ES2007367A6 - Un procedimiento mejorado de hidroformiliacion no acuosa para producir aldehidos - Google Patents

Un procedimiento mejorado de hidroformiliacion no acuosa para producir aldehidos

Info

Publication number
ES2007367A6
ES2007367A6 ES8702037A ES8702037A ES2007367A6 ES 2007367 A6 ES2007367 A6 ES 2007367A6 ES 8702037 A ES8702037 A ES 8702037A ES 8702037 A ES8702037 A ES 8702037A ES 2007367 A6 ES2007367 A6 ES 2007367A6
Authority
ES
Spain
Prior art keywords
hydroformylation
low volatile
organic soluble
phosphine ligands
soluble phosphine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
ES8702037A
Other languages
English (en)
Inventor
Anthony George Abatjoblu
David Robert Bryant
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Publication of ES2007367A6 publication Critical patent/ES2007367A6/es
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • 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
    • C07F9/50—Organo-phosphines
    • C07F9/5004—Acyclic saturated phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

UN PROCEDIMIENTO MEJORADO DE HIDROFORMILACION NO ACUOSA PARA PRODUCIR ALDEHIDOS, EN EL QUE SE HACE REACCIONAR UN COMPUESTO ORGANICO OLEFINICAMENTE INSATURADO CON MONOXIDO DE CARBONO E HIDROGENO, EN UN MEDIO NO ACUOSO QUE CONTIENE UN LIGANDO DE FOSFORO LIBRE Y UN CATALIZADOR COMPLEJO DE METAL DE TRANSICION LIGANDO DE FOSFORO, CONSISTIENDO AMBOS LIGANDOS EN UNA SAL DE FOSFINA TERCIARIA MONOSULFONADA DE FORMULA:DONDE R ES ALQUILO, ARILO, ALCARILO, ARALQUILO O CICLOALQUILO Y M ES UN CATION AMINICO DE FORMULA:DONDE R1 ES HIDROGENO, ALQUILO, ARILO, ALCARILO, ARALQUILO O CICLOALQUILO Y CADA RY-R4 ES ALQUILO, ARILO, ALCARILO, ARALQUILO O CICLOHEXILO. LA TEMPERATURA DE REACCION ES DE 45-200GC, LA PRESION ES MENOR DE 105 KG/CMY ABSOLUTOS Y LA RELACION MOLAR DE HIDROGENO A MONOXIDO DE CARBONO ES DE 1:10-100:1. EL INVENTO ES UTIL PARA HIDROFORMILAR OLEFINAS DE ALTO PESO MOLECULAR.
ES8702037A 1986-07-10 1987-07-10 Un procedimiento mejorado de hidroformiliacion no acuosa para producir aldehidos Expired ES2007367A6 (es)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/884,197 US4716250A (en) 1986-07-10 1986-07-10 Hydroformylation using low volatile/organic soluble phosphine ligands

Publications (1)

Publication Number Publication Date
ES2007367A6 true ES2007367A6 (es) 1989-06-16

Family

ID=25384155

Family Applications (1)

Application Number Title Priority Date Filing Date
ES8702037A Expired ES2007367A6 (es) 1986-07-10 1987-07-10 Un procedimiento mejorado de hidroformiliacion no acuosa para producir aldehidos

Country Status (29)

Country Link
US (1) US4716250A (es)
EP (1) EP0254937B1 (es)
JP (1) JPS6388150A (es)
KR (1) KR910008369B1 (es)
CN (1) CN1020720C (es)
AR (1) AR243490A1 (es)
AT (1) ATE74120T1 (es)
AU (1) AU605773B2 (es)
BE (1) BE1001190A5 (es)
BR (1) BR8703510A (es)
CA (1) CA1307006C (es)
CS (1) CS271475B2 (es)
DE (2) DE3722928A1 (es)
DK (1) DK359987A (es)
ES (1) ES2007367A6 (es)
FI (1) FI89351C (es)
FR (1) FR2603579B1 (es)
GB (1) GB2193494B (es)
HU (1) HU202468B (es)
IN (1) IN169702B (es)
IT (1) IT1221979B (es)
MX (1) MX166891B (es)
NL (1) NL8701626A (es)
NO (1) NO165877C (es)
PL (1) PL151795B1 (es)
SE (1) SE8702822L (es)
SU (1) SU1715202A3 (es)
YU (1) YU46424B (es)
ZA (1) ZA875058B (es)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4731486A (en) * 1986-11-18 1988-03-15 Union Carbide Corporation Hydroformylation using low volatile phosphine ligands
US5180854A (en) * 1988-07-14 1993-01-19 Union Carbide Chemicals & Plastics Technology Corporation Process for catalyst aldehyde product separation
US5059710A (en) * 1988-08-05 1991-10-22 Union Carbide Chemicals And Plastics Technology Corporation Ionic phosphites and their use in homogeneous transition metal catalyzed processes
US5113022A (en) * 1988-08-05 1992-05-12 Union Carbide Chemicals & Plastics Technology Corporation Ionic phosphites used in homogeneous transition metal catalyzed processes
US4935550A (en) * 1988-08-12 1990-06-19 Union Carbide Chemicals And Plastics Company Inc. Catalytic metal recovery from non-polar organic solutions
US4929767A (en) * 1988-08-12 1990-05-29 Union Carbide Chemicals And Plastics Company Inc. Treatment of rhodium catalysts
US4861918A (en) * 1988-08-12 1989-08-29 Union Carbide Corporation Reactivation of hydroformylation catalysts
DE3942954A1 (de) * 1989-12-23 1991-06-27 Hoechst Ag Verfahren zur herstellung von aldehyden
JPH06503808A (ja) * 1990-08-31 1994-04-28 ザ　ガヴァナーズ　オヴ　ザ　ユニヴァーシティ　オヴ　アルバータ 新規の遷移金属触媒先駆物質を用いるメタノールのカルボニル化
US5087763A (en) * 1990-11-09 1992-02-11 Union Carbide Chemicals & Plastics Technology Corporation Hydroformylation process
US5288818A (en) * 1991-08-20 1994-02-22 Exxon Chemical Patents Inc. Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction
US5215667A (en) * 1991-08-20 1993-06-01 Exxon Chemical Patents Inc. Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction
CN1036388C (zh) * 1992-12-29 1997-11-12 中国石化兰州炼油化工总厂 烯烃氢甲酰化合成醛的方法
DE19619528A1 (de) * 1996-05-15 1997-11-20 Hoechst Ag Substituierte Diphosphine und ein Verfahren zu ihrer Herstellung
EP0823282B1 (de) * 1996-05-15 2001-11-14 Celanese Chemicals Europe GmbH Verfahren zur Herstellung von Aldehyden
ID21537A (id) * 1997-12-22 1999-06-24 Celanese Gmbh Proses pembuatan aldehid
DE19756945C2 (de) * 1997-12-22 2000-08-03 Celanese Chem Europe Gmbh Nichtwäßrige ionogene Ligandflüssigkeiten, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatorbestandteil
JP3921853B2 (ja) * 1998-12-10 2007-05-30 三菱化学株式会社 アルデヒド類及びアルコール類の製造方法
FR2813305B1 (fr) * 2000-08-23 2004-02-13 Inst Francais Du Petrole Procede ameliore d'hydroformylation mettant en oeuvre un catalyseur a base de cobalt et/ou de rhodium dans un solvant ionique non aqueux
SG93931A1 (en) * 2001-04-13 2003-01-21 Kuraray Co Phosphonium salts and processes for production of and uses for the same, and phosphines deriving the same and processes for production of the phosphines
JP2007509093A (ja) * 2003-10-21 2007-04-12 ビーエーエスエフ　アクチェンゲゼルシャフト アルデヒドの連続的な製造方法
CN102826974B (zh) * 2011-06-17 2015-11-25 中国石油化工股份有限公司 一种丙烯氢甲酰化反应制备丁醛的方法
KR101987513B1 (ko) * 2011-09-30 2019-06-10 다우 테크놀로지 인베스트먼츠 엘엘씨. 정제 방법
CN104045532B (zh) 2013-03-15 2018-05-25 陶氏技术投资有限责任公司 加氢甲酰化方法
KR102217415B1 (ko) 2013-03-27 2021-02-18 주식회사 쿠라레 비스(6-메틸-3-술포페닐)페닐포스핀 및 그 암모늄염 그리고 그들의 제조 방법
CA2907619C (en) * 2013-03-27 2021-06-15 Kuraray Co., Ltd. Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, ammonium salt thereof, and method for producing same
JP6225170B2 (ja) 2013-03-27 2017-11-01 株式会社クラレ ２，７−オクタジエン−１−オールの製造方法
CN104248860A (zh) 2013-06-27 2014-12-31 陶氏技术投资有限责任公司 热管理方法
BR112016008906B1 (pt) 2013-10-28 2021-12-07 Rohm And Haas Company Processo para preparar metil metacrilato
CN110573484B (zh) 2017-05-25 2022-11-01 罗门哈斯公司 用于制备甲基丙烯醛的方法
WO2018217964A1 (en) 2017-05-25 2018-11-29 Rohm And Haas Company Process for preparing methacrolein
WO2020057878A1 (en) * 2018-09-17 2020-03-26 Exxonmobil Chemical Patents Inc. Transfer hydroformylation for the production of oxygenates
EP4412975A1 (en) 2021-10-08 2024-08-14 Dow Global Technologies LLC Process for methacrylic acid production
MX2024004169A (es) 2021-10-08 2024-04-23 Rohm & Haas Proceso para la produccion de metacrilato de alquilo.
WO2023059673A1 (en) 2021-10-08 2023-04-13 Rohm And Haas Company Process for an oxidative esterification reactor
MX2024004085A (es) 2021-10-08 2024-04-18 Rohm & Haas Proceso para baja formacion de subproducto de metacrilato de metilo de un reactor de esterificacion oxidativa.
US20240400492A1 (en) 2021-10-08 2024-12-05 Rohm And Haas Company Process for methyl methacrylate production
MX2024004086A (es) 2021-10-08 2024-04-18 Rohm & Haas Proceso para la produccion de metacrilato de metilo.
CA3233789A1 (en) 2021-10-08 2023-04-13 Dow Global Technologies Llc Process for low byproduct formation from an oxidative esterification reactor with base addition
US20240400493A1 (en) 2021-10-08 2024-12-05 Rohm And Haas Company Process for methyl methacrylate production from ethanol
JP2025542575A (ja) 2022-12-08 2025-12-26 ダウ グローバル テクノロジーズ エルエルシー メタクリル酸アルキルを調製するためのプロセス
WO2024123530A1 (en) 2022-12-08 2024-06-13 Rohm And Haas Company Process for concurrent methyl methacrylate and methacrylic acid production
GB202307175D0 (en) 2023-05-15 2023-06-28 Johnson Matthey Davy Technologies Ltd Process for hydrogenating a substrate
GB202404300D0 (en) 2024-03-26 2024-05-08 Johnson Matthey Davy Technologies Ltd Process for the production of 2-alkylalkanol

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US31812A (en) * 1861-03-26 Stump-extractor
US3527809A (en) * 1967-08-03 1970-09-08 Union Carbide Corp Hydroformylation process
BE758502A (fr) * 1969-11-06 1971-05-05 Basf Ag Preparation d'alcools et d'aldehydes
NL7106084A (es) * 1970-05-06 1971-11-09
US3928232A (en) * 1972-10-24 1975-12-23 Chevron Res Aryl sulfonate stabilized cobalt carbonyl complex compounds
US4148830A (en) * 1975-03-07 1979-04-10 Union Carbide Corporation Hydroformylation of olefins
US4248802A (en) 1975-06-20 1981-02-03 Rhone-Poulenc Industries Catalytic hydroformylation of olefins
US4247486A (en) * 1977-03-11 1981-01-27 Union Carbide Corporation Cyclic hydroformylation process
JPS55164640A (en) * 1979-06-12 1980-12-22 Agency Of Ind Science & Technol Preparation of aldehyde
US4283562A (en) * 1979-10-26 1981-08-11 Union Carbide Corporation Hydroformylation process using stable rhodium catalyst
GB2085874B (en) * 1980-09-04 1984-08-08 Johnson Matthey Plc Hydroformylation of olefins
US4400548A (en) * 1981-08-17 1983-08-23 Union Carbide Corporation Hydroformylation process using bisphosphine monooxide ligands
JPS58157739A (ja) * 1982-03-12 1983-09-19 Kuraray Co Ltd １，９−ノナンジア−ルの製造方法
FR2532318B1 (fr) * 1982-08-31 1985-06-14 Rhone Poulenc Chim Base Procede de preparation de triarylphosphines sulfonees
DE3234701A1 (de) * 1982-09-18 1984-04-05 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von aldehyden
DE3235030A1 (de) * 1982-09-22 1984-03-22 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von sulfonierten arylphosphinen
DE3235029A1 (de) * 1982-09-22 1984-03-22 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur rueckgewinnung von wasserloeslichen, rhodium enthaltenden hydroformylierungskatalysatoren
CA1231346A (en) * 1982-09-30 1988-01-12 Eit Drent Process for the carbonylation of olefinically unsaturated compounds with a palladium catalyst
FR2550202B1 (fr) * 1983-08-03 1986-03-21 Rhone Poulenc Rech Procede de preparation de tri(m-sulfophenyl) phosphine
DE3341035A1 (de) * 1983-11-12 1985-05-23 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von aldehyden
DE3347406A1 (de) * 1983-12-29 1985-07-11 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur abtrennung und wiedergewinnung von rhodium aus den produkten der oxosynthese
DE3412335A1 (de) * 1984-04-03 1985-10-10 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von aldehyden
FR2561650B1 (fr) * 1984-03-26 1987-10-23 Rhone Poulenc Rech Perfectionnement au procede de preparation de tri(m-sulfophenyl)phosphine par hydrolyse et dilution controlees du sulfonat
DE3411034A1 (de) * 1984-03-26 1985-09-26 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur rueckgewinnung von rhodium aus reaktionsprodukten der oxosynthese
DE3413427A1 (de) * 1984-04-10 1985-10-17 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von aldehyden
DE3415968A1 (de) * 1984-04-28 1985-10-31 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von aldehyden
DE3420491A1 (de) * 1984-06-01 1985-12-05 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur herstellung von aldehyden
DE3420493A1 (de) * 1984-06-01 1985-12-05 Ruhrchemie Ag, 4200 Oberhausen Quartaere ammoniumsalze sulfonierter triarylphosphine
US4593127A (en) * 1985-01-11 1986-06-03 Union Carbide Corporation Hydroformylation process
US4578523A (en) * 1985-05-29 1986-03-25 Ruhrchemie Aktiengesellschaft Process for the preparation of aldehydes
DE3534314A1 (de) * 1985-09-26 1987-04-02 Ruhrchemie Ag Verfahren zur herstellung von aldehyden
CA1264521A (en) * 1985-12-24 1990-01-23 Minoru Kuriyama Degassing apparatus for a metal mold

Also Published As

Publication number Publication date
AU7553187A (en) 1988-01-14
SU1715202A3 (ru) 1992-02-23
FR2603579A1 (fr) 1988-03-11
AU605773B2 (en) 1991-01-24
SE8702822D0 (sv) 1987-07-09
HU202468B (en) 1991-03-28
YU129787A (en) 1988-04-30
DE3722928A1 (de) 1988-01-21
IT8721213A0 (it) 1987-07-08
IT1221979B (it) 1990-08-31
EP0254937A3 (en) 1989-04-19
BR8703510A (pt) 1988-03-22
JPS6388150A (ja) 1988-04-19
GB2193494B (en) 1991-01-02
CA1307006C (en) 1992-09-01
NL8701626A (nl) 1988-02-01
CS527687A2 (en) 1990-02-12
NO165877B (no) 1991-01-14
ATE74120T1 (de) 1992-04-15
EP0254937A2 (en) 1988-02-03
IN169702B (es) 1991-12-14
JPH0548214B2 (es) 1993-07-20
KR910008369B1 (ko) 1991-10-12
PL266758A1 (en) 1988-09-01
AR243490A1 (es) 1993-08-31
FI873054A0 (fi) 1987-07-10
FR2603579B1 (fr) 1990-05-25
FI89351B (fi) 1993-06-15
NO872887D0 (no) 1987-07-10
FI89351C (fi) 1993-09-27
SE8702822L (sv) 1988-01-11
DE3777714D1 (de) 1992-04-30
GB2193494A (en) 1988-02-10
DK359987D0 (da) 1987-07-10
US4716250A (en) 1987-12-29
ZA875058B (en) 1988-03-30
NO165877C (no) 1991-04-24
FI873054L (fi) 1988-01-11
KR880001557A (ko) 1988-04-25
GB8716161D0 (en) 1987-08-12
EP0254937B1 (en) 1992-03-25
CN87105466A (zh) 1988-02-03
MX166891B (es) 1993-02-11
DK359987A (da) 1988-01-11
PL151795B1 (en) 1990-10-31
CN1020720C (zh) 1993-05-19
NO872887L (no) 1988-01-11
BE1001190A5 (fr) 1989-08-16
YU46424B (sh) 1993-10-20
CS271475B2 (en) 1990-10-12
HUT48193A (en) 1989-05-29

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Effective date: 20000202