated and stirred is reacted
Between 8-10 hours, cooling, filter, filter cake be glyphosate original powder, drying, mass concentration be more than 95%, in terms of the sweet phosphine of hydroxyl or with
The sweet phosphine ester meter of hydroxyl, the yield of glyphosate original powder is 88%；Water in filtrated stock is steamed out, under conditions of 78-118 DEG C,
Continue insulation reaction 1-2 hour, lower the temperature, secondary filter, filter cake are urea-formaldehyde fertilizer, the filtrated stock can be careless directly as preparing
The solvent of sweet phosphine water preparation.
Embodiment 11
N prepared by the step of choosing above-described embodiment 11,38 grams of N- dihydroxymethyl glycine hydrochlorides liquid crystal, input stirring
In reactor, 22-24 gram of the dimethylphosphite methanol solution that mass concentration is 50-98% is slowly added into, or is slowly added into
Mass concentration is 17-24 gram of the phosphorous acid of 70-98%, is warming up to 60 DEG C -105 DEG C, and under conditions of normal pressure or decompression, stirring is anti-
4-8 hours are answered, and middle control analysis are carried out with glyphosate GB chromatography, N in reaction mass, N- dihydroxymethyls glycine and its salt
Reaction end is when the quality of hydrochlorate is containing amount≤1%, reaction mass at this moment is N- methylol glyphosate diformazan ester hydrochlorides
Salt product, or be N- methylol glyphosate hydrochloride products, the 120-170 gram of dissolving of absolute methanol or deionized water is added, is matched somebody with somebody
Be made for the N- methylol glyphosate dimethyl ester methanol solutions of 20-30%, or prepare become 30-60% N- methylol grass it is sweet
Phosphine aqueous solution, can be directly as the raw material of production glyphosate or merchandise sales, and product yield is more than 90%.
Embodiment 12
The mass concentration for choosing the preparation of above-described embodiment 11 is 20% N- methylol glyphosate dimethyl esters methanol solution 100
Gram, or 100 grams of the N- methylol glyphosates aqueous solution that mass concentration is 40% is chosen, in input stirring reactor, while
60-90 gram of the dilute hydrochloric acid that mass concentration is 10-15% is added, is started stirring, is slowly warming up to 65-75 DEG C, stir distillation reaction
1-2 hours；85-95 DEG C is continuously heating to, distillation reaction 1-2 hours are stirred；105-115 DEG C is continuously heating to, stirring distillation is anti-
1-2 hours are answered, 118-120 DEG C is continuously heating to, distillation reaction 0.5-1 hours are stirred, deacidification of then reducing pressure is evaporated net reactant
Hydrogen chloride in material, plus 15-20 gram of deionized water, are cooled to room temperature, crystallize 8 hours, filter, and obtain 13 grams of glyphosate original powder or 29
Gram or so, content is more than 95%, coproduction chloromethanes and dimethoxym ethane, without any salts such as triethylamine hydrochlorides in filtrated stock
Material, can be directly as the solvent application for preparing gyphosate solution.
Embodiment 13
Acidproof electric stirring reactor is selected, 30.6 grams of the glycine that mass concentration is 98% is put into, input quality is dense
25.5 grams of the paraformaldehyde for 94% is spent, 118 grams of the technical hydrochloric acid that mass concentration is 30% is put into, is started stirring, in fine vacuum
Under conditions of, 59-60 DEG C is slowly warming up to, vacuum distillation 3-5 hours, distillation substrate are N, N- dihydroxymethyl glycine hydrochlorides
Salt liquid crystal；Under conditions of normal pressure or decompression and 60 DEG C, start Deca mass concentration for the dimethylphosphite of 80-98%
48-55 gram of methanol solution, under conditions of 60-105 DEG C, continues insulation reaction 4-8 hour, is then slowly added into absolute methanol
50-100 gram, room temperature is cooled to, obtains the N- methylol glyphosate diformazan ester hydrochlorides that mass concentration is 20-40% --- also referred to as
For N- methylols (N- dimethyl phosphate ylmethyls) glycine hydrochloride product, with glycine, the yield of the product is 90%
Left and right；The product is sent to the hydrolysis deacidification work that traditional glycine dimethyl phosphate method produces glyphosate as intermediate or raw material
Sequence, by the hydrolysis of traditional handicraft, crystallization, filtration, drying process, obtain glyphosate that mass concentration is 95% original powder, with
Glycine, glyphosate original powder yield up to 78%, while coproduction chloromethanes and dimethoxym ethane.
Embodiment 14
Acidproof electric stirring reactor is selected, N prepared by above-described embodiment 13 or embodiment 1, N- dihydroxymethyls is put into
100 grams of glycine hydrochloride liquid crystal, starts stirring, controls temperature for 58-60 DEG C, and Deca mass concentration is in atmospheric conditions
48-58 gram of the phosphorous acid of 80-98%, after completion of dropping, is warming up to 80-98 DEG C, and stirring reaction 1-2 hour uses glyphosate GB
Chromatography trace analysises, are during quality Han Liang≤1% of the N in reaction mass, N- dihydroxymethyl glycine hydrochloride anti-
Terminal, reaction mass is answered to be N- methylols (N- phosphonic acids ylmethyls) glycine hydrochloride product, mass content is 75.8-
78.8%, with N, N- dihydroxymethyl glycine hydrochloride meters, product yield is 90%.
Embodiment 15
Acidproof electric stirring reactor, supporting installation reaction mass outer circulation pump and defecator are selected, quality is put into
Concentration is 100 grams of 40% N- methylols glyphosate or its hydrochloric acid saline solution, starts stirring, while opening outer circulation pump and mistake
Filter system, under conditions of normal pressure, controls temperature for 25-55 DEG C, is slowly added into 20-40 gram of the carbamide that mass concentration is 50%,
Stirring insulation reaction is about 4-8 hours, carries out middle control analysis with glyphosate GB liquid chromatography, the N- hydroxyls in reaction mass
Reaction end is during quality Han Liang≤1% of methyl glyphosate, room temperature is cooled to, stirring and outer circulation pump is closed, from filtration
Take out filter cake in device, as the mixture product of glyphosate original powder and oligomeric methylene urea (urea-formaldehyde fertilizer), the mixture is sent to
Separation circuit obtains glyphosate original powder, and content is 97%, and in terms of N- methylol glyphosates, the yield of glyphosate original powder is 97%,
The yield of the oligomeric methylene urea (urea-formaldehyde fertilizer) of coproduction is 97% or so.
Embodiment 16
Acidproof electric stirring reactor is selected, N- methylols glyphosate or its hydrochlorate that mass concentration is 20% is put into
100 grams of aqueous solution, start stirring, under conditions of normal pressure, with 2-aminopropane. or potassium hydroxide or sodium hydroxide water transfer solution
PH value is 4-5, controls temperature for 25-55 DEG C, is slowly added into 5-10 gram of the carbamide that mass concentration is 98%, insulated and stirred reaction 4-
8 hours, cooling, standing, filtration, oligomeric methylene urea of the filter cake for coproduction, in terms of N- methylol glyphosates, oligomeric methylene urea yield
For 95%, preparing after filtrated stock concentration becomes the glyphosate isopropylamine salt water solution or glyphosate potassium that mass concentration is 40%
Water preparation or sodium glyphosate water preparation, gyphosate solution yield are 97% or so.
Embodiment 17
Reaction mass to terminal is reacted in the reactor for selecting above-described embodiment 15, the reaction mass has been sent into stirring
Formula autoclave pressure reactor, while 5-10 gram of activated-carbon catalyst is put into in the autoclave pressure reactor, starts stirring, slowly heats up
The air of oxygen or excess to 70-80 DEG C, is added, and reactor pressure is controlled for 0.15-0.2MPa, insulated and stirred reaction 15-
17 hours, at this moment the glyphosine in reaction mass have been converted into glyphosate, glyphosine conversion ratio is more than 98%, with glyphosine
Meter, glyphosate yield are more than 95%, cooling, filtration, and filter cake is the mixture of glyphosate original powder and activated-carbon catalyst, should
Mixture is sent to separation circuit, isolates glyphosate and activated-carbon catalyst, and filtrated stock can be directly as preparation glyphosate
The solvent of water preparation.
Claims (6)
1. it is a kind of combination glycine and Phosphorous chloride. and these three Material synthesis glyphosates of formaldehyde and its gyphosate solution method,
Or a kind of method of combination glycine and phosphorous acid and these three Material synthesis glyphosates of formaldehyde and its water preparation, or a kind of group
The method for closing glycine and dimethylphosphite and these three Material synthesis glyphosates of formaldehyde and its water preparation, it is characterised in that sweet
Propylhomoserin and Phosphorous chloride. and formaldehyde these three material combinations synthesize together N- methylols glyphosate and its hydrochloride intermediate or
Synthesis N- methylol glyphosate dimethyl esters and its hydrochloride intermediate, or it is a kind of glycine and phosphorous acid and formaldehyde these three
Material combination synthesizes N- methylols glyphosate and its hydrochloride intermediate, or one kind together glycine and dimethylphosphite
Synthesize N- methylol glyphosate dimethyl esters and its hydrochloride intermediate together with formaldehyde these three material combinations, and by this centre
Body eliminates this functional group of methylol by the approach of reversible reaction balanced sequence, so as to be converted into glyphosate original powder and glyphosate
Water preparation；Distinct feature is that and Sodium Chloride effluent brine will not be produced due to whole preparation process, therefore also just eliminate traditional mode of production
The package unit of PROCESS FOR TREATMENT glyphosate effluent brine, including the sodium chloride salt incinerator that current manufacturing enterprise is currently in use.
2. a kind of combination glycine and Phosphorous chloride. and these three Material synthesis of formaldehyde N- methylols glyphosate and its hydrochlorate or
Person synthesizes the method for N- methylol glyphosate dimethyl esters and its hydrochlorate, or a kind of combination glycine and phosphorous acid and formaldehyde this
The method of three kinds of Material synthesis N- methylols glyphosates and its hydrochlorate, or a kind of combination glycine and dimethylphosphite and
The method of formaldehyde these three Material synthesis N- methylol glyphosate dimethyl esters and its hydrochlorate, it is characterised in that glycine and three
Phosphorus chloride and these three material combinations of formaldehyde are together as preparation N- methylols glyphosate and its hydrochlorate or preparation N- hydroxyl first
The purposes of the reaction substrate of base glyphosate dimethyl ester and its hydrochlorate, or glycine and dimethylphosphite and formaldehyde this
Three kinds of material combinations are together as the reaction bottom for preparing N- methylols (N- dimethyl phosphonate ylmethyls) glycine and its hydrochlorate
The purposes of thing, or glycine and phosphorous acid and formaldehyde these three material combinations are prepared N- methylols (N- phosphonate groups together
Methyl) glycine and its hydrochlorate reaction substrate purposes.
3. a kind of application and method as the raw material for preparing glyphosate of carbamide and N- methylols glyphosate, it is characterised in that help a small child urinate by holding his legs apart
Element and N- methylols glyphosate or its hydrochlorate this two kinds of material combinations prepare glyphosate original powder and its water preparation together while coproduction
Oligomeric methylene urea or ureaformaldehyde.
4. it is a kind of three kinds of material combinations of glycine and Phosphorous chloride. and formaldehyde together synthesizing glyphosate original powder and its water preparation side
Method, including several steps of following sequence：
Step 1, N, the preparation of N- dihydroxymethyls glycine and its hydrochlorate
The glycine and formalin of amount of calculation are added in stirring reactor, while the technical hydrochloric acid of amount of calculation is added,
Start stirring, be slowly ramped to 60 DEG C；Then in fine vacuum and less than under conditions of 60 DEG C, distillation 3-5 hours or so, distillation
Substrate is N, N- dihydroxymethyl glycine hydrochloride liquid crystal；
The preparation of step 2, N- methylols glyphosate and its hydrochlorate or N- methylol glyphosate dimethyl esters and its hydrochlorate
2.1 N, N- dihydroxymethyl glycine hydrochloride liquid crystal is cooled to subzero 5 degrees Celsius (- 5 DEG C) below, and slowly Deca is calculated
The temperature of amount is -8 DEG C of Phosphorous chloride., probably the Phosphorous chloride. of the 70% of Deca amount of calculation when stop stirring, continue slowly plus
Enter and do not drip remaining Phosphorous chloride., 24 hours are stood below 4 DEG C, then drained unnecessary three in net reactor with vacuum
Phosphorus chloride, the pure water of Deca amount of calculation below 2 DEG C, or the absolute methanol of Deca amount of calculation, start after standing 10 hours and stir
Mix, in 20 DEG C of -30 DEG C of insulated and stirred reaction 2-3 hours；High vacuum distillation, control temperature are less than 70 DEG C, steam chlorination as far as possible
Hydrogen and water, distill the mixture that substrate is N- methylols glyphosate and N- methylol glyphosate salt hydrochlorates, or distillation substrate
The as mixture of N- methylols glyphosate dimethyl ester and N- methylol glyphosate diformazan ester hydrochlorides；
2.2 select acidproof electric stirring reactor, put into the Phosphorous chloride. of the amount of calculation that temperature is -8 DEG C, start stirring, control
Temperature processed below 10 DEG C, slowly Deca above-mentioned steps 1 prepare amount of calculation N, N- dihydroxymethyl glycine hydrochloride liquid crystal,
Time for adding and insulation reaction time common 5-7 hours, then less than 10 DEG C and under conditions of isolation air, filter out residue
Phosphorous chloride., filter cake be N- methylols (N- phosphonyl dichloride ylmethyls) glycine intermediate；Then the intermediate is put into
In reactor, slowly dropping temperature is the absolute methanol of the amount of calculation that the pure water or dropping temperature of 2 DEG C of amount of calculation are 2 DEG C,
20-30 DEG C of insulated and stirred reacts 2-3 hours；High vacuum distillation, control temperature are less than 70 DEG C, steam hydrogen chloride and water as far as possible,
Distillation substrate is the mixture of N- methylols glyphosate and N- methylol glyphosate salt hydrochlorates, or distillation substrate is N- hydroxyls
Methyl glyphosate dimethyl ester and its hydrochloride product；
2.3rd, acidproof electric stirring reactor is selected, puts into the N of the amount of calculation prepared by above-mentioned steps 1, N- dihydroxymethyls are sweet
Propylhomoserin hydrochlorate liquid crystal, is warming up to 60-105 DEG C, under conditions of normal pressure or decompression, is slowly added into the phosphorous acid diformazan of amount of calculation
The phosphorous acid of ester or addition amount of calculation, stirring reaction 4-8 hour, reaction mass become N- methylol glyphosate diformazan ester hydrochlorides
Or N- methylol glyphosate salt hydrochlorates.
The preparation of step 3, glyphosate original powder and its water preparation
3.1st, acidproof stirring-type autoclave pressure reactor is selected, puts into the N- methylol of the mass concentration for 20-40 ﹪ of amount of calculation
Glyphosate and its hydrochloric acid saline solution, or input amount of calculation mass concentration be 20 ﹪ N- methylol glyphosate dimethyl esters it is molten
Liquid, starts stirring, and it is 2 to adjust solution ph with alkali, adds the sodium tungstate of amount of calculation, in the matter of 60 DEG C or so slowly Deca amounts of calculation
Amount concentration is 30% hydrogen peroxide, time for adding and insulated and stirred response time common 10-12 hours；Then add the urine of amount of calculation
Element or without carbamide, addition amount of calculation formic acid or without formic acid, be slowly warming up to 78-104 DEG C, start Deca calculate
The mass concentration of amount is the ferrous sulfate aqueous solution of 10 ﹪, time for adding and insulated and stirred response time common 5-7 hours；It is cooled to
Less than 10 DEG C, crystallize 2 hours, filter, drying obtains glyphosate original powder, and content is more than 95%.
3.2nd, acidproof stirring-type autoclave pressure reactor is selected, puts into the N- methylol of the mass concentration for 20-40% of amount of calculation
Glyphosate and its HCI solution, or input amount of calculation mass concentration be 20% N- methylol glyphosate dimethyl esters and its
HCI solution, while the activated carbon or iron-molybdic catalyst and carbamide of amount of calculation are put into, or the activated carbon or ferrum of input amount of calculation
Molybdenum catalyst and formic acid；Start stirring, it is 4.5-8.5 the pH value of solution to be adjusted with 2-aminopropane. or potassium hydroxide or sodium hydroxide, or
Person controls temperature for 78-104 DEG C without adjusting PH with base value, and control pressure is 0.15-4MPa, and the quality for starting Deca amount of calculation is dense
Spend the hydrogen peroxide for 30%, or add the oxygen of certain pressure, or continuously add excess air, time for adding and
Insulated and stirred response time common 4-8 hours, until N- methylols glyphosate or N- methylol glyphosate diformazan ester hydrolysis reactions are complete
Entirely, room temperature is cooled to, filters out activated carbon and glyphosate original powder；Under vacuum filtrated stock is distilled to molten condition,
Temperature is controlled for 78-104 DEG C, then insulation reaction 2 hours carries out secondary filter, and filter cake is urea-formaldehyde fertilizer, secondary filter
Mother solution is glyphosate isopropylamine salt water solution or sylvine aqua with glyphosate or sodium glyphosate water preparation, and the water in the water preparation is evaporated
Only, dry, as glyphosate isopropyl amine salt original powder or glyphosate potassium original powder or sodium glyphosate original powder.
5. with N- methylols (N- phosphonic acids ylmethyls) glycine and its hydrochlorate as raw material or intermediate prepare glyphosate original powder and
The application of its water preparation；With N- methylols (N- dimethyl phosphonate ylmethyls) glycine and its hydrochlorate as raw material or prepared by intermediate
The application of glyphosate original powder and its water preparation.
6. a kind of method for adopting glycine and dimethylphosphite that glyphosate is prepared for raw material, it is characterised in that entirely preparing
During need not add the alkaline reagents such as triethylamine or potassium hydroxide or sodium hydroxide, do not produce N- methylols (N- phosphonic acids two
Methyl ester ylmethyl) glycine triethylamine salt intermediate, or the salts substances such as triethylamine hydrochloride and Sodium Chloride are not produced, it is not required to
Want the device such as triethylamine removal process and its Sodium Chloride incinerator.
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| CN101851253A (en) * | 2009-04-02 | 2010-10-06 | 李坚 | Triethylamine-free method for preparing glyphosate |
| CN101885740A (en) * | 2009-05-11 | 2010-11-17 | 李坚 | New preparation method of herbicide glyphosate |
| CN102161678A (en) * | 2010-02-23 | 2011-08-24 | 李坚 | Glycine and application of acid salt thereof in preparation of glyphosate |
| CN102649799A (en) * | 2011-02-23 | 2012-08-29 | 重庆紫光化工股份有限公司 | Preparation method for glyphosate |
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|---|---|---|---|---|
| CN101851253A (en) * | 2009-04-02 | 2010-10-06 | 李坚 | Triethylamine-free method for preparing glyphosate |
| CN101885740A (en) * | 2009-05-11 | 2010-11-17 | 李坚 | New preparation method of herbicide glyphosate |
| CN102161678A (en) * | 2010-02-23 | 2011-08-24 | 李坚 | Glycine and application of acid salt thereof in preparation of glyphosate |
| CN102649799A (en) * | 2011-02-23 | 2012-08-29 | 重庆紫光化工股份有限公司 | Preparation method for glyphosate |
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