WO1987004147A1 - Catalyst system and process for producing alcohols from olefines and synthesis gases - Google Patents

Catalyst system and process for producing alcohols from olefines and synthesis gases Download PDF

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Publication number
WO1987004147A1
WO1987004147A1 PCT/FI1986/000155 FI8600155W WO8704147A1 WO 1987004147 A1 WO1987004147 A1 WO 1987004147A1 FI 8600155 W FI8600155 W FI 8600155W WO 8704147 A1 WO8704147 A1 WO 8704147A1
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catalyst system
amine
catalyst
alcohols
mixture
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French (fr)
Inventor
Leila Alvila
Tapani Pakkanen
Outi Krause
Matteus Joutsimo
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Neste Oyj
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Neste Oyj
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Priority to DE8787900159T priority Critical patent/DE3682774D1/en
Priority to AT87900159T priority patent/ATE70042T1/en
Publication of WO1987004147A1 publication Critical patent/WO1987004147A1/en
Priority to NO873569A priority patent/NO167009C/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • 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
    • B01J31/20—Carbonyls
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
    • 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
    • B01J2531/822—Rhodium
    • 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
    • B01J2531/845—Cobalt

Definitions

  • the present invention concerns a catalyst system and process by the aid of which alcohol can be produced from olefines and synthesis gases (H 2 +CO) .
  • This synthesis belongs to the group of hydroformylation, or oxo, reactions, by which compounds containing oxygen, such as aldehydes and alcohols, are usually produced from olefines.
  • the catalysts to be used in the reaction are typically homogeneous and they contain rhodium or cobalt either in the form of carbonyls or phosphines.
  • isolation of the catalyst dissolved in the reaction mixture poses a difficult problem, particularly when catalysts containing rhodium are used, and it affects the process costs.
  • Metal cluster compounds constitute a group of compounds which have favourable properties as catalyst precursors.
  • a bimetallic carbonyl cluster compound catalyst for producing alcohols by hydroformylation is disclosed.
  • cluster compound either Rh 2 Co 2 (CO) 12 or Rh 3 Co(Co) 12 is used, bound to an organic polymer containing amine groups.
  • the catalyst operates at low temperature and produces almost exclusively alcohols.
  • the object of the present invention is a catalyst system in which the above-mentioned drawbacks are avoided and which thus enables alcohols to be produced with high selectivity and at relatively high temperatures.
  • the catalyst system of the invention for producing alcohols selectively from defines and synthesis gases is characterized in that it comprises one or several metal duster compounds belonging to the cobalt group on an inorganic carrier and an amine of the form NR 1 R 2 R 3 , where R 1 ,R 2 and R 3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms.
  • NR 3 tertiary amines NR 3 , where R is any aliphatic or aromatic group.
  • the characteristics of the catalyst of the invention are influenced by factors related both to production technology and reaction technique.
  • the catalyst is prepared by mixing a carrier and a metal duster compound in a solvent. After the binding process has been completed, the solvent is removed, the catalyst rinsed with pure solvent, and dried in vacuum.
  • the binding depends on the oxide carrier, on the chemical and mechanical characteristics. Aluminium oxide is one of the best agents for binding cobalt and rhodium compounds. Binding can also be observed en silicon oxide, zeolites and several silicates, for instance magnesium silicate.
  • the binding efficiency of the carrier is also affected by its degree of grinding. The most finely ground carriers bind best, and they are also the most active in catalytic reactions. In practice, more coarsely ground materials are easier to handle.
  • Impregnating a tertiary amine directly into the carrier material prior to binding the cluster compound also results in an active hydroformylation catalyst producing alcohols. Admittedly, amineimpregnated aluminium oxide and silicon oxide bind duster compounds less well, the consequence being that greater catalyst quantities have to be used.
  • the amine may also be added, not to the carrier, but directly to the reaction mixture, or part of the amine may be added to the reaction mixture and part of it to the catalyst.
  • the quantity of amine is advantageously 0.1 to 10 % by weight of the reactionmixture.
  • Adding a tertiary amine to the cluster catalyst mixture is not the only remarkable factor controlling the product distribution.
  • the amount of the duster compound an the carrier also exerts an influence an the activity and selectivity of the catalyst. low metal content and longer reaction time result in more selective catalysis than a correspondingly larger catalyst quantity and shorter reaction time.
  • the mixture is simpler and also enables the metal proportions to be optimized.
  • the performing of the hydroformylation reaction with the catalysts described in the foregoing is not significantly limited by external reaction conditions. Alcohol production takes place in the pressure range 1 to 7 MPa and in the temperature range 300 K to 450 K.
  • the composition of the catalyst and the reaction conditions may be optimized within these limits for a large group of starting material olefines.
  • the catalyst was prepared by mixing 1.0 g aluminium oxide (Alumina grades D, dried at 800oC), 0.1 g CO 2 Rh 2 (CO) 12 (Martinego, S et al., J. Organomet. Chem. 59 (1973), p. 379) and 0.020 dm 3 hexylene in nitrogen atmosphere for 15 hrs. The hexylene containing unbound duster material was removed. The catalyst was rinsed with hexylene and dried in vacuum.
  • Example 2 The catalysts were prepared as in Example 1, except that in Example 2 the carrier was zeolite (Zeolon 900 Na), in Example 3 the carrier was a silicon dioxide (silika grades F 22), and in Example 4 the carrier was magnesium silicate.
  • Example 3 the carrier was zeolite (Zeolon 900 Na)
  • Example 3 the carrier was a silicon dioxide (silika grades F 22)
  • Example 4 the carrier was magnesium silicate.
  • the catalysts were prepared as in Example 1, except that the quantity of cluster compound Co 2 Rh 2 (CO) 12 was 0.05 g.
  • the catalyst was prepared as in Example 1, except that instead of the mixed cluster compound was used a cluster compound with 0.035 g Co 4 (CO) 12 (Strem Chemicals), and 0.071 g Rh 4 (CO) 12
  • the catalyst was prepared as in Example 1, except that the aluminium oxide used for carrier was impregnated with 2 ml triethylamine (16 hrs) . The excess was evaporated in vacuum.
  • Example 8 but the triethylamine quantity was 0.10 x 10 -3 dm 3 .
  • the reaction product contained 79% C 7 alcohols and 20% C 7 aldehydes.
  • Example 8 but triethylamine quantity 0.05 x 10 -3 dm 3 .
  • the reaction product contained 30% C 7 alcohols and 55% C 7 aldehydes.
  • Example 8 but triethylamine quantity 0.025 x 10 -3 dm 3 .
  • the reaction product contained 14 % C 7 alcohols and 70 % C 7 aldehydes.
  • Examples 9-12 show clearly that when the amount of amine is reduced in the catalyst system of the invention, the selectivity of alcohol forming deteriorates rapidly.
  • Example 14 As Example 9, but the amine was Et 2 NH (0.79 mmol) .
  • the reaction product contained 62% C 7 alcohols and 19 % C 7 aldehydes, and 19 % byproducts containing amine.
  • Example 14
  • Example 8 but using the catalyst of Example 6 (0.353 g) and for alkene, propylene (0.8 g).
  • the reaction mixture contained 90 % C 7 alcohols.
  • Example 8 but using the catalyst of Example 3 (0.1 g) .
  • the reaction mixture contained 56% C 7 alcohols and 39% C 7 aldehydes.
  • Example 4 but using the catalyst of Example 5 (0.1 g).
  • the reaction mixture contained 55% C 7 alcohols and 35% C 7 aldehydes.
  • Example 8 but using the catalyst of Example 7 (0.1 g) .
  • the reaction mixture contained 70% C 7 alcohols, 16 % C 7 aldehydes and 12 % C 14 alcohols.

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

Catalyst system and process for selectively producing alcohols from olefines and synthesis gas. The catalyst system comprises one or several metal cluster compounds belonging to the cobalt group on an inorganic carrier and an amine of the form NR1R2R3, where R1, R2 and R3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms.

Description

Catalyst system and process for producing alcohols from defines and synthesis gases
The present invention concerns a catalyst system and process by the aid of which alcohol can be produced from olefines and synthesis gases (H2+CO) . This synthesis belongs to the group of hydroformylation, or oxo, reactions, by which compounds containing oxygen, such as aldehydes and alcohols, are usually produced from olefines. The catalysts to be used in the reaction are typically homogeneous and they contain rhodium or cobalt either in the form of carbonyls or phosphines. However, isolation of the catalyst dissolved in the reaction mixture poses a difficult problem, particularly when catalysts containing rhodium are used, and it affects the process costs. Endeavours have been made to avoid the drawbacks of homogeneous catalysis by binding the metal compounds on a solid carrier, which may be of organic or inorganic origin. However, heterogeneous hydroformylation catalysts are often less active than homogeneous ones, the metals are solved off the carriers in reaction conditions, and their thermal durability is limited.
Metal cluster compounds constitute a group of compounds which have favourable properties as catalyst precursors. In the U.S. Patent No. 4,144,191, a bimetallic carbonyl cluster compound catalyst for producing alcohols by hydroformylation is disclosed. For cluster compound, either Rh2Co2(CO)12 or Rh3Co(Co)12 is used, bound to an organic polymer containing amine groups. The catalyst operates at low temperature and produces almost exclusively alcohols.
In the Finnish patent application No. 844634 the observation is made that a mixture of the monometal cluster compounds Rh4(CO)12 and Co4(CO)12 bound to an amine resin carrier serves as the extremely selective catalyst in producing alcohols. An advantage of the cluster mixture catalyst is that it is simpler to prepare and its activity can be optimized as a function of the mole proportion of the metals.
Increasing the reaction rate in the hydroformylation reaction would be desirable, and feasible by raising the reaction temperature, but the thermal sensitivity of amine resin carriers restricts the raising of the reaction temperature. When using inorganic carrier materials, the use of higher temperatures would be possible. It was noted, however, in attempts to use monometal cluster compound mixtures containing rhodium and cobalt, or bimetallic compounds containing rhodium and cobalt, on inorganic carriers that the hydroformylation reaction in fact produced aldehydes only.
The object of the present invention is a catalyst system in which the above-mentioned drawbacks are avoided and which thus enables alcohols to be produced with high selectivity and at relatively high temperatures. The catalyst system of the invention for producing alcohols selectively from defines and synthesis gases is characterized in that it comprises one or several metal duster compounds belonging to the cobalt group on an inorganic carrier and an amine of the form NR1R2R3, where R1,R2 and R3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms.
Adding amine either into the reaction mixture, on the carrier, or to both, is indispensable for achieving sufficient alcohol conversion. The bimetallic Co2Rh2(CO)12 mixture as well as a mixture of monometal dusters Co4(CO)12 and Rh4(CO)12 bound to aluminium oxide or silicon dioxide-based carriers produce nothing but aldehydes if no amines are present.
The most efficient amines have turned out to be tertiary amines NR3, where R is any aliphatic or aromatic group.
The characteristics of the catalyst of the invention are influenced by factors related both to production technology and reaction technique. The catalyst is prepared by mixing a carrier and a metal duster compound in a solvent. After the binding process has been completed, the solvent is removed, the catalyst rinsed with pure solvent, and dried in vacuum. The binding depends on the oxide carrier, on the chemical and mechanical characteristics. Aluminium oxide is one of the best agents for binding cobalt and rhodium compounds. Binding can also be observed en silicon oxide, zeolites and several silicates, for instance magnesium silicate. The binding efficiency of the carrier is also affected by its degree of grinding. The most finely ground carriers bind best, and they are also the most active in catalytic reactions. In practice, more coarsely ground materials are easier to handle.
Impregnating a tertiary amine directly into the carrier material prior to binding the cluster compound also results in an active hydroformylation catalyst producing alcohols. Admittedly, amineimpregnated aluminium oxide and silicon oxide bind duster compounds less well, the consequence being that greater catalyst quantities have to be used.
The amine may also be added, not to the carrier, but directly to the reaction mixture, or part of the amine may be added to the reaction mixture and part of it to the catalyst. The quantity of amine is advantageously 0.1 to 10 % by weight of the reactionmixture.
Secondary and primary amines also act as factors catalyzing the hydroformylation reaction of rhodium-cobalt duster compounds bound on a carrier into alcohols. For instance, the conversion of 1-hexylene an adding diethylamine, Et2NH, is certainly complete, but C7 alcohols are produced, even in advantageous circumstances, only with about 70% selectivity. Moreover, the diethylamine is used up completely in hydroformamination with that 1-hexylene which is not converted into C7 alcohols. It is thus noted that the metal compound catalyzes also this side reaction. R-CH=CH2+CO+H2+Et2NH → R-(CH2)3NEt2+H2O
Primary amines, such as aniline, behave in the same way and form the corresponding hydroformamination products. When the amine is replaced with ammonia in the hydroformylation mixture of 1-hexylene in the presence of [Co2Rh2(CO)12]-alumIinium oxide, the ability of the catalyst to produce C7 products ceases altogether.
Adding a tertiary amine to the cluster catalyst mixture is not the only remarkable factor controlling the product distribution. The amount of the duster compound an the carrier also exerts an influence an the activity and selectivity of the catalyst. low metal content and longer reaction time result in more selective catalysis than a correspondingly larger catalyst quantity and shorter reaction time.
In producing the catalyst, either a mixed cluster compound CoxRh4-x(CO)12, x=1,2 or 3, or a Co4(CO)12 and Rh4(CO)12 mixture can be used, without significant difference in catalytic characteristics in similar reaction conditions. In practice, the mixture is simpler and also enables the metal proportions to be optimized.
The performing of the hydroformylation reaction with the catalysts described in the foregoing is not significantly limited by external reaction conditions. Alcohol production takes place in the pressure range 1 to 7 MPa and in the temperature range 300 K to 450 K. The composition of the catalyst and the reaction conditions may be optimized within these limits for a large group of starting material olefines.
Example 1
The catalyst was prepared by mixing 1.0 g aluminium oxide (Alumina grades D, dried at 800ºC), 0.1 g CO2Rh2(CO)12 (Martinego, S et al., J. Organomet. Chem. 59 (1973), p. 379) and 0.020 dm3 hexylene in nitrogen atmosphere for 15 hrs. The hexylene containing unbound duster material was removed. The catalyst was rinsed with hexylene and dried in vacuum.
Examples 2-4
The catalysts were prepared as in Example 1, except that in Example 2 the carrier was zeolite (Zeolon 900 Na), in Example 3 the carrier was a silicon dioxide (silika grades F 22), and in Example 4 the carrier was magnesium silicate.
Example 5
The catalysts were prepared as in Example 1, except that the quantity of cluster compound Co2Rh2 (CO) 12 was 0.05 g.
Example 6
The catalyst was prepared as in Example 1, except that instead of the mixed cluster compound was used a cluster compound with 0.035 g Co4(CO)12 (Strem Chemicals), and 0.071 g Rh4(CO)12
(Martinego, S. et al. Inorganic Synthesis, Vol. 20, 1980, p. 209) .
Example 7
The catalyst was prepared as in Example 1, except that the aluminium oxide used for carrier was impregnated with 2 ml triethylamine (16 hrs) . The excess was evaporated in vacuum.
Example 8
The catalyst of Example 1 (0.1 g), 1-hexylene (1.0 dm3), toluene (3.0 dm3), and triethylamine Et3N (0.11 x 10-3 dm3, 0.79 mmol) were transferred in nitrogen atmosphere into an autoclave (V=0.075 dm3) , into which 2.5 MPa H2 and 2.5 MPa CO were added. The autoclave was kept at 373 K for 17 hrs. The product mixture was cooled and analyzed with IR and NMR spectrometers, and by capillary gas chromatography. The reaction product contained 97 % C7 alcohols.
Example 9
As Example 8, but the triethylamine quantity was 0.10 x 10-3 dm3. The reaction product contained 79% C7 alcohols and 20% C7 aldehydes.
Example 10
As Example 8, but triethylamine quantity 0.05 x 10-3 dm3. The reaction product contained 30% C7 alcohols and 55% C7 aldehydes.
Example 11
As Example 8, but triethylamine quantity 0.025 x 10-3 dm3. The reaction product contained 14 % C7 alcohols and 70 % C7 aldehydes.
Example 12
As Example 8, but no amine was added. The reaction product conteined 85% C7 aldehydes.
Examples 9-12 show clearly that when the amount of amine is reduced in the catalyst system of the invention, the selectivity of alcohol forming deteriorates rapidly.
Example 13
As Example 9, but the amine was Et2NH (0.79 mmol) . The reaction product contained 62% C7 alcohols and 19 % C7 aldehydes, and 19 % byproducts containing amine. Example 14
As Example 8, but using the catalyst of Example 6 (0.353 g) and for alkene, propylene (0.8 g). The reaction mixture contained 90 % C7 alcohols.
Example 15
As Example 8, but using the catalyst of Example 3 (0.1 g) . The reaction mixture contained 56% C7 alcohols and 39% C7 aldehydes.
Example 16
As Example 4, but using the catalyst of Example 5 (0.1 g). The reaction mixture contained 55% C7 alcohols and 35% C7 aldehydes.
Example 17
As Example 8, but using the catalyst of Example 7 (0.1 g) . The reaction mixture contained 70% C7 alcohols, 16 % C7 aldehydes and 12 % C14 alcohols.

Claims

Claims
1. A catalyst system for selectively producing alcohols from defines and synthesis gases, characterized in that it comprises one or several metal duster compounds belonging to the cobalt group on an inorganic carrier and an amine of the form NR1R2R3, where R1,R2 and R3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms.
2. Catalyst system according to claim 1, characterized in that the metal duster compound is Co4(CO)12, Rh4(CO)12 or a mixture thereof.
3. Catalyst system according to claim 1, characterized in that the metal duster Compound is a mixed duster compound of the form CoxRh4-x(CO)12, where x=1-3.
4. Catalyst system according to any one of the preceding claims, characterized in that the amine has been added into the reaction mixture.
5. Catalyst system according to any one of claims 1-3, characterized in that the amine has been added onto the inorganic carrier substance.
6. Catalyst system according to any one of the preceding claims, characterized in that the amine quantity is 0.1 to 10 % by weight of the quantity of the reaction mixture.
7. Catalyst system according to any one of the preceding claims, characterized in that the amine is triethylamine.
8. Catalyst system according to any one of the preceding claims, characterized in that the carrier substance is aluminium oxide, silicon dioxide, zeolite or magnesium silicate.
9. A process for selectively producing alcohols from defines and synthesis gas, characterized in that a mixture containing olefine, hydrogen and carbon monoxide is reacted in the presence of a catalyst system according to claims 1 to 8.
PCT/FI1986/000155 1985-12-27 1986-12-22 Catalyst system and process for producing alcohols from olefines and synthesis gases Ceased WO1987004147A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE8787900159T DE3682774D1 (en) 1985-12-27 1986-12-22 CATALYST SYSTEM AND METHOD OF PRODUCING ALCOHOLS FROM OLEFINS AND SYNTHESIS GASES.
AT87900159T ATE70042T1 (en) 1985-12-27 1986-12-22 CATALYST SYSTEM AND PRODUCTION PROCESS OF ALCOHOLS FROM OLEFINS AND SYNTHESIS GASES.
NO873569A NO167009C (en) 1985-12-27 1987-08-24 CATALYST SYSTEM AND PROCEDURE FOR THE PREPARATION OF ALCOHOLS FROM OLEFINES AND SYNTHESIC GASES.

Applications Claiming Priority (2)

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FI855157A FI76317C (en) 1985-12-27 1985-12-27 Catalyst arrangement and process for the production of alcohols from olefin and synthesis gases
FI855157 1985-12-27

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EP (1) EP0253827B1 (en)
AT (1) ATE70042T1 (en)
DE (1) DE3682774D1 (en)
FI (1) FI76317C (en)
NO (1) NO167009C (en)
WO (1) WO1987004147A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2357645A1 (en) * 1973-05-29 1974-12-19 Mobil Oil Corp Alcohol prodn from aldehyde, acetal or olefin - by reaction with hydrogen and carbon monoxide using rhodium and tertiary amine catalyst
US4144191A (en) * 1977-06-06 1979-03-13 The Dow Chemical Company Amine-resin supported rhodium-cobalt carbonyl bimetallic clusters as novel hydroformylation catalysts
US4438287A (en) * 1981-03-27 1984-03-20 Uop Inc. Preparation of alcohols

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NO167009C (en) 1991-09-25
NO873569L (en) 1987-08-24
FI855157L (en) 1987-06-28
EP0253827B1 (en) 1991-12-04
EP0253827A1 (en) 1988-01-27
DE3682774D1 (en) 1992-01-16
FI76317B (en) 1988-06-30
US5124294A (en) 1992-06-23
NO873569D0 (en) 1987-08-24
FI855157A0 (en) 1985-12-27
FI76317C (en) 1988-10-10
ATE70042T1 (en) 1991-12-15
NO167009B (en) 1991-06-17

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