GB2306344A - Catalysed hydroformylation - Google Patents

Catalysed hydroformylation Download PDF

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Publication number
GB2306344A
GB2306344A GB9521840A GB9521840A GB2306344A GB 2306344 A GB2306344 A GB 2306344A GB 9521840 A GB9521840 A GB 9521840A GB 9521840 A GB9521840 A GB 9521840A GB 2306344 A GB2306344 A GB 2306344A
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source
halide
anions
substituted
group viii
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GB9521840D0 (en
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Peter Arnoldy
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to GB9521840A priority Critical patent/GB2306344A/en
Publication of GB9521840D0 publication Critical patent/GB9521840D0/en
Priority to ZA9608894A priority patent/ZA968894B/en
Publication of GB2306344A publication Critical patent/GB2306344A/en
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    • 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
    • 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
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • 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
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • 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
    • 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
    • B01J31/1895—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 arsenic or antimony

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Ethylenically unsaturated compounds are reacted with carbon monoxide and hydrogen in the presence of a catalyst. The catalyst components are:- a) a source of Group VIII metal cations - preferably a palladium salt, b) a source of anions, other than halide ions; the preferred source being trifluoromethane sulphonic acid, c) a source of bidentate ligands of formula: R 1 R 2 M 1 RM 2 R 3 R 4 wherein:- M 1 and M 2 are, independently, P,As and Sb, ```R is a 1-4 atom bridge, ```R 1 and R 2 together represent a bivalent cyclic group, as may ```R 3 and R 4 , which may also be independent hydrocarbyl groups, and d) is a iodide of an alkali or alkaline-earth metal.

Description

HYDROFORMYLATION PROCESS The invention relates to a process for the hydroformylation of ethylenically unsaturated compounds by reaction thereof with carbon monoxide and hydrogen in the presence of a catalyst.
The hydroformylation of ethylenically unsaturated compounds, to form oxo-aldehydes and/or oxo-alcohols, hereinafter referred to as oxo-products, is of considerable industrial importance. The process has been in commercial operation for decades and over the years much development work has been done to optimise the reaction conditions, the catalyst system and the equipment. Although significant progress regarding higher yield and selectivity to the desired reaction products has been made, it is felt that in some aspects further improvement of the process is still needed.
In International application WO 95/05354 a process is disclosed wherein excellent yields and selectivity's towards hydroformylation products are achieved. In particular the use of a source of halide anions, more in particular chloride anions, as catalyst promoter besides the catalyst system was found very advantageous. However, the linearity of the hydroformylation products so produced, especially when the Group VIII metal component is a palladium cation leaves, reaches only about 70% (cf.
Table III of WO 95/05354) for C15 oxo-products. On the other hand, commercial oxo-alcohols tend to have a linearity in the order of 80%. It hence is desirable to further improve the process of WO 95/05354 in this regard.
Surprisingly, it has now been found that the process of WO 95/05354 may be improved as regards the linearity by selection of a specific iodide source as catalyst promoter.
Accordingly, the present invention provides a process for the hydroformylation of ethylenically unsaturated compounds by reaction thereof with carbon monoxide and hydrogen in the presence of a catalyst system comprising: a) a source of Group VIII metal cations; b) a source of anions, other than halide anions; c) a source of bidentate ligands of the formula R1R2M1RM2R3R4 (I) wherein M1 and M2 independently represent a phosphorus, arsenic or antimony atom, R represents a bivalent bridging group containing from 1 to 4 atoms in the bridge, R1 and R2 together represent a bivalent substituted or non-substituted cyclic group whereby the two free valences are linked to M1 and R3 and R4 independently represent a substituted or non-substituted hydrocarbyl group, or together represent a bivalent substituted or non-substituted cyclic group whereby the two free valences are linked to M2; and d) a source of halide anions as catalyst promoter in a molar ratio between halide anion and Group VIII metal cation of at most 5:1, characterised in that the source of halide anions is an alkali metal iodide or earth-alkaline metal iodide, preferably sodium and/or potassium iodide.
In WO 95/05354 both hydrogen halides, e.g., HC1, HBr and HI, and metal halides, e.g., NaCl, MgBr2, ZnC12, ZnI2, KBr, RbCl, CsCl, CsI, MgI2 and CuCl have been mentioned. Indeed, in Table III and VI examples are given of hydroformylations in the presence of several hydrogen halides and some of the aforementioned metal halides.
These examples support the preference for hydrogen chloride and metal chlorides over the corresponding iodides in view of the better rate of reaction. That equal rate and better linearity could be obtained with alkali metal iodides, in particular sodium iodide, could not be learned from this International application.
The ethylenically unsaturated compound, used as starting material, is preferably an olefin having from 2 to 30 carbon atoms per molecule, or a mixture thereof. It may comprise one or more double bonds per molecule.
Preferred are internal olefins having from 4 to 24 carbon atoms, or mixtures thereof. Such olefin mixtures are commercially readily available as products of a process for the oligomerization of ethylene, followed by a double bond isomerization and disproportionation reaction.
Typical examples are mixtures of linear internal Cg to C8 olefins, of linear internal Cii to C12 olefins and of linear internal C13 to C14 olefins.
Carbon monoxide and hydrogen may be supplied in equimolar or non-equimolar ratios, e.g. in a ratio within the range of 5:1 to 1:5, typically 3:1 to 1:3. Preferably they are supplied in a ratio within the range of 2:1 to 1:2.
In the present specification the metals of Group VIII are identified by their symbol as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt. Preferred are the metals of the platinum group, i.e., Ni, Pd and Pt. Of these, palladium is most preferred. Examples of suitable metal sources are compounds such as salts of the metal and nitric acid, sulphuric acid, sulphonic acids, or carboxylic acids with up to 12 carbon atoms; metal complexes, e.g. with carbon monoxide or acetylacetonate; or the metal combined with a solid material such as an ion exchanger or carbon.
Palladium(II) acetate and platinum(II) acetylacetonate are examples of preferred metal sources.
As component (b), any compound generating these nonhalide anions may be used. Such compounds may comprise acids or salts thereof. For example, any of the acids mentioned above, which may also participate in the salts of the Group VIII metals, may be used. The anions are preferably derived from strong acids, i.e., acids having a pKa value of less than 3, preferably less than 2 as measured in aqueous solution at 18 OC. The anions derived from these acids are non-coordinating or weakly coordinating with the Group VIII metals.
Typical examples of suitable anions are anions of phosphoric acid, sulphuric acid, sulphonic acids and halogenated carboxylic acids such as trifluoroacetic acid. Also, complex anions are suitable, such as the anions generated by a combination of a Lewis acid such as BF3, B(C6Fs)3, AlCl3, SnF2, Sn(CF3SO3)2, SnCl2 or GeCl2, with a protic acid, such as a sulphonic acid, e.g.
CF3SO3H or CH3SO3H or a hydrohalogenic acid such as HF of HCl, or a combination of a Lewis acid with an alcohol.
Examples of such complex anions are BF4, SnC13-, [SnCl2.CF3SO3]~ and PF6-. The preferred anion source for a Pd-based catalyst is trifluoromethanesulphonic acid.
The bidentate ligands of formula (I), i.e., component c) of the catalyst system, is preferably selected from 1,2-bis (1, 4-cyclooctylenephosphino)ethane, 1,2-bis(1,5cyclooctylenephosphino)ethane and mixtures thereof; in which case M1 and M2 are both phosphorus atoms, R is composed of two carbon atoms and both R1 together with R2 and R3 together with R4, represent a 1,4- or 1,5-cyclooctylene group. Alternative bidentate ligands have been described in the International application mentioned above, subject-matter of which is incorporated by reference. For the preparation of the bidentate ligands, reference is made to known techniques, for example the method disclosed in GB-A-1,127,965.
The quantity in which the catalyst system is used, is not critical and may vary within wide limits. Usually amounts in the range of 10-8 to 10-1, preferably in the range of 10-7 to 10-2 mole atom of Group VIII metal per mole of ethylenically unsaturated compound are used. The amounts of the participants in the catalyst system are conveniently selected such that per mole atom of Group VIII metal from 0.5 to 6, preferably from 1 to 2 moles of bidentate ligand are used, and from 0.5 to 15, preferably from 1 to 8 moles of anion source or a complex anion source (i.e., component b) are used.
Preferably, the molar ratio between dissociated iodide anions and Group VIII metal cations is at most 3:1, since a too high concentration of iodide may lead to catalyst poisoning. More preferably, the molar ratio is less than 1:1, for instance from 0.02:1 to 1:1. Very good results have been achieved at a molar ratio ranging from 0.25:1 to 0.6:1.
The hydroformylation can be suitably carried out at moderate reaction conditions. Hence temperatures in the range of 50 to 200 OC are recommended, preferred temperatures being in the range of 70 to 160 OC. Reaction pressures in the range of 1 to 300 bar abs are suitable, but in the range of 5 to 100 bar abs are preferred. Lower or higher pressures may be selected, but are not considered particularly advantageous. Moreover, higher pressures require special equipment provisions.
In the process of the invention, the ethylenically unsaturated starting material and the formed hydroformylation product may act as reaction diluent.
Conveniently, however, the hydroformylation reaction may be carried out in the additional presence of a solvent such as sulfolane.
The process of the invention is eminently suitable to be used for the preparation of alcohols from internal olefins at high rate, in particular by using a catalyst system as defined above, based on palladium as Group VII metal.
The invention will be illustrated by the non-limiting examples, as described hereinafter.
Comparative Examples A - C, Example 1 Four sets of experiments were carried out using ZnCl2 (Comp. A), NaCl (Comp. B), ZnI2 (Comp. C), that are known from WO 95/05354, and NaI as catalyst promoter. The experiments were conducted in a 300 ml magnetically stirred autoclave ("Hastelloy", a trademark) at 105 OC and 50 bar abs (hydrogen gas/carbon monoxide ratio of 2:1 v/v). The autoclave was charged with 62 ml of an internal C11-C12 olefin (40% C1l, 60% C12, ex. SHELL), 50 ml of 2-ethylhexanol, 0.6 ml water and 13 ml sulfolane (including 0.39 mmol of palladium(II) acetate, 0.55 mmol of diphosphine (90% isomeric pure 1,2-bis(1,5-cyclo- octylenephosphino)ethane) 0.91 mmol of trifluoromethanesulphonic acid and varying amounts of halide-containing catalyst promoter.As a consequence, the Pd concentration in the reactor was 3.1 mmol/l, and the molar ratio of palladium(II) acetate, diphosphine and trifluoromethanesulphonic acid was 1:1.4:2.3.
The reaction was followed by means of GC. Typically, at virtual complete conversion (better than 99%) an overall alcohol yield of around 98% was observed. Byproducts are paraffin and, at incomplete conversion, aldehydes and heavy ends of the acetal type. Linearity (ratio n over n and branched in percent) was also determined by GC. Kinetic analysis provided pseudo firstorder rate constants.
Further details and analytical results are compiled in the following sets of figures. Of these, Figures 1, 3, 5 and 7 illustrate the linearity of the alcohol at varying amounts of the catalyst promoter, expressed as molar ratio of halide over metal. Figures 2, 4, 6 and 8 display the rate constant as a function of the relative amount of catalyst promoter.
As can be seen from Figs. 2 and 4, C1--based catalyst promoters provide a good activity (highest first-order rate constant of more than 1 her~1), although ZnCl2 at a wider operating window. However, as shown in Figs. 1 and 3, linearity remains around 75% for all amounts of promoter tested. Paraffin make was slightly lower for ZnC12.
Ignoring the difference in price and the amount needed to promote the reaction, ZnCl2, rather than NaCl is the preferred C1'-based catalyst promoter.
Turning now to Fig. 6, an activity is found for ZnI2 that is comparable to that of NaCl. A linearity of about 80% is achievable, however, only at a I/Pd molar ratio of 0.5. Using an I/Pd molar ratio of 0.3 or 0.8, linearity was down to 788. Paraffin make for ZnI2 is excellent (only traces of paraffins found), albeit that the concentration of heavy ends and aldehydes is substantially higher than in the previous experiments.
Figs. 7 and 8 illustrate the performance of a catalyst promoter according to the present invention. A linearity of 80% is reached at a relatively low I/Pd molar ratio of 0.3, and is maintained for higher ratios.
The activity peaks at a slightly higher concentration than in Fig. 3, but the decline in activity at either side of the maximum is substantially less. The behaviour regarding byproducts is similar to that of ZnI2 in respect of the paraffin make and similar to that of NaCl in respect of the occurrence of aldehydes and heavy ends.
Experiments with F--based catalyst promoters showed no promoting effect, whereas Br--based catalyst promoters showed behaviour as regards linearity and other properties similar to C1'-based catalyst promoters.
These experiments demonstrate that alkali or earth alkaline metal iodides are the preferred catalyst promoters to obtain linearities of around 80% from the range of catalyst promoters mentioned in WO 95/05354.

Claims (9)

1. A process for the hydroformylation of ethylenically unsaturated compounds by reaction thereof with carbon monoxide and hydrogen in the presence of a catalyst system comprising: a) a source of Group VIII metal cations; b) a source of anions, other than halide anions; c) a source of bidentate ligands of the formula R1R2N1RN2R3R4 (I) wherein M1 and M2 independently represent a phosphorus, arsenic or antimony atom, R represents a bivalent bridging group containing from 1 to 4 atoms in the bridge, R1 and R2 together represent a bivalent substituted or non-substituted cyclic group whereby the two free valences are linked to M1 and R3 and R4 independently represent a substituted or non-substituted hydrocarbyl group, or together represent a bivalent substituted or non-substituted cyclic group whereby the two free valences are linked to M2; and d) a source of halide anions as catalyst promoter in a molar ratio between halide anion and Group VIII metal cation of at most 5:1, characterised in that the source of halide anions is an alkali and/or earth-alkaline metal iodide.
2. A process as claimed in claim 1, wherein the ethylenically unsaturated compound is a linear internal olefin having from 4 to 24 carbon atoms.
3. A process as claimed in claim 1 or 2, wherein carbon monoxide and hydrogen are supplied in a ratio within the range of 5:1 to 1:5.
4. A process as claimed in any one of claims 1 to 3, wherein component a) of the catalyst system is a palladium salt.
5. A process as claimed in any one of claims 1 to 4, wherein component b) of the catalyst system is a trifluoromethanesulphonic acid.
6. A process as claimed in any one of claims 1 to 5, wherein component c) of the catalyst system is selected from 1,2-bis (1, 4-cyclooctylenephosphino)ethane, 1,2 bis (1, 5-cyclooctylenephosphino) ethane and mixtures thereof.
7. A process as claimed in any one of claims 1 to 6, wherein the source of halide anions consists of sodium and/or potassium iodide.
8. A process as claimed in claim 7, wherein the molar ratio between halide and Group VIII metal cations is in the range from 0.02:1 to 1:1.
9. A process as claimed in claim 7, wherein the molar ratio between halide and Group VIII metal cations is in the range from 0.25:1 to 0.6:1.
GB9521840A 1995-10-25 1995-10-25 Catalysed hydroformylation Withdrawn GB2306344A (en)

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GB9521840A GB2306344A (en) 1995-10-25 1995-10-25 Catalysed hydroformylation
ZA9608894A ZA968894B (en) 1995-10-25 1996-10-23 Hydroformylation process of ethylenically unsaturated compounds.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0943597A2 (en) * 1998-03-16 1999-09-22 Shell Internationale Researchmaatschappij B.V. Hydroformylation of olefin feeds containing dienes
US6156936A (en) * 1998-03-16 2000-12-05 Shell Oil Company Hydroformylation of olefin feeds containing dienes
WO2002064250A2 (en) * 2001-01-31 2002-08-22 Shell Internationale Research Maatschappij B.V. Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition
WO2004028689A3 (en) * 2002-09-26 2004-07-29 Shell Int Research Process for the hydroformylation of an ethylenically unsaturated compound using a bidentate diphosphine composition with a bridging group comprising sp2 hybridized carbon atoms bound to the phosphorous atoms
US6806391B2 (en) 2002-07-31 2004-10-19 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process
US7084089B2 (en) 2002-07-31 2006-08-01 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and a process for preparation of this bidentate diphosphine composition
US7098369B2 (en) 2002-09-26 2006-08-29 Shell Oil Company Process for the production of primary alcohols
US7217848B2 (en) 2004-11-29 2007-05-15 Dow Global Technologies Inc. Tridentate phosphines and method of forming aldehyde hydrogenation catalysts
GB2451325A (en) * 2007-07-24 2009-01-28 Shell Int Research Hydroformylation process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5144068A (en) * 1984-05-03 1992-09-01 Hoechst Celanese Corporation Methanol carbonylation process
WO1995005354A1 (en) * 1993-08-19 1995-02-23 Shell Internationale Research Maatschappij B.V. Hydroformylation process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5144068A (en) * 1984-05-03 1992-09-01 Hoechst Celanese Corporation Methanol carbonylation process
WO1995005354A1 (en) * 1993-08-19 1995-02-23 Shell Internationale Research Maatschappij B.V. Hydroformylation process

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0943597A2 (en) * 1998-03-16 1999-09-22 Shell Internationale Researchmaatschappij B.V. Hydroformylation of olefin feeds containing dienes
EP0943597A3 (en) * 1998-03-16 2000-01-12 Shell Internationale Researchmaatschappij B.V. Hydroformylation of olefin feeds containing dienes
US6156936A (en) * 1998-03-16 2000-12-05 Shell Oil Company Hydroformylation of olefin feeds containing dienes
WO2002064250A2 (en) * 2001-01-31 2002-08-22 Shell Internationale Research Maatschappij B.V. Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition
WO2002064250A3 (en) * 2001-01-31 2003-01-30 Shell Int Research Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition
US6806391B2 (en) 2002-07-31 2004-10-19 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process
US7056854B2 (en) 2002-07-31 2006-06-06 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process
US7084089B2 (en) 2002-07-31 2006-08-01 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and a process for preparation of this bidentate diphosphine composition
US7161043B2 (en) 2002-07-31 2007-01-09 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process
WO2004028689A3 (en) * 2002-09-26 2004-07-29 Shell Int Research Process for the hydroformylation of an ethylenically unsaturated compound using a bidentate diphosphine composition with a bridging group comprising sp2 hybridized carbon atoms bound to the phosphorous atoms
US7098369B2 (en) 2002-09-26 2006-08-29 Shell Oil Company Process for the production of primary alcohols
US7250538B2 (en) 2002-09-26 2007-07-31 Shell Oil Company Process for the hydroformylation of an ethylenically unsaturated compound
US7414155B2 (en) 2002-09-26 2008-08-19 Shell Oil Company Process for the hydroformylation of an ethylenically unsaturated compound
US7217848B2 (en) 2004-11-29 2007-05-15 Dow Global Technologies Inc. Tridentate phosphines and method of forming aldehyde hydrogenation catalysts
GB2451325A (en) * 2007-07-24 2009-01-28 Shell Int Research Hydroformylation process

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GB9521840D0 (en) 1996-01-03
ZA968894B (en) 1997-10-23

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