RU2301704C2 - Способ получения катализатора никель/фосфорсодержащего лиганд для гидроцианирования - Google Patents

Способ получения катализатора никель/фосфорсодержащего лиганд для гидроцианирования Download PDF

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Publication number
RU2301704C2
RU2301704C2 RU2004116079/04A RU2004116079A RU2301704C2 RU 2301704 C2 RU2301704 C2 RU 2301704C2 RU 2004116079/04 A RU2004116079/04 A RU 2004116079/04A RU 2004116079 A RU2004116079 A RU 2004116079A RU 2301704 C2 RU2301704 C2 RU 2301704C2
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RU
Russia
Prior art keywords
alkyl
nickel chloride
nicl
alkoxy
catalyst
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RU2004116079/04A
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English (en)
Russian (ru)
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RU2004116079A (ru
Inventor
Луис А. ЧУ (US)
Луис А. ЧУ
Норман ХЕРРОН (US)
Норман Херрон
Кеннет Г. МОЛОЙ (US)
Кеннет Г. МОЛОЙ
Лаки М. КЛАРКСОН (US)
Лаки М. КЛАРКСОН
Рональд Дж. МАККИННИ (US)
Рональд Дж. МАККИННИ
Зеру ТЕКИ (US)
Зеру ТЕКИ
Original Assignee
Е.И.Дюпон Де Немур Энд Компани
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/08—Halides; Oxyhalides
    • C01G53/09—Chlorides; Oxychlorides
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
RU2004116079/04A 2001-11-26 2002-11-14 Способ получения катализатора никель/фосфорсодержащего лиганд для гидроцианирования RU2301704C2 (ru)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/994,102 US6893996B2 (en) 2001-11-26 2001-11-26 Process for the preparation of a nickel/phosphorous ligand catalyst for olefin hydrocyanation
US09/994,102 2001-11-26

Publications (2)

Publication Number Publication Date
RU2004116079A RU2004116079A (ru) 2005-03-27
RU2301704C2 true RU2301704C2 (ru) 2007-06-27

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RU2004116079/04A RU2301704C2 (ru) 2001-11-26 2002-11-14 Способ получения катализатора никель/фосфорсодержащего лиганд для гидроцианирования

Country Status (17)

Country Link
US (1) US6893996B2 (cg-RX-API-DMAC10.html)
EP (2) EP1604954A1 (cg-RX-API-DMAC10.html)
JP (2) JP2005510346A (cg-RX-API-DMAC10.html)
KR (2) KR20090048517A (cg-RX-API-DMAC10.html)
CN (2) CN100445210C (cg-RX-API-DMAC10.html)
AT (1) ATE307669T1 (cg-RX-API-DMAC10.html)
AU (1) AU2002356942A1 (cg-RX-API-DMAC10.html)
BR (1) BR0214260B1 (cg-RX-API-DMAC10.html)
CA (1) CA2468293A1 (cg-RX-API-DMAC10.html)
DE (1) DE60206958T2 (cg-RX-API-DMAC10.html)
ES (1) ES2250748T3 (cg-RX-API-DMAC10.html)
MX (1) MXPA04004942A (cg-RX-API-DMAC10.html)
MY (1) MY129876A (cg-RX-API-DMAC10.html)
PL (1) PL371463A1 (cg-RX-API-DMAC10.html)
RU (1) RU2301704C2 (cg-RX-API-DMAC10.html)
TW (1) TW592817B (cg-RX-API-DMAC10.html)
WO (1) WO2003045555A2 (cg-RX-API-DMAC10.html)

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US20030100803A1 (en) * 2001-11-26 2003-05-29 Lu Helen S.M. 3-Alkylated-5,5',6,6',7,7,'8,8'-octahydro-2,2'-binaphthols and 3,3'-dialkylated-5,5',6,6',7,7',8,8'-octahydro-2,2'-binaphthols and processes for making them
FR2849027B1 (fr) * 2002-12-23 2005-01-21 Rhodia Polyamide Intermediates Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques
US6897329B2 (en) * 2003-01-14 2005-05-24 Invista North America S.A.R.L. Process for the preparation of nickel/phosphorous ligand catalyst for olefin hydrocyanation
FR2850966B1 (fr) 2003-02-10 2005-03-18 Rhodia Polyamide Intermediates Procede de fabrication de composes dinitriles
FR2854891B1 (fr) 2003-05-12 2006-07-07 Rhodia Polyamide Intermediates Procede de preparation de dinitriles
FR2854892B1 (fr) * 2003-05-12 2005-06-24 Rhodia Polyamide Intermediates Procede de fabrication de dinitriles
DE10351002A1 (de) * 2003-10-30 2005-05-25 Basf Ag Einsatz von azeotrop-getrockneten Nickel(II)-halogeniden
DE10351003A1 (de) * 2003-10-30 2005-05-25 Basf Ag Verfahren zur Herstellung von Nickel-Phosphorligand-Komplexen
DE10351000A1 (de) * 2003-10-30 2005-06-09 Basf Ag Verfahren zur Herstellung von Nickel(O)-Phosphorligand-Komplexen
DE102004004718A1 (de) * 2004-01-29 2005-08-18 Basf Ag Verfahren zur Hydrocyanierung
EP1825914A1 (de) * 2006-02-22 2007-08-29 Basf Aktiengesellschaft Verbessertes Verfahren zur Herstellung von Nickel(0)-Phophorligand-Komplexen
CA2644961A1 (en) * 2006-03-17 2007-09-27 Invista Technologies S.A.R.L. Method for the purification of triorganophosphites by treatment with a basic additive
US7659422B2 (en) * 2006-07-14 2010-02-09 Invista North America S.A.R.L. Hydrocyanation process with reduced yield losses
US7709673B2 (en) * 2006-07-14 2010-05-04 Invista North America S.A R.L. Process for making 3-pentenenitrile by hydrocyanation of butadiene
US7709674B2 (en) * 2006-07-14 2010-05-04 Invista North America S.A R.L Hydrocyanation process with reduced yield losses
US7919646B2 (en) * 2006-07-14 2011-04-05 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US7880028B2 (en) * 2006-07-14 2011-02-01 Invista North America S.A R.L. Process for making 3-pentenenitrile by hydrocyanation of butadiene
JP5295512B2 (ja) * 2007-03-29 2013-09-18 三井化学株式会社 ゼロ価ニッケルの有機ホスフィン錯体の製造方法
US7977502B2 (en) * 2008-01-15 2011-07-12 Invista North America S.A R.L. Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
EP2229353B1 (en) * 2008-01-15 2018-01-03 INVISTA Textiles (U.K.) Limited Hydrocyanation of pentenenitriles
WO2011075494A1 (en) 2009-12-18 2011-06-23 Invista Technologies S.A.R.L. Nickel metal compositions and nickel complexes derived from basic nickel carbonates
EP2574191B1 (en) 2010-07-07 2013-11-20 Invista Technologies S.a r.l. Process for making nitriles
WO2012033555A1 (en) 2010-09-07 2012-03-15 Invista Technologies S.A.R.L. Nickel compositions for preparing nickel metal and nickel complexes
EP2718015A2 (en) * 2011-06-10 2014-04-16 Invista Technologies S.à.r.l. Improvement in nickel metal-ligand catalyst formation
EP2763960B1 (en) 2011-10-07 2017-03-01 Invista Technologies S.à.r.l. Process for making nitriles
US10759741B2 (en) 2013-07-17 2020-09-01 Invista North America S.A R.L. Separating a solvent from a nickel catalyst by distillation
EP3406568A4 (en) * 2016-01-21 2019-08-21 JX Nippon Mining & Metals Corporation ANHYDRIC NICKEL CHLORIDE AND METHOD FOR THE PRODUCTION THEREOF
CN114212836A (zh) * 2021-12-31 2022-03-22 金川集团镍盐有限公司 一种无水氯化镍粉体材料的制备方法
CN114835176A (zh) * 2022-05-30 2022-08-02 金川集团镍盐有限公司 一种球形无水氯化镍产品的制备方法
JP7798365B2 (ja) * 2023-01-06 2026-01-14 レアメタルリサイクル環境合同会社 無水塩化ニッケル粉末の製造方法

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US3631191A (en) * 1970-04-08 1971-12-28 Du Pont Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes
US3846461A (en) * 1972-10-25 1974-11-05 Du Pont Process of preparing a zerovalent nickel complex with organic phosphorus compounds
US3847959A (en) * 1972-10-25 1974-11-12 Du Pont Process of preparing a zerovalent nickel complex with organic phosphorus compounds
US5061669A (en) * 1988-11-30 1991-10-29 Eastman Kodak Company Preparation of biaryl compounds
US5510470A (en) * 1991-11-12 1996-04-23 E. I. Du Pont De Nemours And Company Chiral, bidentate organophosphorus ligand
US5512695A (en) * 1994-04-14 1996-04-30 E. I. Du Pont De Nemours And Company Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins
US5523453A (en) * 1995-03-22 1996-06-04 E. I. Du Pont De Nemours And Company Process for hydrocyanation
RU2096365C1 (ru) * 1991-03-25 1997-11-20 Зульцер-эшер Висс ГмбХ Способ термической обработки влажных гидратов
RU98107641A (ru) * 1995-09-29 2000-02-10 Родья Фибер Э Резэн Энтермедиат Способ гидроцианирования органических соединений с ненасыщенной этиленовой связью

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EP0723477B1 (en) * 1993-10-12 2000-04-26 E.I. Du Pont De Nemours And Company Improved synthesis of nickel phosphine and phosphite catalysts
DE69412635T2 (de) 1993-11-23 1999-04-15 E.I. Du Pont De Nemours And Co., Wilmington, Del. Verfahren und katalysator-zusammensetzungen für die anlagerung von cyanwassenstoff an monoolefine
DE4344159A1 (de) 1993-12-23 1995-06-29 Bayer Ag Verfahren zur Herstellung von Dimethylcarbonat
ATE196745T1 (de) * 1994-04-14 2000-10-15 Du Pont Nickel und phosphinebidentat enthaltende katalysatorzusammen- setzungen zur hydrocyanierung von monoolefinen
US5512696A (en) 1995-07-21 1996-04-30 E. I. Du Pont De Nemours And Company Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor
TW315370B (cg-RX-API-DMAC10.html) 1994-10-07 1997-09-11 Du Pont
FR2739378B1 (fr) * 1995-09-29 1997-10-31 Rhone Poulenc Fibres Procede d'hydrocyanation de composes organiques a insaturation ethylenique
US5693843A (en) 1995-12-22 1997-12-02 E. I. Du Pont De Nemours And Company Process for hydrocyanation of diolefins and isomerization of nonconjugated 2 alkyl-3-monoalkenenitriles
JPH1088205A (ja) * 1996-09-10 1998-04-07 Sumitomo Metal Mining Co Ltd 金属ニッケル粉末の製造方法
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JP4918194B2 (ja) * 2001-03-22 2012-04-18 Jfeミネラル株式会社 無水塩化ニッケルの製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3631191A (en) * 1970-04-08 1971-12-28 Du Pont Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes
US3846461A (en) * 1972-10-25 1974-11-05 Du Pont Process of preparing a zerovalent nickel complex with organic phosphorus compounds
US3847959A (en) * 1972-10-25 1974-11-12 Du Pont Process of preparing a zerovalent nickel complex with organic phosphorus compounds
US5061669A (en) * 1988-11-30 1991-10-29 Eastman Kodak Company Preparation of biaryl compounds
RU2096365C1 (ru) * 1991-03-25 1997-11-20 Зульцер-эшер Висс ГмбХ Способ термической обработки влажных гидратов
US5510470A (en) * 1991-11-12 1996-04-23 E. I. Du Pont De Nemours And Company Chiral, bidentate organophosphorus ligand
US5512695A (en) * 1994-04-14 1996-04-30 E. I. Du Pont De Nemours And Company Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins
US5523453A (en) * 1995-03-22 1996-06-04 E. I. Du Pont De Nemours And Company Process for hydrocyanation
RU98107641A (ru) * 1995-09-29 2000-02-10 Родья Фибер Э Резэн Энтермедиат Способ гидроцианирования органических соединений с ненасыщенной этиленовой связью

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JP2005510346A (ja) 2005-04-21
BR0214260B1 (pt) 2014-07-29
EP1450949A2 (en) 2004-09-01
RU2004116079A (ru) 2005-03-27
DE60206958T2 (de) 2006-08-03
MXPA04004942A (es) 2004-08-11
JP2009035482A (ja) 2009-02-19
EP1450949B1 (en) 2005-10-26
CN1293944C (zh) 2007-01-10
AU2002356942A1 (en) 2003-06-10
BR0214260A (pt) 2004-09-21
KR100912331B1 (ko) 2009-08-14
EP1604954A1 (en) 2005-12-14
WO2003045555A3 (en) 2003-11-06
MY129876A (en) 2007-05-31
US6893996B2 (en) 2005-05-17
PL371463A1 (en) 2005-06-13
KR20090048517A (ko) 2009-05-13
CN100445210C (zh) 2008-12-24
CN1596152A (zh) 2005-03-16
WO2003045555A2 (en) 2003-06-05
DE60206958D1 (de) 2005-12-01
US20030100442A1 (en) 2003-05-29
TW592817B (en) 2004-06-21
KR20040060989A (ko) 2004-07-06
ES2250748T3 (es) 2006-04-16
ATE307669T1 (de) 2005-11-15
CA2468293A1 (en) 2003-06-05
CN1899972A (zh) 2007-01-24

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