Hydrogenation catalysts and process for the removal of aldehydes and ketones from gaseous streams rich in carbon monoxide

• US 3,925,490 A
• Filed: 07/13/1970
• Issued: 12/09/1975
• Est. Priority Date: 07/15/1969
• Status: Expired due to Term

• Current Assignee: Manfred Reich, Manfred Zur Hausen, Wolfgang Muller
• Original Assignee: Manfred Reich, Manfred Zur Hausen, Wolfgang Muller
• Inventors: Reich, Manfred, Muller, Wolfgang, ZUR Hausen, Manfred
• Primary Examiner(s): Evans, Joseph E.
• Application Number:
  US05/054,589
• Time in Patent Office: 1,975 Days
• Field of Search: 260/643B,638B,638HF 23/24M
• US Class Current: 568/914
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/868 copper and chromium
• CPC Class Codes: B01J 23/8993 with chromium, molybdenum or tungsten
• CPC Class Codes: C07C 29/141 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/12 containing four carbon atoms
• CPC Class Codes: C10K 3/00 Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide

Abstract

Aldehydes and ketones contained in gaseous streams rich in carbon monoxide, such as produced in the Oxo process, are selectively hydrogenated to alcohols on copper/chromium supported catalysts.

Claims

1. IN A PROCESS FOR THE REMOVAL OF ALKANALS AND ALKANONS HAVING 3 TO 8 CARBON ATOMS FROM GASEOUS STREAMS OBTAINED IN THE OXO PROCESS RICH WITH ABOUT 5 TO 95 PERCENT BY VOLUME OF HYDROGEN, ABOUT 5 TO 60 PERCENT BY VOLUME OF CARBON MONOXIDE AND ABOUT 5 TO 60 GRAMS OF SAID ALKANALS AND ALKANONES PER CUBIC METER AT NORMAL CONDITIONS, THE IMPROVEMENT COMPRISING HYDROGENATING SAID ALDEHYDES AND KETONES TO ALKANOLS AT A TEMPERATURE OF ABOUT 100* TO 200*C, A PRESSURE OF ABOUT 3 TO 50 ATMOSPHERES AND IN THE PRESENCE OF A SUPPORTED METAL CATALYST COMPIRISNG 100 PARTS SUPPORT MATERIAL BY WEIGHT, ABOUT 5 TO 100 PARTS BY WEIGHT OF COPPER AND ABOUT 0.5 TO 50 PERCENT BY WEIGHT OF CHROMIUM BASED ON THE WEIGHT OF THE COPPER, SAID SUPPORTED METAL CATALYST IS PREPARED BY PRECIPITATING SALTS OF THE COPPER AND CHROMIUM FROM SOLUTION, DRYING THE PRECIPITATED MATERIAL AND REDUCING THE SALTS IN A HYDROGEN STREAM AT AN ELEVATED TEMPERATURE OF ABOUT 100* TO 300*C.

2. The process according to claim 1, wherein the hydrogenation is conducted in the presence of an excess of hydrogen of at least ten times the amount theoretically required for the hydrogenation.

3. The process according to claim 2, wherein the hydrogenation is conducted in several partial stages, between which stages the principal amount of the alkanol produced is removed from the gaseous mixture.

4. The process according to claim 1, wherein the alkanol produced is obtained from the gaseous stream by condensation.

5. The process of claim 1, wherein the alkanol produced is obtained from the gaseous stream by scrubbing.

6. The process of claim 1, wherein said supported metal catalyst has a copper concentration of about 3 - 35 parts by weight.

7. The process of claim 6, wherein said supported metal catalyst has a chromium concentration of about 3 to 20 parts by weight of the copper concentration.

8. The process of claim 1, wherein said supported metal catalyst has a nickel concentration of about 0.1 to 80 percent by weight of the copper concentration.

9. The process of claim 7, wherein said supported metal catalyst has a nickel concentration of about 5 to 50 percent by weight of the copper concentration.

10. A process for the removal of n-butyraldehyde and isobutyraldehyde from the expansion gas of the Oxo process wherein butyraldehyde is produced from propylene, carbon monoxide and hydrogen and the expansion gas has about 5 to 60 grams of said n-butyraldehyde and isobutyraldehyde per cubic meter at normal conditions, about 5 to 95 percent by volume of said hydrogen, and about 5 to 60 percent by volume of said carbon monoxide, comprising hydrogenating said n-butyraldehyde to n-butanol and iso-butanol at a temperature of about 100* to 200*C, a pressure of about 3 to 50 atmospheres and in the presence of a supported metal catalyst comprising 100 parts of support material by weight, about 5 to 100 parts by weight of copper and about 0.5 to 50 percent by weight of chromium based on the weight of the copper, said supported metal catalyst is prepared by precipitating salts of the copper and chromium from solution, drying the precipitated material and reducing the salts in a hydrogen stream at an elevated temperature of about 100* to 300*C.

11. The process of claim 10, wherein the hydrogenation is carried out at a temperature of about 120* to 180*C, a pressure of about 5 to 30 atmospheres and about 500 to 10,000 parts by volume of said expansIon gas are passed over one part by volume of said catalyst per hour.