DE1065829B - Process for the production of oxygen-containing organic compounds - Google Patents

Description

GERMAN

The production of oxygen-containing compounds, in particular aldehydes, by reacting an olefinically unsaturated compound with a mixture of carbon oxide and hydrogen at elevated temperature and pressure in the presence of a cobalt-containing one The catalyst is well known. Catalysts have already been used in this synthesis from cobalt carbonate, cobalt oxide or cobalt carbonyl. Catalysts consisting of cobalt compounds apparently form cobalt carbonyl in the first stages of the process. The hydroformylation will then subsequently promoted by the cobalt carbonyl formed as an active catalyst. Cobalt carbonyl of Using it as a catalyst in the first place brings about its toxic nature and instability many disadvantages.

It has now been found that cobalt oxide is used as the catalyst in the claimed process Excellent results can be obtained if you use a cobalt oxide which you previously used by thermal decomposition from cobalt carbonate at a relatively low temperature of 370 to 425 ° C.

The conversion of cobalt oxide into the active cobalt carbonyl is evidently of a special nature de ^ cobalt oxide of great importance, as can be seen from the following experiments:

! .Book. Commercially available pure cobalt carbonate was in a steel autoclave at a temperature of 85 to 120 ° C and a pressure of 230 atmospheres Influence of a synthetic gas mixture, consisting of carbon monoxide and hydrogen, exposed. The captured was then opened. The analysis indicated that 72% cobalt carbonyl had formed.

Second attempt. The experiment was carried out at the same time, for the same length of time and under exactly the same conditions as the third experiment, but instead of the cobalt carbonate a cobalt oxide was used that according to the invention by roasting the cobalt carbonate for a period of 8 hours in air at 370 to 425 ° C was won. The analysis of this experiment showed that 95 ⁰ Zo of the cobalt oxide had been converted into cobalt carbonyl.

These and numerous other comparative tests carried out by the inventor show that absolutely not all cobalt compounds are equivalent as carbonyl forming agents, not even for This is the case with cobalt carbonate and cobalt oxide.

In the claimed process, the reaction is generally carried out in the liquid phase at a temperature between 130 and 250 ° C. and at a pressure between 140 and 630 kg / cm ³ . The reaction participants can either be used as a batch or intermittently or continuously in a reacting process for production

of oxygen-containing organic

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Applicant:

Union Carbide Corporation,
New York, NY (V. St. A.)

Representative: Dr. phil. Dr. rer. pole. K. Koehler,
Patent attorney, Munich 2, Amalienstr. 15th

Claimed priority:
V. St. v. America 7 October 1953

Robert Preston Bowditch and Helmut William Schulz,

Charleston, W.Va. (V. St. A.),
have been named as inventors

tion vessel are introduced. The cobalt oxide catalyst of the reaction is advantageously in the form of a Suspension in a liquid hydrocarbon fed, if desired, one of the reaction participants can be.

The oxygen-containing compounds prepared by the process of the invention are general Hydroformylation products of the organic material used as the starting material. To the Examples include butyraldehyde and isobutyraldehyde from propylene and, as explained in Example 1, aldehydes and alcohols having 13 carbon atoms are obtained from triisobutylene. To the as starting material olefinic organic compounds suitable for the process of the invention include alkene hydrocarbons, Esters of unsaturated acids and the like, such as e.g. B. ethylene, propylene, butylene, pentenes, Hexene, diisobutylene, tripropylene, triisobutylene, methyl acrylate, ethyl crotonate, allylidene diacetate and also olefinic hydrocarbons from the cracking process of oil and gas.

In carrying out the invention, the participants (carbon oxide, hydrogen and the olefinically unsaturated organic compound) preferably in an approximately stoichiometric quantitative ratio used to ensure the completeness of the implementation. For example, the Production of butyraldehydes in high yields

909 629/324

aims when the molar ratio of H ₂ -C O synthesis gas to propylene is adjusted in the range of about 1.1: 1 to about 1.3: 1; a substantial excess of a reactant can be employed if desired.

The process can be carried out at temperatures in the range from 130 to 250 ° C., the optimum temperature according to the reactivity of the unsaturated to hydroformyl reaction organic compound varies.

Overpressure is advantageously used, preferably in the range from 140 to 630 kg / cm ² .

The cobalt oxide catalyst can be prepared by heating a moist cobalt carbonate filter cake with about 50% water for several hours to drive off the water. The troc KENE material is then subjected to a temperature in the range of 370 to 427 ° C for 8 hours and ground to a particle size of about 1 micron after cooling.

The cobalt oxide catalyst produced in this way can be used with greater success for the reaction, when in suspension in a liquid medium, e.g. B. in an olefinic material or in Mineral oil, toluene, or butanol in a portion of the raw converter product that is ready for reuse can be returned. The catalyst is used in amounts of 0.1 to 10% by weight of the olefinic organic compound applied.

The process can be carried out by heating the reactants in a suitable one pressure-tight reaction vessel, e.g. B. an autoclave or converter. When reacting with corrosive Respondents, such as B. unsaturated acids, the steel pressure vessel should advantageously be corrosion-resistant Metal lined, such as stainless steel or silver.

The surprising and peculiar effect, which with the according to the invention in a special way produced cobalt oxide is achieved, results from the following comparative tests:

Experiment 3: In a mixture of 5-C-atomic hydrocarbons (containing 60 * / o diolefins, 20% monoolefins and the remainder pentane) was 0.25 percent by weight commercial cobalt oxide suspended. The mixture was at a temperature of 200 ° C and a pressure of 400 atm with a synthesis gas mixture of hydrogen and carbon oxide in one Converter dealt with.

The reaction had to be ίο after 2 hours ¹ Iz aborted because had been formed by polymerization of the diolefin, a mixture of cobalt oxide and resinous materials, the completely clogged the converter.

Analysis of the product showed 14% of the hexyl alcohol and hexyraldehyde formed.

Experiment 4: The experiment was carried out under otherwise completely identical conditions and in the same time as First attempt carried out, only that a cobalt oxide was used instead of the commercially available cobalt oxide according to the invention by thermal decomposition of cobalt carbonate in air was made at a temperature between 370 and 445 ° C.

The cobalt oxide obtained in this way contained 68 percent by weight of cobalt and had a density of 0.272 g / cm ³ ; it was easily suspended in the olefinic starting material.

The reaction was smooth and uneventful. It led to a yield of 77% in 5 hours Hexyl alcohol and hexyraldehyde; the conversion of the unsaturated portion was therefore 96%.

The following table shows a range of numbers

Attempts in which propylene in the presence of the new cobalt oxide catalyst of the action of

Was subjected to carbon monoxide and hydrogen.

The respondents were in the desired

Mixed proportions and before introduction into

the reaction vessel to certain. Temperatures and pressures preheated while pumping in the ground Carbon oxide catalyst in suspension in mineral oil

into the reaction vessel in such an amount that the

Tempe Molecular Propylene Propylene Too cataly Propylene Exploit Butyr Other pressure rature relationship purity Space- sier conversion Butyr aldehyde
and butanols liquid
Products ( ⁰ C) H ₂ : CO: C ₈ H. (Vo) fast
speed Coals
hydrogen (Vo) aldehyde (V.) (kg / cm ² ) 206 1.27: 1.29: 1.0 87.2 (V / V / hour) C ₃ H, 95.0 (Vo) 85.5 8.2 352 212 1.15: 1.24: 1.0 90.1 347 0.0016 46.7 80.5 83.0 8.0 281 208 1.14: 1.31: 1.0 84.8 448 0.0030 47.3 82.1 83.1 4.8 281 201 1.07: 1.18: 1.0 85.0 412 0.0022 69.6 82.1 87.4 6.1 316 203 1.02: 1.18: 1.0 82.6 441 0.0026 82.1 86.0 77.5 13.6 387 216 1.25: 1.51: 1.0 96.8 424 0.0023 98.4 75.0 76.3 13.5 422 215 1.53: 1.72: 1.0 86.2 505 0.0017 98.7 68.8 79.0 16.2 422 215 1.34: 1.43: 1.0 83.3 424 0.0020 99.1 73.9 73.6 13.9 422 213 1.17: 1.27: 1.0 86.8 424 0.0020 75.8 64.9 81.0 5.9 352 205 1.21: 1.26: 1.0 88.2 437 0.0032 83.8 78.4 86.3 1.5 352 209 1.17: 1.17: 1.0 88.1 439 0.0016 63.6 83.5 80.2 10.8 281 206 1.17: 1.17: 1.0 89.3 224 0.0020 95.0 80.2 85.1 10.6 281 206 1.27: 1.30: 1.0 88.5 239 0.0019 98.9 78.5 80.0 12.9 281 202 1.41: 1.74: 1.0 86.4 258 0.0018 99.2 72.1 86.0 11.0 316 206 1.18: 1.25: 1.0 86.6 257 0.0019 96.9 74.1 82.0 14.8 316 204 1.24: 1.32: 1.0 84.0 217 0.0018 95.9 78.9 74.6 20.8 352 204 1.41: 1.52: 1.0 88.8 204 0.0023 98.9 64.0 79.3 11.4 352 198 1.31: 1.41: 1.0 85.1 271 0.0018 99.0 65.7 77.0 11.8 387 210 1.22: 1.33: 1.0 86.0 258 0.0016 97.9 67.5 66.9 24.0 352 215 1.18: 1.21: 1.0 94.7 207 0.0025 95.6 61.1 73.6 19.4 422 204 1.40: 1.59: 1.0 80.8 279 0.0022 99.2 61.1 72.4 17.5 422 212 0.0024 62.6

rate of catalyst feed in the range from about 0.0010 to about 0.0040 kg of catalyst per kg propylene fed to the reaction vessel is maintained.

The following examples illustrate the general applicability of the method of the invention to unsaturated olefinic compounds other than propylene.

example 1

A suspension of 0.5% of the cobalt oxide prepared as described above in triisobutylene was in a high pressure reaction space with a space velocity of 1.16 volumes of liquid introduced per volume of reaction space per hour at a temperature of 220 ° C.

An equimolecular carbon monoxide-hydrogen gas mixture is sent through the liquid under a pressure of 422 kg / cm ² . Analysis of the liquid products withdrawn from the reaction vessel showed that the yield of aldehydes and alcohols having 13 carbon atoms was 35% based on the weight of the triisobutylene fed to the reaction vessel.

Example 2

A mixture of 550 g of ethyl crotonate and 275 g of toluene was reacted with an equimolecular mixture of carbon monoxide and hydrogen at 155 ° C. and 316 kg / cm ² pressure, using 55 g of cobalt oxide as a catalyst. The distillation of the crude reaction product and the analysis of the fractions showed a 99% conversion of ethyl crotonate and a yield of 55% of hydroformyl products, based on the ethyl crotonate used. The hydroformyl products contained delta-valerol acetone, ethyl 5-hydroxyvalerate, ethyl 2-fornyl butyrate and ethyl 4-formyl butyrate.

Example 3

A slurry of 30 g of the new cobalt oxide, 80 g of toluene and 3050 g of allylidene diacetate was introduced into a high pressure vessel through which an equimolecular carbon monoxide-hydrogen gas mixture was passed while maintaining a pressure of 422 kg / cm ² . The slurry was fed to the reaction vessel at a space velocity of 1.3 volumes of liquid per volume of reaction space per hour; the reaction takes place at 145 ° C .; the crude reaction product was continuously removed through a liquid overflow line. The yield of 4,4-diacetoxybutyraldehyde was 47%, based on the weight of allylidene diacetate fed into the reaction space. existed, was placed in a high pressure vessel;] carbon monoxide-hydrogen mixture was fed separately. The gas space velocity of ι hydrocarbon. Carbon monoxide and hydrogen! was 221, 242 and 351 \ 'volumes per volume of reaction space per hour. The catalyst (cobalt oxide prepared as described above) was introduced as a 1 to 2 weight percent suspension in mineral oil at a rate sufficient to provide a ratio of 0.0023 kg cobalt oxide per kg olefins. The three systems of the substances fed went through the reaction space at 205 ° C., which was kept under a pressure of 422 kg / cm ² . The product contained 86 percent by weight of pentanals and pentanols, based on the oil-free and gas-free product, which corresponds to a yield of 82.7% based on the weight of the hydrocarbon mixture used.

Claims (6)

Patent claims: 1. Process for the preparation of oxygen-containing organic compounds by reaction an olefinically unsaturated compound with a mixture of carbon monoxide and Hydrogen at elevated temperature and pressure in the presence of one in a liquid medium suspended, cobalt-containing catalyst, characterized in that a Cobalt oxide is used, which is produced by thermal decomposition of cobalt carbonate at a Temperature between 370 and 425 ° C was obtained. 2. The method according to claim 1, characterized in that the reaction at a temperature is carried out between 150 and 200 ° C. 3. The method according to claim 1, characterized in that that the reaction is carried out at a pressure between 140 and 622 atmospheres. 4. Further development of the method according to claim 1, characterized in that aldehydes getting produced. 5. Further embodiment of the method according to claim 1, characterized in that butyraldehyde will be produced. 6. The method according to claim 1, characterized in that for the production of butyraldehyde Propylene, carbon monoxide and hydrogen in a ratio of 1 kg propylene to 0.001 0.004 kg of the cobalt oxide catalyst are implemented. Example 4 A hydrocarbon mixture consisting mainly of monoolefins with 4 carbon atoms in the molecule Considered publications: German Patent Nos. 766 152, 863 194, 849; Bics Report, 447, p. 40. ® 909 629/324 9.