CN1308633A - 制备n－膦酰基甲基甘氨酸盐 - Google Patents
制备n－膦酰基甲基甘氨酸盐 Download PDFInfo
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical class OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 55
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000002739 metals Chemical class 0.000 claims description 16
- 239000010970 precious metal Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 239000003637 basic solution Substances 0.000 abstract 1
- 230000002363 herbicidal effect Effects 0.000 abstract 1
- 239000004009 herbicide Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
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- 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)
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种制备N－膦酰基甲基甘氨酸盐的方法,通过N－膦酰基甲基亚氨基双乙酸的盐,其中成盐阳离子选自碱金属、碱土金属、铵和有机铵,在氧气存在下,于碱性水溶液或水溶液中,并在负载在固体载体上的贵金属催化剂存在下,在加压和升温下反应,该方法的特征在于(a)贵金属选自铂、钯或铂与钯的混合物,以及铂或钯分别或一起与钌、铑、锇或铱的混合物,和(b)另外与至少一种选自铋、铅、锡、碲、锗、矾、铬、铁、锰、钼和钨的掺杂金属混合。已知的除草剂N－膦酰基甲基甘氨酸可从N－膦酰基甲基亚氨基双乙酸制备。
Description
本发明涉及一种催化制备N-膦酰基甲基甘氨酸盐的方法，通过在碱性水溶液中，并在负载于固体载体上的贵金属催化剂存在下，N-膦酰基甲基亚氨基双乙酸与氧气的氧化脱烷基化作用，该方法的特征在于(a)贵金属选自铂、钯或铂与钯的混合物，以及铂或钯分别或一起与钌、铑、锇或铱的混合物，和(b)另外与至少一种选自铋、铅、锡、碲、锗、矾、铬、铁、锰、钼和钨的金属混合。
式I所示的N-膦酰基甲基甘氨酸
HO2C-CH2--NH--CH2-PO3H2 (I)是已知的除草剂或已知的植物生长调节剂，参见US-A-4 147 719。
从US-A-4 147 719可知，N-膦酰基甲基甘氨酸盐的催化制备方法是已知的，其中式II所示的N-膦酰基甲基亚氨基双乙酸的盐与氧气在碱性水溶液中，并在负载于作为固体载体的活性炭上的铂催化剂存在下反应。该方法的缺点在于：(a)所用的特定载体必须被活化，这增加了催化剂的成本，(b)贵金属限定为铂，以及(c)大量铂溶解在产物中，这与催化剂的失活有关，从而限制了复用性并导致再次使用期间铂的损失。总而言之，这些缺点导致了在工业中不能使用的不经济方法。
已经令人惊讶的发现，(a)铂和钯可单独或一起混合，且另外与其它贵金属混合使用，(b)可使用未活化的固体载体，(c)未观察到催化剂活性或催化剂选择性的损失，以及(d)如果加入至少一种选自铋、铅、锡、碲、锗、矾、铬、铁、锰、钼和钨的其它金属，则贵金属的损失大大降低。通常，得到较高产率且催化剂可重复使用数次。
因此本发明的目的是一种制备N-膦酰基甲基甘氨酸盐的方法，通过N-膦酰基甲基亚氨基双乙酸的盐，其中成盐阳离子选自碱金属、碱土金属、铵和有机铵，在氧气存在下，于碱性水溶液或水溶液中，并在负载于固体载体上的贵金属催化剂存在下，在加压和升温下反应，该方法的特征在于(a)贵金属选自铂、钯或铂与钯的混合物，以及铂或钯分别或一起与钌、铑、锇或铱的混合物，和(b)另外与至少一种选自铋、铅、锡、碲、锗、矾、铬、铁、锰、钼和钨的掺杂金属混合。
优选的碱金属为Li、Na、K、Rb和Cs，最优选Na和K。优选的碱土金属为Mg、Ca、Ba和Sr。有机铵在本发明内容中应理解为伯、仲、叔和季铵的成盐阳离子。N-原子可被具有6-14个碳原子的芳基，具有7-15个碳原子的芳族-脂族基团，或优选具有1-12个碳原子的直链或支链脂族基团，或优选具有3-12个环碳原子的环状脂族基团取代。特别优选的是具有1-4个相同或不同的取代基的有机铵，其中取代基选自1-8，更优选1-6，最优选1-4个碳原子的直链或支链烷基，以及具有5或6个环碳原子的环烷基。特别优选伯C1-C6-烷基铵。成盐阳离子最优选来自于选自Na、K、Mg、Ca和Ba的金属，以及铵(NH4 +)和C1-C6-烷基铵。
为了成盐，将相应的碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵或有机氢氧化铵加入到N-膦酰基甲基亚氨基双乙酸的水溶液中。N-膦酰基甲基亚氨基双乙酸与氢氧化物(或与成盐阳离子)的摩尔比可以为1∶1-1∶2，优选1∶1.5，最优选1∶1.3。反应混合物因此可为碱性、中性或酸性，这取决于摩尔比。
氧气可以纯的形式使用，或与惰性气体混合，例如氮气或稀有气体。氧气通常处于压力下，使得反应在加压下进行，例如1000hPa-10,000hPa，优选1000-5000hPa。
反应温度可为例如30-200℃，优选60-150℃，最优选80-130℃。
固体载体可为例如细碎的活性炭、细碎的SiO2凝胶、SiO2与Al、Ti和/或Zr氧化物的混合凝胶、细碎的硅酸盐无机物(硅藻土、矾土、沸石、皂土、蒙脱石)以及细碎的氧化铝。优选的载体为活性炭。
以载体为基础计，催化剂金属的量优选为1-10，更优选2-5％重量。掺杂金属的用量可以为0.5-10，更优选1-5％重量。贵金属与掺杂金属的重量比优选为1∶20-1∶1，最优选1∶10-1∶1。
优选的贵金属为Pd，特别为Pt。优选的掺杂金属为Bi、Pb和Sn，最优选Bi和Pb。这些优选的贵金属和掺杂金属特别以负载在载体活性炭上使用。已证明特别有效的催化剂是那些在活性炭上含有铂和掺杂金属铋或铅的催化剂，其中铂以3-6％重量的量存在，掺杂金属以1-6％重量的量存在。
包括载体/贵金属/掺杂金属的催化剂的用量，以N-膦酰基甲基亚氨基双乙酸的量为基础计，优选为4-20，更优选4-15，最优选5-10％重量。
本方法可在例如通过在加压容器中，将N-膦酰基甲基亚氨基双乙酸、催化剂和碱加入到水中，且混合物加热到反应温度进行。然后通过施加氧气压力排出空气，反应混合物搅拌或振荡。通过形成CO2使压力增加约500-1000hPa。然后，排出气相，再施加氧气压力。当没有观察到进一步压力增加时，反应完成。例如通过蒸去水和形成的甲醛来分离所需的N-膦酰基甲基甘氨酸盐。酸可从盐以常用方式，通过用酸处理而制备。
在本发明的方法中，产率大大高于90％且在分离的产物中，N-膦酰基甲基甘氨酸(PMG)的含量为至少70％。在分离的产物中贵金属的含量小于10ppm，然而在没有添加掺杂金属的方法中，贵金属的含量大大高于200ppm。在分离的产物中，最初建立高于500ppm量的掺杂金属。当再次使用催化剂时，这一含量大大降低，这取决于再使用的次数，至低于10ppm。催化剂可重复使用多这十次或更多，仅观察到轻微的活性损失。
催化剂是已知的，部分可商购，或可通过类似方法制备，例如从相应的金属盐溶液通过在载体上的还原来分离。
下列实施例更详细地阐明本发明。
实施例1
a) 使用负载在活性炭上的Pt/Bi催化剂
将100ml水、12g(0.049mol)N-膦酰基甲基亚氨基双乙酸(NPDS)
和3.15g(0.053mol)异丙胺放置在加压容器中。然后加入1.0g催化
剂(载在活性炭上的分别3％的Pt和Bi；Degussa CF 196 XR/W B93/11)并加热到90-105℃。然后，施加氧气压力至2000hPa的压力，减压然后在2000hPa再次施加氧气。在反应期间振荡容器。加压至2500hPa后，排出气相，再次施加2巴氧气压力，并继续振荡。2小时后，反应完成。冷却后，滤除催化剂并将反应混合物蒸干。产量为10.7g(96％)NPDS-异丙胺盐；根据HPLC分析，N-膦酰基甲基甘氨酸(PMG)的含量为84％，Pt的含量仅为4ppm。a) 使用载在活性炭上的Pt催化剂
重复实施例a)并使用1.0g催化剂(载在活性炭上的5％Pt)。产量为9.0g(72％)NPDS-异丙胺盐；根据HPLC分析，PMG的含量为79％，Pt的含量为210ppm。实施例2：使用Pt/Pb催化剂
重复实施例1a)并使用1.0g催化剂(载在活性炭上的5％Pt和1％Pb；Degussa CF 101 R/W)。产量为10.0g(96％)NPDS-异丙胺盐；根据HPLC分析，PMG的含量为85％，Pt的含量为5ppm。实施例3-6：再次使用催化剂
重复实施例1a)，所用催化剂为载在活性炭上的分别3％的Pt和Bi；Degussa CF 196 XR/W B93/11(实施例3和4)。分离的催化剂用去离子水洗涤三次，无需进一步处理即再次使用(实施例5和6)。其它细节见表1。
| 实施例号 | 催化剂(g) | 产量(g)(％理论) | 根据HPLC的PMG含量％ | PMG中的Ptppm | PMG中的Bippm |
| 3 | 1(A) | 11.0(98) | 78 | 4 | 840 |
| 4 | 0.08(B) | 10.6(95) | 85 | 6 | 740 |
| 5 | A | 10.4(93) | 85 | 6 | 230 |
| 6 | B | 10.8(96) | 80 | 5 | 33 |
Claims (10)
1.一种制备N-膦酰基甲基甘氨酸盐的方法，通过N-膦酰基甲基亚氨基双乙酸的盐，其中成盐阳离子选自碱金属、碱土金属、铵和有机铵，在氧气存在下，于碱性水溶液或水溶液中，并在负载在固体载体上的贵金属催化剂存在下，在加压和升温下制备，该方法的特征在于(a)贵金属选自铂、钯或钯与铂的混合物，以及铂或钯分别或一起与钌、铑、锇或铱的混合物，和(b)它另外与至少一种选自铋、铅、锡、碲、锗、钒、铬、铁、锰、钼和钨的掺杂金属混合。
2.根据权利要求1的方法，其中成盐阳离子来自于选自Na、K、Mg、Ca和Ba的金属以及铵(NH4 +)和C1-C6-烷基铵。
3.根据权利要求2的方法，其中烷基铵为异丙胺。
4.根据权利要求1的方法，其中N-膦酰基甲基亚氨基双乙酸与成盐阳离子的摩尔比为1∶1-1∶2。
5.根据权利要求1的方法，其中加压为1-10巴。
6.根据权利要求1的方法，其中反应温度为30-200℃。
7.根据权利要求1的方法，其中以载体为基础计，催化剂金属的含量为1-10％重量，掺杂金属的用量为0.5-10％重量。
8.根据权利要求1的方法，其中贵金属与掺杂金属的重量比为1∶20-1∶1。
9.根据权利要求1-8的方法，其中贵金属为Pt，掺杂金属为Bi和Pb，载体为活性炭。
10. 根据权利要求9的方法，其中催化剂是载于活性炭上的铂且含有掺杂金属铋或铅，其中以载体为基础计，铂的含量为3-6％重量，掺杂金属的量为1-6％重量。
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| US (1) | US20010002424A1 (zh) |
| EP (1) | EP1095049B1 (zh) |
| JP (1) | JP2003508344A (zh) |
| CN (1) | CN1308633A (zh) |
| AT (1) | ATE234314T1 (zh) |
| AU (1) | AU5030099A (zh) |
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|---|---|---|---|---|
| CN100372857C (zh) * | 2004-05-12 | 2008-03-05 | 江苏好收成韦恩农药化工有限公司 | N-膦酰基甲基甘氨酸的生产方法 |
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| US6417133B1 (en) | 1998-02-25 | 2002-07-09 | Monsanto Technology Llc | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
| DK1242433T3 (da) | 1999-12-21 | 2004-10-04 | Monsanto Technology Llc | Anvendelse af en supplerende promotor i forbindelse med en carbonstöttet, ædelmetalholdig katalysator i væskefaseoxidationsreaktioner |
| ES2253383T3 (es) | 2000-05-22 | 2006-06-01 | Monsanto Technology Llc | Sistemas de reaccion para fabricar compuestos n-(fosfonometil)glicina. |
| WO2002095373A1 (en) | 2001-05-22 | 2002-11-28 | Monsanto Technology Llc | Use of infrared spectroscopy for on-line process control and endpoint detection |
| AR040319A1 (es) * | 2002-06-28 | 2005-03-23 | Monsanto Technology Llc | Uso de telurio en catalizadores con contenido de metales nobles y con soporte de carbon para reacciones de oxidacion en fase liquida |
| ATE382626T1 (de) | 2003-09-17 | 2008-01-15 | Monsanto Technology Llc | Verfahren zur rückgewinnung eines kristallinen produkts aus einer lösung |
| AR051926A1 (es) | 2004-09-15 | 2007-02-21 | Monsanto Technology Llc | Catalizadores de oxidacion, procedimientos de preparacion de dichos catalizadores y proceso para la elaboracion de n-( fosfonometil)glicina o una sal de la misma |
| US7771494B2 (en) | 2007-01-31 | 2010-08-10 | Monsanto Technology Llc | Process for selective removal of water and impurities from N-(phosphonomethyl)glycine |
| US8252953B2 (en) | 2008-05-01 | 2012-08-28 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
| 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 |
| BR112019027682A2 (pt) | 2017-06-26 | 2020-09-15 | Monsanto Technology Llc | controle de fósforo para fluxos de resíduos provenientes de processos de produção de glifosato |
| CN113684541B (zh) * | 2021-07-15 | 2022-11-01 | 东华大学 | 一种火草绒剥离及收集装置 |
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| US3950402A (en) * | 1972-05-31 | 1976-04-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| NL7713959A (nl) * | 1976-12-20 | 1978-06-22 | Monsanto Co | Werkwijze voor het bereiden van n-fosfono- methylglycinezouten. |
| IL66824A0 (en) * | 1982-06-25 | 1982-12-31 | Geshuri Lab Ltd | Process for producing n-phosphonomethylglycine derivatives and herbicidal compounds and compositions prepared thereby |
| ES2021229A6 (es) * | 1990-03-12 | 1991-10-16 | Ercros Sa | Perfeccionamientos introducidos en un procedimiento de obtencion de n-fosfonometilglicina por oxidacion de n-fosfonometiliminodiacetico. |
| US6417133B1 (en) * | 1998-02-25 | 2002-07-09 | Monsanto Technology Llc | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
-
1999
- 1999-07-02 DE DE69905894T patent/DE69905894T2/de not_active Expired - Fee Related
- 1999-07-02 IL IL14048899A patent/IL140488A0/xx unknown
- 1999-07-02 CN CN99808294.5A patent/CN1308633A/zh active Pending
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- 1999-07-02 CA CA002336568A patent/CA2336568A1/en not_active Abandoned
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| CN100372857C (zh) * | 2004-05-12 | 2008-03-05 | 江苏好收成韦恩农药化工有限公司 | N-膦酰基甲基甘氨酸的生产方法 |
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| JP2003508344A (ja) | 2003-03-04 |
| DE69905894D1 (de) | 2003-04-17 |
| ATE234314T1 (de) | 2003-03-15 |
| WO2000001707A1 (en) | 2000-01-13 |
| EP1095049A1 (en) | 2001-05-02 |
| AU5030099A (en) | 2000-01-24 |
| DE69905894T2 (de) | 2003-12-04 |
| EP1095049B1 (en) | 2003-03-12 |
| IL140488A0 (en) | 2002-02-10 |
| US20010002424A1 (en) | 2001-05-31 |
| CA2336568A1 (en) | 2000-01-13 |
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