PROCEDURE FOR PRODUCING ALCOHOLS AND ALDEHYDES FROM ALKENES AND SYNTHESIS GASES

Abstract: The present invention concerns a procedure for preparing alcohols and aldehydes from alkenes and synthesis gas by a heterogeneous hydroformulation reaction in which the catalyst system is composed of Ru3(CO)12 and a heterocyclic base in suspension or absorbed in a fixed carrier.

Description: Procedure for producing alcohols and aldehydes from alkenes and synthesis gases 5 The present invention concerns a procedure for producing alcohols and aldehydes from alkenes and synthesis gases. Oxygen containing compounds such as alcohols and aldehydes are ■in generally produced by hydroformulation process. The catalysts of industrial processes are typically homogeneous rhodium or cobalt carbonyls or phosphines. Heterogeneous catalysts can be produced by binding a metal compound on a fixed organic or inorganic carrier, whereby certain advantages are gained. The heterogeneous catalyst ■jg is easy and advantageous to separate from the products, which is specifically advantageous in using expensive rhodium catalysts. The heterogeneous catalyst is also thermally more stable than the homogeneous catalyst and causes less corrosion. In addition, the metal compound and the carrier may have useful combined effects. Of) The process of the homogeneous catalysts are however more specific and repeatable. Metal cluster compounds are provided with advantageous character¬ istic features as precursors to catalysts because their specific 5 structures as catalysts enable to have better activities and particularly selectivities in comparison with simple metal complexes. The greatest difficulty is, however, the instability of metal cluster compounds. Advantages of heterogeneous cluster cata¬ lysts are lack of halides (a halide can be a catalytic toxic agent 0 and cause aggregation and sintration) , and provision of exact combination. In the Finnish Patent No. 69620 is disclosed a catalyst for pro¬ ducing hydrogen gas from carbon monoxide and water (transfer 5 reaction of aqueous gas). The catalyst is produced from the group VIII metal carbonyls and heterocyciic base. The metal carbonyl of the group is Ru 3 (CO) * L 2. FeRu 2 (CO)]_2, Fe 2 Ru(CO) 1 2> or their deriva- 1 tive M3(CO)i2- - --- 11 w ic M is Ru or Fe, x is 1 or 2, and L is a trialkyl or triaryl phosphine or phosphite. As the heterocyciic base is a 2,2'-bipyridine or 1,10 phenantroline. As taught by the invention, the dissolvent containing the metal carbonyl compound 5 and heterocyciic base was refluxed at 80 °C, whereby an active complex was produced in the transfer reaction of the aqueous gas. The heterogeneous catalyst was produced directly on the surface of the carrier by heating at 100 °C protective gas or vacuum silicon gel in which cluster compound and base were impregnated. Hereby •jO was produced a dark blue active catalyst. Advantages of the catalyst of the invention are outstanding activity and stability whereas a disadvantage sensitivity to air. As taught by the invention, it has been found that from the above ■ J5 described metal cluster base system a new catalyst can be syn- thetized for producing alcohols or aldehydes from alkenes and synthesis gas by means of a hydroformulation reaction. Thus, the procedure of the invention for producing alcohols or aldehydes from alkenes and synthesis gas by means of hydroformulation reaction 20 is characterized in that a gas mixture containing alkene, hydrogen and carbon monoxide is made to react at over 100 °C in the presence of the heterogenic catalyst system, comprising a solid catalyst compound produced from a cluster compound Ru3(CO)- j _2 and from a heterogeneous base in a suspension, or bound on the surface of a 25 solid carrier substance. In the procedure of the invention is gained the surprising advantage that alcohols are produced in the hydroformulation at a high selec¬ tivity rate. In certain instances, from alkenes are produced almost 30 exclusively alcohols. This is a very great improvement in comparison with conventional hydroformulation catalysts which merely yield either aldehydes or mixtures of aldehydes and alcohols, and thus require an extra processing phase for hydrating aldehydes into alcohols. In addition, with the procedure of the invention the 35 desired direct-chain alcohol is obtained in a remarkably selective manner. The activity of the catalyst is also significant in hydro¬ formulation of merely end-double-bound alkenes at 373 °K. 1 In the catalyst system used in the procedure of the invention, the heterocyciic base can be selected from the group which contains , for instance 2,2' bipyridine, 2,3' bipyridine, 2,4' bipyridine: 6,2" terpyridine, and 1,10 phenan hroline, or compounds in which c the aromatic ring system is composed of two or several nitrogen atoms. The best results are obtained when the base is a 2,2' bipyridine, whereby the conversion of alkenes into alcohols can be almost complete. Also other of said bases are useful, even though the conversion degree therein is lower. In that instance, the ■|0 conversion degree may however be improved by returning part of the products back to the hydroformulation reaction. The catalyst system used in the procedure of the invention can be prepared by mixing ruthenium carbonyl Ru CO)-*^ and a heterocyciic •J5 base, and heating the obtained complex system for obtaining an active catalyst. The heating temperature is not critical, and it may therefore vary between 50 to 200 °C. An appropriate temperature has proved to be about 100 °C. The heating need to be performed either in a sheltering gas, for instance in nitrogen, or alter- 20 nately, in vacuum, because the catalyst complex to be produced is sensitive to air. In the procedure of the invention, the hydroformulation is performed in a heterogeneous phase, which means that the catalyst is not 5 soluble in a solvent used possibly in the hydroformulation. An active catalyst complex may be applied in a heterogeneous hydro¬ formulation reaction as such, whereby the hydroformulation is accomplished in suspension or performing the activation when the catalyst complex is absorbed in a carrier. For the carrier, it is 0 advantageous to use inorganic silicon compounds, for instance silica gel or magnesium silicates, or other inert inorganic carriers, such as aluminium oxide. In the procedure of the in¬ vention, the heterogeneous hydroformulation can be accomplished either in liquid or gas phase. In the reaction can be used a 5 solvent, for which the catalyst being used is non-soluble. For obtaining good results, the pressure and especially the temperature is required to be on a sufficiently high level. A recommendable 1 pressure is at least 1 MPa, and the temperature is over 360 K. The hydroformulation temperature to be recommended is of the order 460 K. g The selectivity of formation of compounds containing oxygen, or alcohols and aldehydes, is high in the procedure of the invention, and no hydration of olefines takes place in the hydroformulation process. The non-reactive defines can easily separated from the products by distilling and circulating them back into the reactor. 10 The reaction is extremely exothermal and therefore, it is advantageous to act on lower conversion levels. The ruthenium concentration and H2:C0 ratio exerts an effect on the product distribution, that is, alcohols are most produced when ■ J5 H2:C0 ratio is of the order 1:1. The invention is described in the following more in detail with the aid of the embodiment examples. 20 Example 1 A catalyst was prepared by mixing 3.0 g silicon dioxide (silika grades F-22) , 0.096 g Ru 3 (CO)- L2 , 0.073 g 2,2' bipyridine, and 50 ml CH2CI2. The solvent was evaporated, the catalyst was trans- 25 ferred into an airproof metal tube and rinsed with nitrogen. The catalyst was activated by heating the metal tube at 100 °C, whereby In the carrier was produced a blue active compound. Example 2 30 A catalyst was prepared as in Example 1, with the exception that of the carrier was used 1.0 g and of u β ζCO -*^, 0.1 g. Examples 3 and 4 35 The catalysts were prepared as in Example 1, with the exception that in Example 3 the carrier was Davison silika, and in Example 4 , the carrier was magnesium silicate . Examples 5 to 8 The catalysts were prepared as in Example 1, with the exception that in Example 5, the base was 2,3' bipyridine (64 μl) , in Example 6, the base was 2,4' bipyridine (0.073 g) , in Example 7, the base was 1,10 phenanthroniline (0.093 g) , and in Example 8, the base was 2,2-:6,2" terpyridine (0.109 g) . Example 9 The catalyst was prepared in a glass retort by activating a Ru3(C0) * L2 (0.2 g) and 2,2' bipyridine (0.15 g) mixture in nitrogen atmosphere at 100 °C. On the glass surface was produced an active dark blue complex. Example 10 A catalyst (0.5 g) , 1-hexene (1 ml) and toluene (5 ml) as in Example 1 was transferred in nitrogen atmosphere into an autoclave to which was added 2.5 MPa H2 and 2.5 MPa CO. The autoclave was held for 17 hrs at 423 °K. The product was cooled and analyzed with IR and NMR spectrometers and with capillary gas chromatography. The reaction product contained 96% Cη alcohols in which the ratio of the direct chained and the branch chained was 1.1. Example 11 As in Example 10, but for the alkene was used trans-2-hexene. The reaction product contained 97% C7 alcohols (direct chained/branch chained -= 0.9). Example 12 As in Example 10, but for the alkene was used 1-decene. The reaction product contained 95% (_- ■ _ ■ -_ alcohols. 1 Example 13 As in Example 10, but the temperature was 373 K, The reaction product contained 2% alcohols. The example shows that when a too 5 low hydroformulation temperature is used, the conversion degree remains too low. Example 14 • JO As in Example 10, but with a catalyst (0.5 g) such as in Example 2 and at 373 K temperature. The reaction product contained 50% C alcohols (direct chained/branch chained — 2.4). Example 15 15 As in Example 10, but with the catalyst (0.5 g) as In Example 2 and at 373 K temperature. The reaction product contained 10% C alcohols. 0 Example 16 As in Example 10, but with the catalyst (0.5 g) as In Example 2, at 373 K temperature, and for the alkene a trans-2-hexene. The reaction product contained 4% Cη alcohols. 5 Example 17 As in Example 10, but with the catalyst (0.5 g) as in Example 3, and at 373 K temperature. The reaction product contained 2% C7 0 alcohols. Example 18 As in Example 10, but with the catalyst (0.5 g) as in Example 3, 5 and at 373 K temperature. The reaction product contained 26% C- j alcohols (direct chained/branch chained = 3.5). Example 19 As in Example 10, but with the base as that in Example 10, and at 373 K temperature. The reaction product contained 60% Cy aldehydes. Example 20 As in Example 10, but with the base as that in Example 6, and at 373 K temperature. The reaction product contained 18% Gη aldehydes. Example 21 According to Example 10, but with the base as in Example 7, and at 373 K temperature. The reaction product contained 25% Cη aldehydes and 9% C alcohols. Example 22 As in Example 10, but with the base as in Example 8, and at 373 K temperature. The reaction product contained 25% C aldehydes and 11% C*7 alcohols. Example 23 As in Example 10, but with the catalyst (0.1 g) as in Example 9, and at 373 K temperature. The reaction product contained 40% Cη aldehydes and 25% Cη alcohols.

Claims: Claims 1. A procedure for preparing alcohols and aldehydes from alkenes and synthesis gas selectively by hydroformulation, characterized in that a gas mixture containing alkene, hydrogen and carbon monoxide is caused to react in the presence of a heterogeneous catalyst system being composed of a fixed catalyst compound produced from a cluster compound ano - a hase containing heterocyciic nitrogen as suspension or bound on the surface of a solid carrier. 2. Procedure according to claim 1, characterized in that the hetero¬ cyciic base has been selected from the group 2,2' bipyridine, 2,3' bipyridine, 2,4' bipyridine, 2,2':6,2" terpyridine and 1,10 phenan- throline. 3. Procedure according to claim 1 or 2, characterized in that the cluster compound is prepared by activating the mixture of the cluster compound R 3(CO)--_2, heterocyciic base and fixed carrier by heating at 50 to 200 °C. 4. Procedure according to any one of the preceding claims, charac¬ terized in that the carrier is a silicon containing compound. 5. Procedure according to any one of the preceding claims, charac- terized in that the heterocyciic base Is a 2,2' bipyridine and the fixed carrier is a silica gel. 6. Procedure according to any one of the preceding claims, charac¬ terized in that the hydroformulation is performed in a solvent in which the catalyst system is mainly non-soluble.

Inventors: ALVILA LEILA, KRAUSE OUTI, PAKKANEN TAPANI, VENAELAEINEN TAPANI, ALVILA, LEILA, KRAUSE, OUTI, PAKKANEN, TAPANI, VENAELAEINEN, TAPANI
Applicants: NESTE OY
Application year: 1989
Main classification: C07C45
IPC codes: C07C29, C07C45