JP3987488B2 - N−ホスホノメチルグリシンの回収方法 - Google Patents
N−ホスホノメチルグリシンの回収方法 Download PDFInfo
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- JP3987488B2 JP3987488B2 JP2003507107A JP2003507107A JP3987488B2 JP 3987488 B2 JP3987488 B2 JP 3987488B2 JP 2003507107 A JP2003507107 A JP 2003507107A JP 2003507107 A JP2003507107 A JP 2003507107A JP 3987488 B2 JP3987488 B2 JP 3987488B2
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- phosphonomethylglycine
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 44
- 239000012528 membrane Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 37
- 239000012466 permeate Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 26
- -1 ammonium halide Chemical class 0.000 claims description 18
- 239000012527 feed solution Substances 0.000 claims description 14
- 150000004820 halides Chemical group 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001728 nano-filtration Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000011026 diafiltration Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 6
- 150000008045 alkali metal halides Chemical class 0.000 claims description 6
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003204 osmotic effect Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 206010021036 Hyponatraemia Diseases 0.000 description 2
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 101000995114 Doryteuthis pealeii 70 kDa neurofilament protein Proteins 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940090948 ammonium benzoate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-O benzylaminium Chemical compound [NH3+]CC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-O 0.000 description 1
- 239000012455 biphasic mixture Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical group CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 150000003681 vanadium Chemical class 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)]
-
- 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)
- Separation Using Semi-Permeable Membranes (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
で表されるヘキサヒドロトリアジン誘導体を、式:P(OCOR3)3[但し、R3が、特にフェニルを表す。]で表されるトリアシルホスフィットと反応させ、そして得られた生成物を加水分解する、N−ホスホノメチルグリシンの製造方法が開示されている。N−ホスホノメチルグリシンはpH0.5〜2において晶析により反応混合物から回収される。母液は、ホスホノメチルイミノ二酢酸の酸化で得られる母液とは完全に異なる組成を有する。それは、さらにかなりの量のN−ホスホノメチルグリシン、少量のアミノメチルホスホン酸、グリシン及びビス(ホスホノメチル)グリシン、及び大量の塩化物の塩を含んでいる。重要な物質の損失を最小にし、また廃水による汚染を最小にすることが望まれる。
(a)混合物のpHを2〜8の範囲の値に調節する工程、
(b)選択ナノろ過膜で混合物の分離を行い、N−ホスホノメチルグリシンがより多く且つハロゲン化物がより少ない残留物(retentate)、及びハロゲン化物がより多く且つN−ホスホノメチルグリシンがより少ない透過物(permeate)を得る工程、そして
(c)N−ホスホノメチルグリシンを、所望により残留物から、回収する工程、
を行うことを特徴とする回収方法。
R1及びR2が、同一でも異なっていても良く、H又はC1〜C4−アルキルを表す。]
で表されるヘキサヒドロトリアジン誘導体を、
式III:
で表されるトリアシルホスフィットと反応させ、そして得られた生成物をハロゲン化水素酸で加水分解する、N−ホスホノメチルグリシンの製造に由来している。反応は溶剤があっても無くても行うことができる。不活性な有機溶剤が使用されることが好ましく、特にハロゲン化炭化水素、例えば1,2−ジクロロエタンを使用することが好ましい。反応成分は、実質的に化学量論量で使用することが便宜である。反応温度は、一般に−10℃〜140℃の範囲である。
0.5〜3質量%、特に0.5〜2.5質量%のN−ホスホノメチルグリシン、
0.01〜0.5質量%のアミノメチルホスホン酸、
0.1〜0.4質量%のグリシン、
0.2〜0.8質量%のビス(ホスホノメチル)グリシン、
10〜25質量%、特に12〜20質量%のハロゲン化アンモニウム/ハロゲン化アルカリ金属又はハロゲン化アルカリ土類金属。
混合物の連続的分離のために、供給溶液Fを膜の位置が定められているハウジングを有する膜ユニットMへ、クロスフロー法で供給する。供給溶液Fは膜に流れ、残留物Rは除去される。所望により、残留物Rの一部が戻される。透過物Pは除去される。
テフロン(登録商標)ブレード攪拌器及び還流冷却器を備えた2Lの撹拌フラスコに、284gの安息香酸アンモニウムを先ず1000mlの1,2−ジクロロエタン中に導入し、そして91.5gの三塩化リンを、窒素雰囲気下、30分間に亘って滴下した。滴下中、温度は36℃の最大値まで上昇した。その後撹拌を25〜36℃で30分間続けた。反応混合物を圧力吸引フィルタを通してろ過し、ろ過ケーキを、窒素雰囲気下、各回、500gのジクロロエタンで2回洗浄した(2054gのろ過物)。
2.10質量%のN−ホスホノメチルグリシン
0.10質量%のアミノエチルホスホン酸
0.20質量%のグリシン
0.45質量%のビス(ホスホノメチル)グリシン
16.70質量%のNaCl/NH4Cl。
ホスホノメチルグリシン94.7%(HPLC)
母液: 106.8gの溶液
実施例1と同様にして得た母液のバッチ式2段階濃縮
母液のpHを実施例1と同様に4に調節した。その後、母液を、実施例1と同じタイプの同じ膜を備えた撹拌受圧器においてバッチ式で濃縮した。条件は実施例1に記載通りである。透過物を同じ膜を備えた同じタイプの別の撹拌受圧器に供給し、濃縮した。濃縮を40℃、40バールで行った。平均透過物流率は25.70kg/m2hであった。両方のナノろ過段階で計算されたN−ホスホノメチルグリシンの残留物は99.99%で、そして塩化物塩の消耗は77.82%であった。結果を下記の表2にまとめる。
Claims (13)
- N−ホスホノメチルグリシン、ハロゲン化アンモニウム、及びハロゲン化アルカリ金属若しくはハロゲン化アルカリ土類金属、さらに任意に、溶解状態の有機不純物を含む水性混合物から、N−ホスホノメチルグリシンを回収する方法であって、
(a)混合物のpHを2〜8の範囲の値に調節する工程、
(b)選択ナノろ過膜で混合物の分離を行い、N−ホスホノメチルグリシンがより多く、ハロゲン化物がより少ない残留物、及びハロゲン化物がより多く、N−ホスホノメチルグリシンがより少ない透過物を得る工程、そして
(c)N−ホスホノメチルグリシンを残留物から回収する工程、
を行うことを特徴とする回収方法。 - 式IIのトリアジンと式IIIのトリアシルホスフィットとの反応、得られた生成物の塩酸を用いた加水分解、及びpH0.5〜2でのN−ホスホノメチルグリシン分離の後に、母液として得られる混合物を使用する請求項2に記載の方法。
- 混合物が、0.5〜3質量%のN−ホスホノメチルグリシン及び10〜25質量%の塩化物の塩を含んでいる請求項3に記載の方法。
- 混合物のpHが、2.5〜6.5の範囲の値に調節される請求項1〜4のいずれかに記載の方法。
- 工程(b)で、50〜1000Dの範囲の分離限界を有する膜を使用する請求項1〜5のいずれかに記載の方法。
- 膜が、100〜500Dの範囲の分離限界を有する請求項6に記載の方法。
- 工程(b)における混合物の分離を、残留物側と透過物側との間の膜透過圧力を30〜100バールの範囲にして行う請求項1〜7のいずれかに記載の方法。
- 工程(b)における混合物の分離を、0.1〜5m/秒の範囲の流速で行う請求項1〜8のいずれかに記載の方法。
- 工程(b)における分離を、透過物を供給溶液としてある段階から次の段階に供給することにより、多段階で行う請求項1〜9のいずれかに記載の方法。
- 第2段階或いはさらなる段階での残留物を、少なくとも一部、第1の又は前の段階に供給する請求項10に記載の方法。
- 工程(b)で得られる残留物を、少なくとも一つのダイアフィルトレーション工程に付す請求項1〜11のいずれかに記載の方法。
- 透過物を、ハロゲン化アンモニウムに含まれるアンモニア又はアミンを遊離させるために、強塩基で処理する請求項1〜12のいずれかに記載の方法。
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DE10130136A DE10130136A1 (de) | 2001-06-22 | 2001-06-22 | Verfahren zur Gewinnung von N-Phosphonomethylglycin |
PCT/EP2002/006903 WO2003000704A2 (de) | 2001-06-22 | 2002-06-21 | Verfahren zur gewinnung von n-phosphonomethylglycin |
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AR039201A1 (es) * | 2003-03-28 | 2005-02-09 | Atanor S A | Procedimiento para purificar soluciones de glifosato mediante nanofiltracion |
TW200538459A (en) * | 2004-05-21 | 2005-12-01 | Dow Agrosciences Llc | Purification of n-(phosphonomethyl)glycine |
EP1886976A1 (en) | 2006-08-09 | 2008-02-13 | Thermphos Trading GmbH | Method of scale inhibition |
US7771494B2 (en) * | 2007-01-31 | 2010-08-10 | Monsanto Technology Llc | Process for selective removal of water and impurities from N-(phosphonomethyl)glycine |
EP2090646A1 (en) | 2008-01-22 | 2009-08-19 | Thermphos Trading GmbH | Surface treatment composition containing phosphonic acid compounds |
EP2082991A1 (en) | 2008-01-22 | 2009-07-29 | Thermphos Trading GmbH | Method of Water Treatment |
CN102459091B (zh) * | 2009-05-18 | 2014-06-18 | 孟山都技术公司 | 含水废物流中磷有用成分和盐杂质的回收 |
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US3950402A (en) * | 1972-05-31 | 1976-04-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
US3969398A (en) * | 1974-05-01 | 1976-07-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
RO65811A (fr) | 1974-06-26 | 1979-07-15 | Budapesti Vegyimuevek | Procede pour obtenir du n-phosphonombethyl-glycine |
HU184601B (en) * | 1979-07-09 | 1984-09-28 | Alkaloida Vegyeszeti Gyar | Process for producing n-/phosphono-methyl/-glycine |
PL159424B1 (pl) * | 1989-04-18 | 1992-12-31 | Sposób wytwarzania N-fosfonometyloglicyny PL | |
EP0806428B1 (en) | 1994-11-09 | 2003-01-29 | Showa Denko Kabushiki Kaisha | Method for isolating N-phosphonomethylglycine |
US5587083A (en) | 1995-04-17 | 1996-12-24 | Chemetics International Company Ltd. | Nanofiltration of concentrated aqueous salt solutions |
IT1281094B1 (it) * | 1995-12-21 | 1998-02-11 | Graziello Donadello | Procedimento per la produzione di n-fosfonometilglicina e/o suoi sali |
AR027024A1 (es) | 1999-12-23 | 2003-03-12 | Basf Ag | Procedimiento para la preparacion de n-fosfonometilglicina |
AR029508A1 (es) | 2000-04-14 | 2003-07-02 | Dow Agrosciences Llc | Proceso para remover y recuperar cloruro de sodio de los efluentes de desecho provenientes de los procesos de fabricacion del acido n-fosfometiliminodiacetico (pmida) |
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