CATALYST SYSTEM AND PROCESS FOR PRODUCING ALCOHOLS FROM OLEFINES AND SYNTHESIS GASES

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 syn¬ thesis gases (H2+OO) . This synthesis belongs to the group of hyelvo- formylation, or oxo, reactions, by which c * ompc * unds containing oxygen, such as aldehydes and alcohols, are usually produced from olefines. The catalysts to be used in the reaction are typically hc-mogerieous and they contain * rtιcdi * um or cobalt either in the form of carbonyls or phosphines. However, isolation of the catalyst dissolved in the reaction -flύ-xture poses a difficult problem, par¬ ticularly when catalysts cxιn * r^ ning rhodium are used, and it affects the process costs. Endeavours have been made to avoid the drawbacks of homogeneous catalysis by binding the metal αxipounds on a solid carrier, which may be of organic or inorganic origin. However, heterogeneous h * yτdroformylation catalysts are often less active than hcxncgeneous ones, the metals are solved off the carriers in reaction conditions, and their thermal durability is limited. Metal cluster compounds constitute a group of ccan^ounds which have favourable properties as catalyst precursors. In the U.S. Patent No. 4,144,191, a bimetallic carbonyl cluster c ipound catalyst for producing alcohols by h * yτdroformylation is disclosed. For cluster cai-pc-und, either bound to an organic polymer containing amine groups. The catalyst operates at low temperature and produces almost exclusively alcohols. In the F-Lnnish patent application No. 844634 the observation is made that a -mixture of the iKjnometal cluster cxxpounds R14(00) _2 and 00 (00)12 bound to an amine resin carrier serves as the ex¬ tremely selective catalyst in producing alcohols. An advantage of the cluster inixture catalyst is that it is simpler to prepare and its activity can be optimized as a fimction of the mole proportion of the metals. Increasing the reaction rate in the hydrofor ylation reaction would be desirable, and feasible by raising the reaction tempera¬ ture, 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 inonometal cluster cαiipσund mixtures containing rhodium and cobalt, or bimetallic αxipαunds containing rhodium and cobalt, on inorganic carriers that the h * ydroformylation 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 p * roduced with high selectivity and at relatively high temperatures. The catalyst system of the invention for pro¬ ducing alcohols selectively from defines and synthesis gases is characterized in that it comprises one or several metal duster ccrapσunds belonging to the cobalt group on an inorganic carrier and an amine of the form NR1R2R3, where Rχ,R2 and R3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms. Adding amine either into the reaction m rt ** ure, on the carrier, or to both, is indispensable for achieving sufficient alcohol con¬ version. The bimetallic Cc^ ^(00) _2 mixture as well as a mixture of inonometal dusters Co 4 (00)3 and 4(00) 2 bound to aluminium oxide or silicon dioxide-based carriers produce nothing but alde¬ hydes 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 rdated both to production technology and reaction technique. The catalyst is prepared by mixing a carrier and a metal duster cccpcund in a solvent. After the binding process has been completed, the solvent is * re * moved, the catalyst rinsed with pure solvent, and dried in vacuum. The binding depends on the oxide carrier, on the chemical and r-echanical 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 fin y ground carriers bind best, and they are also the most active in catalytic reactions. In practice, more coarsdy ground materials are easier to handle. Impregnating a tertiary amine directly into the carrier material prior to b * ύτding the cluster compound also results in an active hydroformylation catalyst producing alcohols. Admittedly, amine- impregnated alumi um oxide and silicon oxide bind duster xupounds 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 -tαixture and part of it to the catalyst. The quantity of amine is advantageously 0.1 to 10 % by weight of the reaction • mixture. Secondary and primary amines also act as factors catalyzing the hydroformylation reaction of rhcdium-cobalt duster exxtpounds bound on a carrier into alcohols. For i-ristance, the conversion of l-hexylene an adding diethylamine, Et 2 NH, is certainly complete, but C 7 alcohols are produced, even in advantageous circumstances, only with about 70 % sdectivity. Moreover, the cUethylamine is used up completely in hydroformamination with that l-hexylene which is not converted into C7 alcohols. It is thus noted that the me al cc * tmpound catalyzes also this side reaction. -CH=CH2+0D+H2+Et2NH > R-(GH 2 )3 Et2 * +H2 0 Primary amines, such as aniline, behave in the same way and form the cxsrresponding hvdroforπiamination products. When the amine is replaced with ammonia in the hydroformylation inixture of l-hexylene in the presence of [Cr Rh2(CD)i2]- * uιι * r um oxide, the ability of the catalyst to produce C 7 products ceases altogether. Adding a tertiary amine to the cluster catalyst m * ixture is not the only remarkable factor controlling the product distribution. The amount of the duster c * cmpound an the carrier also exerts an influ¬ ence an the activity and sdectivity 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 cαtpound Oo x Rh 4 _ x (O0) 1 2, or 3, or a 004(00)12 and Rh 4 (00)i2 mixture can be used, without significant difference in catalytic character- istics in similar reaction cxanditions. 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. Alcchoi 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 a uminium oxide (Alumina grades D, dried at βOO^), 0.1 g O^Rt^OO)^ (Martinego, S et al., J. Crrgancmet. Chem. *59 (1973), p. 379) and 0.020 dm 3 hexylene in nitrogen atmosphere for 15 hrs. The hexylene α»ϊteining 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 carrierwas 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 quan¬ tity of cluster coiupciund C02PJ121 00 )12 ' was °* 05 9* Example 6 The catalyst was prepared as in Example 1, except that instead of the mixed cluster ccrpound was used a cluster compound with 0.035 g 004(00) 2 (Strem Chemicals), and 0.071 g 4 (00)i2 (Martinego, S. et al. Inorganic Synthesis, Vol. 20, 1980, p. 209) . Example 7 The catalyst was prepared as in Example 1, except that the duminium 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) , l-hexylene (1.0 dm 3 ), toluene (3.0 dm 3 ), and triethylamine Et 3 N (0.11 x 10~ 3 dm 3 , 0.79 mmol) were transferred in nitrogen atmosphere into an autoclave (V=0.075 dm 3 ) , into which 2.5 MPa H 2 and 2.5 MPa 00 were added. The autodave was kept at 373 K for 17 hrs. The product -mixture was cooled and analyzed with IR and NMR spectrometers, and by capillary gas cihrorMtography. The reaction product contained 97 % C 7 alcohols. Example 9 As Example 8, but the triethylamine quantity was 0.10 x 10" 3 dm 3 . The reaction product contained 79 % C 7 dcohols and 20 % C 7 alde¬ hydes. Example 10 As Example 8, but trieteylamine quantity 0.05 x 10~ 3 dm 3 . The reaction product conteined 30 % C 7 alcohols and 55 % C 7 aldehydes. Example 11 As Example 8, but teieteylamine quantity 0.025 x 10~ 3 dm 3 . The reaction product contained 14 % C 7 cohols and 70 % C 7 aldehydes. Example 12 As Example 8, but no amine was added. The reaction product conteined 85 % 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 13 As Example 9, but the amine was Et 2 NH (0.79 mmol) . The reaction product conteined 62 % C 7 alcohols and 19 % C 7 aldehydes, and 19 % byproducts cc-nteining amine. Example 14 As Example 8, but using the catalyst of Example 6 (0.353 g) and for aUene, propylene (0.8 g). The reaction mixture cx-ntained 90 % C 7 alcohols. Example 15 As Example 8, but using the catalyst of Example 3 (0.1 g) . The reaction mixture conteined 56 % C 7 alcohols and 39 % C 7 aldehydes. Example 16 As Example 4, but using the catalyst of Example 5 (0.1 g) . The reaction mixture conteined 55 % C 7 dσohols and 35 % C 7 aldehydes. Example 17 As Example 8, but using the catalyst of Example 7 (0.1 g) . The reaction mixture conteined 70 % C 7 cohols, 16 % C 7 aldehydes and 12 % Ci4 alcohols.

Claims: Claims 1. A catalyst system for sdectivdy producing alcohols from defines and synthesis gases, characterized in that it comprises one or several metal duster cx-mpounds belonging to the cobalt group on an inorganic carrier and an amine of the form N 123, where R R2 and R 3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms. 2. Catalyst system according to dai 1, characterized in that the metal duster compound is 004(00)12, R 4 (C0)i2 or a -mixture thereof. 3. Catalyst system according to claim 1, characterized in that the metal duster α-impcund is a mixed duster cαπpcund of the form Co x Rh4_ x (CO)i2, where x=l-3. 4. Catalyst system according to any one of the preceding claims, ciiarac±erized 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 * bιorganic carrier sub¬ stance. 6. Catalyst system according to any one of the preceding claims, ciiaracterized 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, c-haracterized in that the amine is triethylamine. 8. Catalyst system a x>rding to any one of the preceding daims, cha-ractørized in that the carrier substance is uπdnium oxide, silicon dioxide, zeolite or magnesium silicate. 9. A process for sdectivdy proiducing alcohols from defines and synthesis gas, ciiaracterized in that a mixture containing olef ine, hydrogen and carbon inonoxide is reacted in the presence of a cata¬ lyst system according to claims 1 to 8.

Inventors: ALVILA LEILA, JOUTSIMO MATTEUS, KRAUSE OUTI, PAKKANEN TAPANI, ALVILA, LEILA, JOUTSIMO, MATTEUS, KRAUSE, OUTI, PAKKANEN, TAPANI
Applicants: NESTE OY
Application year: 1986
Main classification: C07C29
IPC codes: B01J23, B01J31, C07C29