BR9912923A - Processo contìnuo para preparação de ácido n-(fosfonometil) iminodiacético - Google Patents
Processo contìnuo para preparação de ácido n-(fosfonometil) iminodiacéticoInfo
- Publication number
- BR9912923A BR9912923A BR9912923-0A BR9912923A BR9912923A BR 9912923 A BR9912923 A BR 9912923A BR 9912923 A BR9912923 A BR 9912923A BR 9912923 A BR9912923 A BR 9912923A
- Authority
- BR
- Brazil
- Prior art keywords
- stream
- acid
- amidocarboxymethylation
- phosphonomethyl
- iminodiacetic acid
- Prior art date
Links
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 title abstract 5
- 238000010924 continuous production Methods 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 12
- 239000003054 catalyst Substances 0.000 abstract 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract 6
- 230000006315 carbonylation Effects 0.000 abstract 5
- 238000005810 carbonylation reaction Methods 0.000 abstract 5
- 239000007795 chemical reaction product Substances 0.000 abstract 5
- ULRFBIKSYXNUND-UHFFFAOYSA-N 2-[acetyl(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(C(=O)C)CC(O)=O ULRFBIKSYXNUND-UHFFFAOYSA-N 0.000 abstract 4
- 239000002253 acid Substances 0.000 abstract 3
- 239000000047 product Substances 0.000 abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 239000000706 filtrate Substances 0.000 abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 150000003869 acetamides Chemical class 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
- C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- 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
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
"PROCESSO CONTìNUO PARA A PREPARAçãO DE áCIDO N-(FOSFONOMETIL)IMINODIACéTICO". No processo da presente invenção, forma-se ácido N-acetilaminodiacético via uma reação contínua de amidocarboximetilação. Nesta reação, o ácido N-(acetil)iminodiacético é formado em um sistema de reator de amidocarboximetilação, em que uma fonte de cada um dos seguintes é alimentada de maneira contínua: (1) acetamida ou um derivado de acetamida, (2) formaldeído ou um gerador ou derivado de formaldeído, (3) um catalisador de carbonilação, (4) monóxido de carbono, e, opcionalmente, (5) hidrogênio. Por sua vez, um fluxo de produto de reação de amidocarboximetilação, que contém ácido N-(acetil)-iminodiacético e o catalisador de carbonilação, é removido do sistema de reator de amidocarboximetilação. O catalisador de carbonilação é separado do fluxo de produto de reação de amidocarboximetilação para recuperar o catalisador de carbonilação e formar um fluxo de produto depletado de catalisador que contém ácido N-(acetil)iminodiacético. O catalisador de carbonilação separado é retornado ao sistema de reator de amidocarboximetilação, e o ácido N-(acetil)iminodiacético no fluxo de produto depletado de catalisador é : (1) reagido com uma fonte de fósfoto e uma fonte de formaldeído na presença de um ácido para formar um fluxo de produto de reação de fosfonometilação contendo ácido N-(fosfonometil)-iminodiacético e ácido acético; ou (2) desacilado e ciclizado para formar uma 2,5-dicetopiperazina, e, depois, reagido com uma fonte de fósforo e uma fonte de formaldeído na presença de um ácido para formar um fluxo de produto de reação de fosfonometilação contendo ácido N-(fosfonometil)-iminodiacético e ácido acético. De qualquer uma destas maneiras, o ácido N-(fosfonometil)-iminodiacético é precipitado do fluxo de produto de reação de fosfonometilação na presença de ácido acético, e o precipitado é recuperado para formar um fluxo de filtrado. O fluxo de filtrado é separado em um fluxo enriquecido com ácido acético e um fluxo depletado de ácido acético. Pelo menos uma parte do fluxo enriquecido com ácido acético é alimentada em um reator de síntese de acetamida em que se alimenta simultaneamente amónia para formar um fluxo de produto de acetamida, que é alimentado (diretamente ou indiretamente) de volta ao sistema de reator de amidocarboximetilação.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9620598P | 1998-08-12 | 1998-08-12 | |
| PCT/US1999/018501 WO2000009520A1 (en) | 1998-08-12 | 1999-08-12 | Continuous process for the preparation of n-(phosphonomethyl) iminodiacetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BR9912923A true BR9912923A (pt) | 2001-10-09 |
Family
ID=22256348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BR9912923-0A BR9912923A (pt) | 1998-08-12 | 1999-08-12 | Processo contìnuo para preparação de ácido n-(fosfonometil) iminodiacético |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US6130351A (pt) |
| EP (1) | EP1104428A1 (pt) |
| JP (1) | JP2002522549A (pt) |
| CN (1) | CN1319102A (pt) |
| AU (1) | AU754281B2 (pt) |
| BR (1) | BR9912923A (pt) |
| CA (1) | CA2339839A1 (pt) |
| ID (1) | ID28485A (pt) |
| WO (1) | WO2000009520A1 (pt) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9912923A (pt) * | 1998-08-12 | 2001-10-09 | Monsanto Co | Processo contìnuo para preparação de ácido n-(fosfonometil) iminodiacético |
| KR20020073147A (ko) * | 1999-12-21 | 2002-09-19 | 몬산토 테크놀로지 엘엘씨 | 탄소-지지된, 귀금속-함유 촉매의 존재하에 보충적촉진제의 액상 산화 반응에서의 용도 |
| AR038654A1 (es) | 2000-05-22 | 2005-01-26 | Monsanto Technology Llc | Sistemas de reaccion para producir compuestos de n-(fosfonometil) glicina |
| AU2001275182A1 (en) * | 2000-06-01 | 2001-12-11 | Monsanto Technology Llc | Metal-catalysed carboxymethylation in the presence of a promoter |
| GB0113079D0 (en) | 2001-05-30 | 2001-07-18 | Kvaerner Process Tech Ltd | Process |
| EP1560648A1 (en) * | 2002-06-28 | 2005-08-10 | Monsanto Technology LLC | Use of tellurium in carbon-supported, noble metal-containing catalysts for liquid phase oxidation reactions |
| GB0413092D0 (en) * | 2004-06-11 | 2004-07-14 | Degussa | Process for preparing amino acids using the amidocarbonylation reaction (1) |
| GB0413090D0 (en) * | 2004-06-11 | 2004-07-14 | Degussa | Process for preparing amino acids using the amidocarbonylation reaction (2) |
| 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 |
| TW200624151A (en) | 2004-11-12 | 2006-07-16 | Monsanto Technology Llc | Recovery of noble metals from aqueous process streams |
| TW200642745A (en) | 2005-02-03 | 2006-12-16 | Shell Int Research | Process for inhibiting deposition of solids from a gaseous stream |
| TW200630156A (en) * | 2005-02-03 | 2006-09-01 | Shell Int Research | Treatment of an aqueous mixture containing an alkylene oxide with an ion exchange resin |
| AR056660A1 (es) * | 2005-04-25 | 2007-10-17 | Monsanto Technology Llc | Alteracion de la distribucion de tamanos de cristales de acido n-(fosfonometil) iminodiacetico para mejorar la filtracion y la calidad del producto |
| TW200732292A (en) * | 2006-02-01 | 2007-09-01 | Shell Int Research | A method of treating an aldehyde mixture, use of the treated aldehyde, and an alcohol |
| CN100400543C (zh) * | 2006-09-08 | 2008-07-09 | 四川贝尔实业有限责任公司 | 亚氨基二乙腈水解制备双甘膦的方法 |
| US8252953B2 (en) | 2008-05-01 | 2012-08-28 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
| PL2493902T3 (pl) * | 2009-10-27 | 2015-02-27 | Straitmark Holding Ag | Sposób wytwarzania kwasów fosfonoalkiloiminodioctowych |
| CN102101873B (zh) * | 2011-01-14 | 2013-06-12 | 捷马化工股份有限公司 | 一种双甘膦的制备方法 |
| EP2875036A1 (en) | 2012-07-17 | 2015-05-27 | Straitmark Holding AG | Method for the synthesis of aminoalkylenephosphonic acid |
| BR112015000995B1 (pt) | 2012-07-17 | 2020-04-28 | Monsanto Technology Llc | método para a síntese de n-(fosfonometil)glicina ou um de seus derivados selecionados a partir do grupo que consiste em seus sais, seus ésteres de fosfonato e seus sais de éster de fosfonato |
| RU2674022C9 (ru) | 2012-07-17 | 2019-01-24 | МОНСАНТО ТЕКНОЛОДЖИ ЭлЭлСи | Способ синтеза альфа-аминоалкиленфосфоновой кислоты |
| BR112015000966B1 (pt) | 2012-07-17 | 2020-04-28 | Monsanto Technology Llc | método para a síntese de n-(fosfonometil)glicina ou um de seus derivados selecionados a partir do grupo que consiste em seus sais, seus ésteres de fosfonato e seus sais de éster de fosfonato |
| RU2015103314A (ru) | 2012-07-17 | 2016-09-10 | Страйтмарк Холдинг Аг | Способ синтеза N-фосфонометилиминодиуксусной кислоты |
| US9745506B2 (en) | 2015-06-01 | 2017-08-29 | Halliburton Energy Services, Inc. | Treatment fluids for use in removing acid-soluble materials in subterranean formations |
| CN106746135A (zh) * | 2017-03-09 | 2017-05-31 | 江苏省环境科学研究院 | 一种双甘膦废水的处理系统及工艺 |
| CN109942626A (zh) * | 2019-04-19 | 2019-06-28 | 山东润博生物科技有限公司 | 一种草甘膦的合成方法 |
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| US2757200A (en) * | 1951-03-29 | 1956-07-31 | Exxon Research Engineering Co | Decobalting of oxo aldehydes with nonaqueous oxalic acid |
| US2757204A (en) * | 1951-04-27 | 1956-07-31 | Exxon Research Engineering Co | Acid decobalting of oxo products |
| US2757205A (en) * | 1952-04-30 | 1956-07-31 | Exxon Research Engineering Co | Oxo process-acid decobalting in presence of carbon monoxide |
| US2757206A (en) * | 1952-09-08 | 1956-07-31 | Exxon Research Engineering Co | Oxo catalyst removal process |
| CA775575A (en) * | 1961-11-13 | 1968-01-09 | R. Irani Riyad | Organic phosphorus compounds |
| US3260745A (en) * | 1962-04-18 | 1966-07-12 | Socony Mobil Oil Co Inc | N-t-alkyl-beta-amino propionic acids |
| US3246024A (en) * | 1962-10-16 | 1966-04-12 | Gulf Research Development Co | Process for converting cobalt compounds to cobalt acetate and/or cobalt propionate |
| US3847997A (en) * | 1969-06-12 | 1974-11-12 | Phillips Petroleum Co | Hydroformylation process and catalyst |
| US3998887A (en) * | 1969-06-12 | 1976-12-21 | Phillips Petroleum Company | P-styryldiethylphosphine |
| JPS4817259B1 (pt) * | 1970-04-04 | 1973-05-28 | ||
| US3904668A (en) * | 1973-11-15 | 1975-09-09 | Grace W R & Co | Process for preparing iminodiacetonitrile and alkali metal iminodiacetates |
| US3969398A (en) * | 1974-05-01 | 1976-07-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| FR2395252A1 (fr) * | 1977-06-21 | 1979-01-19 | Inst Francais Du Petrole | Procede de fabrication de derive n-acyle d'acide amine |
| US4225458A (en) * | 1979-01-30 | 1980-09-30 | Exxon Research & Engineering Co. | Process for the continuous manufacture and separation of oxo catalysts |
| US4312662A (en) * | 1979-12-31 | 1982-01-26 | Monsanto Company | N-Substituted carboxy-N-phosphonomethylglycines and the salts thereof as herbicides |
| FR2523576A1 (fr) * | 1982-03-17 | 1983-09-23 | Inst Francais Du Petrole | Procede de preparation d'acides n-acyliminodiacetiques |
| US4400330A (en) * | 1982-07-29 | 1983-08-23 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
| US4710574A (en) * | 1983-11-16 | 1987-12-01 | The Standard Oil Company | α-amino acids through catalytic reaction of CO and a hydroxyl compound with enamides |
| US4624937A (en) * | 1984-05-10 | 1986-11-25 | Monsanto Company | Process for removing surface oxides from activated carbon catalyst |
| US4918222A (en) * | 1984-07-27 | 1990-04-17 | Texaco Inc. | Process for synthesis of N-acetylglycine |
| EP0170830B1 (en) * | 1984-07-27 | 1989-03-22 | Texaco Development Corporation | A process for amido carbonylation of an aldehyde to n-acetyl alpha-amino acids |
| US5068404A (en) * | 1984-12-28 | 1991-11-26 | Monsanto Company | Thermal dealkylation of N-alkyl N-phosphonomethylglycine |
| US4696772A (en) * | 1985-02-28 | 1987-09-29 | Monsanto Company | Amine oxidation using carbon catalyst having oxides removed from surface |
| DE3663661D1 (en) * | 1985-04-05 | 1989-07-06 | Texaco Development Corp | Process for synthesizing n-acetylglycine using novel promoters |
| DE3664632D1 (en) * | 1985-04-05 | 1989-08-31 | Texaco Development Corp | Process for the synthesis of n-acetyl amino acids from olefins, acetamide and syngas |
| US4804499A (en) * | 1985-09-23 | 1989-02-14 | Monsanto Company | Process for the preparation of N-substituted aminomethylphosphonic acids |
| US4657705A (en) * | 1985-09-23 | 1987-04-14 | Monsanto Company | Process for the preparation of N-substituted aminomethylphosphonic acids |
| EP0413068A1 (en) * | 1985-10-29 | 1991-02-20 | The Standard Oil Company | Process for making an optically active mixture of an n-acyl-amino acid or ester containing at least two chiral centers |
| US4749811A (en) * | 1985-10-29 | 1988-06-07 | The Standard Oil Company | Method of making a diastereomeric mixture containing two diastereomeric α-acyloxy acid esters |
| US4892687A (en) * | 1986-10-08 | 1990-01-09 | Texaco Inc. | Process for synthesis of amidoacids using a cobalt catalyst and a bidental phosphine ligand |
| US4891442A (en) * | 1987-03-09 | 1990-01-02 | Texaco Inc. | Process for synthesis of β-phenylalanine |
| US4954466A (en) * | 1989-11-30 | 1990-09-04 | Monsanto Company | Recovery of cobalt catalyst values |
| GB2252770A (en) * | 1991-02-14 | 1992-08-19 | Shell Int Research | The preparation of n-acyl-alpha-amino acids |
| US5237104A (en) * | 1992-05-29 | 1993-08-17 | Exxon Chemical Patents Inc. | Cobalt catalyst recovery using heavy olefin absorbent |
| GB9300641D0 (en) * | 1993-01-14 | 1993-03-03 | Zeneca Ltd | Process |
| DE4415312A1 (de) * | 1994-05-02 | 1995-11-09 | Hoechst Ag | Verfahren zur Herstellung von N-Acylglycinderivaten |
| US5948938A (en) * | 1995-03-07 | 1999-09-07 | Sankyo Company, Limited | Process for preparing N-phosphonomethylglycine |
| DE19545641A1 (de) * | 1995-12-07 | 1997-06-12 | Hoechst Ag | Verfahren zur Wiedergewinnung von bei der Herstellung von N-Acyl-alpha-aminosäurederivaten durch Amidocarbonylierung eingesetzten Cobaltcarbonylkatalysatoren |
| JP2001511810A (ja) * | 1997-02-13 | 2001-08-14 | モンサント カンパニー | アミノカルボン酸の製造方法 |
| BR9912923A (pt) * | 1998-08-12 | 2001-10-09 | Monsanto Co | Processo contìnuo para preparação de ácido n-(fosfonometil) iminodiacético |
-
1999
- 1999-08-12 BR BR9912923-0A patent/BR9912923A/pt not_active IP Right Cessation
- 1999-08-12 JP JP2000564971A patent/JP2002522549A/ja active Pending
- 1999-08-12 WO PCT/US1999/018501 patent/WO2000009520A1/en not_active Ceased
- 1999-08-12 ID IDW20010583A patent/ID28485A/id unknown
- 1999-08-12 AU AU54851/99A patent/AU754281B2/en not_active Ceased
- 1999-08-12 EP EP99941139A patent/EP1104428A1/en not_active Withdrawn
- 1999-08-12 CN CN99811123A patent/CN1319102A/zh active Pending
- 1999-08-12 US US09/373,106 patent/US6130351A/en not_active Expired - Lifetime
- 1999-08-12 CA CA002339839A patent/CA2339839A1/en not_active Abandoned
-
2000
- 2000-07-10 US US09/612,705 patent/US6278017B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU5485199A (en) | 2000-03-06 |
| WO2000009520A1 (en) | 2000-02-24 |
| JP2002522549A (ja) | 2002-07-23 |
| US6130351A (en) | 2000-10-10 |
| WO2000009520A9 (en) | 2000-09-28 |
| EP1104428A1 (en) | 2001-06-06 |
| AU754281B2 (en) | 2002-11-14 |
| US6278017B1 (en) | 2001-08-21 |
| ID28485A (id) | 2001-05-31 |
| CN1319102A (zh) | 2001-10-24 |
| CA2339839A1 (en) | 2000-02-24 |
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