CATALYSTS FOR ISOBUTANOL SYNTHESIS FROM SYNGAS AND ETHANOL OR PROPANOL

Abstract

A process for the production of propanol and/or isobutanol is disclosed. The process comprises reacting ethanol or propanol with synthesis gas in the presence of an alkali or alkaline earth doped CuMn oxide catalyst under reaction conditions to produce propanol and/or isobutanol. The catalyst may include one or more additional metal oxides as catalyst support.

Claims

1. A process for the production of propanol and/or isobutanol comprising: reacting ethanol or propanol with synthesis gas in the presence of an alkali or alkaline earth doped CuMn oxide catalyst under reaction conditions to produce propanol and/or isobutanol.

2. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises Cu oxide in an amount of 0.1 wt% to 90 wt%, and Mn oxide in an amount of 0.1 wt% to 90 wt%.

3. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises at least one alkali or alkaline earth metal in an amount of 0.1 wt% to 30 wt%.

4. The process of claim 3 wherein the at least one alkali or alkaline earth metal comprises at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba. 5.

5. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst further comprises a catalyst support comprising one or more additional metal oxides.

6. The process of claim 5 wherein the one or more additional metal oxide is present in an amount of 0.1 wt% to 95 wt%.

7. The process of claim 5 wherein the one or more additional metal oxide comprises oxides of one or more of: Zn, Cr, Zr, Al, Si, Ti, Ga, Sn, Y, rare earth metals, and combinations thereof.

8. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnCr oxide catalyst.

9. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnZn oxide catalyst.

10. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnZnCr oxide catalyst.

11. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises a Cs doped CuMnZnCr oxide catalyst.

12. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnZr oxide catalyst.

13. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises a CuMnMgZr oxide catalyst.

14. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises a Cs.sub.2O doped CuMnMgZr oxide catalyst.

15. The process of claim 1 wherein the reaction conditions comprise one or more of: a temperature in a range of 150° C. to 500° C.; a pressure in a range of 0.1 to 30 MPa; or a gas hourly space velocity in a range of 100 to 500,000 liters of gas per kg of catalyst per hr (L/kg-h).

16. The process of claim 1 wherein at least one of: a total amount of ethanol or propanol or both is in a range of 0.1 mol% to 50 mol% with the balance being synthesis gas; or the synthesis gas has a ratio of H.sub.2 to CO is in a range of 5:1 to 1:5.

17. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises: 1 wt% to 60 wt% Cu oxide; 1 wt% to 50 wt% Mn oxide; 1 wt% to 20 wt% of the at least one alkali or alkaline earth metal; and 1 wt% to 50 wt% of the one or more additional metal oxides.

18. The process of claim 1 wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnZnCr oxide catalyst comprising: 5 wt% to 60 wt% Cu oxide; 5 wt% to 40 wt% Mn oxide; 2 wt% to 15 wt% of the at least one alkali or alkaline earth metal; 5 wt% to 40 wt% Zn oxide; and 5 wt% to 30 wt% Cr oxide.

Description

DESCRIPTION OF THE INVENTION

[0023] The alkali or alkaline earth doped CuMn oxide catalyst which exhibits good propanol and isobutanol synthesis performance in the aldol condensation reaction between syngas and ethanol or propanol. On the catalyst, the Cu is the active metal for dehydrogenation and hydrogenation in the aldol condensation process, while Mn oxide disperses and stabilizes Cu. The alkali or alkaline earth oxides or salts are used for enhancing C-C coupling in the reaction.

[0024] The alkali or alkaline earth doped CuMn oxide catalyst may include Cu oxide in an amount of 0.1 wt% to 90 wt%, or 1 wt% to 90 wt%, or 1 wt% to 80 wt%, or 1 wt% to 70 wt%, or 1 wt% to 60 wt%, or 1 wt% to 50 wt%, or 1 wt% to 40 wt%, or 1 wt% to 30 wt%, or 1 wt% to 20 wt%, or 5 wt% to 90 wt%, or 5 wt% to 80 wt%, or 5 wt% to 70 wt%, or 5 wt% to 60 wt%, or 5 wt% to 50 wt%, or 5 wt% to 40 wt%, or 5 wt% to 30 wt%, or 5 wt% to 20 wt%, or 10 wt% to 90 wt%, or 10 wt% to 80 wt%, or 10 wt% to 70 wt%, or 10 wt% to 60 wt%, or 10 wt% to 50 wt%, or 10 wt% to 40 wt%, or 10 wt% to 30 wt%, or 10 wt% to 20 wt%, or 20 wt% to 90 wt%, or 20 wt% to 80 wt%, or 20 wt% to 70 wt%, or 20 wt% to 60 wt%, or 20 wt% to 50 wt%, or 15 wt% to 40 wt%, or 20 wt% to 30 wt%, or 20 wt% to 90 wt%, or 25 wt% to 90 wt%, or 30 wt% to 90 wt%, or 30 wt% to 80 wt%, or 30 wt% to 70 wt%, or 30 wt% to 60 wt%, or 30 wt% to 50 wt%, or 30 wt% to 40 wt%, or 40 wt% to 90 wt%, or 40 wt% to 80 wt%, or 40 wt% to 70 wt%, or 40 wt% to 60 wt%, or 40 wt% to 50 wt%, or 35 wt% to 90 wt%, or 45 wt% to 90 wt%, or 50 wt% to 90 wt%.

[0025] The alkali or alkaline earth doped CuMn oxide catalyst may include Mn oxide in an amount of 0.1 wt% to 90 wt%, or 1 wt% to 90 wt%, or 1 wt% to 80 wt%, or 1 wt% to 70 wt%, or 1 wt% to 60 wt%, or 1 wt% to 50 wt%, or 1 wt% to 40 wt%, or 1 wt% to 30 wt%, or 1 wt% to 25 wt%, or 1 wt% to 20 wt%, or 5 wt% to 90 wt%, or 5 wt% to 80 wt%, or 5 wt% to 70 wt%, or 5 wt% to 60 wt%, or 5 wt% to 50 wt%, or 5 wt% to 40 wt%, or 5 wt% to 30 wt%, or 5 wt% to 25 wt%, or 5 wt% to 20 wt%, or 10 wt% to 90 wt%, or 10 wt% to 80 wt%, or 10 wt% to 70 wt%, or 10 wt% to 60 wt%, or 10 wt% to 50 wt%, or 10 wt% to 40 wt%, or 10 wt% to 30 wt%, or 10 wt% to 25 wt%, or 10 wt% to 20 wt%, or 15 wt% to 90 wt%, or 15 wt% to 80 wt%, or 15 wt% to 70 wt%, or 15 wt% to 60 wt%, or 15 wt% to 50 wt%, or 15 wt% to 40 wt%, or 15 wt% to 30 wt%, or 15 wt% to 25 wt%, or 15 wt% to 20 wt%, or 15 wt% to 90 wt%, or 20 wt% to 90 wt%,.

[0026] By “alkali or alkaline earth doped” we mean that the CuMn oxide catalyst contains an alkali or alkaline earth metal cation. There can be one or more alkali or alkaline earth metal in the alkali or alkaline earth doped CuMn oxide catalyst. The alkali or alkaline earth metal can be incorporated in the catalyst by any suitable method including, but not limited to, impregnation and co-precipitation. When the alkali or alkaline earth metal is impregnated on the CuMn oxide catalyst, the alkali or alkaline earth metal will appear before the CuMn oxide (e.g., Cs (or Cs.sub.2O) doped CuMnCr oxide catalyst). When the alkali or alkaline earth metal is co-precipitated with the Cu and Mn oxide precursors, it will appear in the CuMn oxide (e.g., CuMnMgZr oxide). Suitable alkali and alkaline earth metals include Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and combinations thereof. The alkali or alkaline earth metal can be present in an amount of 0.1 wt% to 30 wt%, or 1 wt% to 30 wt%, or 1 wt% to 25 wt%, or 1 wt% to 20 wt%, or 1 wt% to 15 wt%, or 1 wt% to 10 wt%, or 2 wt% to 30 wt%, or 2 wt% to 25 wt%, or 2 wt% to 20 wt%, or 2 wt% to 15 wt%, or 2 wt% to 10 wt%, or 4 wt% to 30 wt%, or 4 wt% to 25 wt%, or 4 wt% to 20 wt%, or 4 wt% to 15 wt%, or 4 wt% to 10 wt%, or 5 wt% to 30 wt% or 5 wt% to 25 wt%, or 5 wt% to 20 wt%, or 5 wt% to 15 wt%, or 5 wt% to 10 wt%, or 10 wt% to 30 wt%, or 10 wt% to 25 wt%, or 10 wt% to 20 wt%, or 10 wt% to 15 wt% or 15 wt% to 30 wt%, or 15 wt% to 25 wt%, or 15 wt% to 20 wt%, or 20 wt% to 30 wt%, or 20 wt% to 25 wt%.

[0027] The alkali or alkaline earth doped CuMn oxide catalyst may include a catalyst support comprising one or more additional metal oxides. Suitable additional metal oxides for the catalyst support include, but are not limited to Zn, Cr, Zr, Al, Si, Ti, Ga, Sn, Y and rare earth metals, and combinations thereof. The additional metal oxide for the support can be present in an amount of 0.1 wt% to 95 wt%, or 1 wt% to 95 wt%, or 1 wt% to 90 wt%, or 1 wt% to 80 wt%, or 1 wt% to 70 wt%, or 1 wt% to 60 wt%, or 1 wt% to 50 wt%, or 1 wt% to 40 wt%, or 1 wt% to 30 wt%, or 1 wt% to 25 wt%, or 1 wt% to 20 wt%, or 5 wt% to 95 wt%, or 5 wt% to 90 wt%, or 5 wt% to 80 wt%, or 5 wt% to 70 wt%, or 5 wt% to 60 wt%, or 5 wt% to 50 wt%, or 5 wt% to 40 wt%, or 5 wt% to 30 wt%, or 5 wt% to 25 wt%, or 5 wt% to 20 wt%, or 10 wt% to 95 wt%, or 10 wt% to 90 wt%, or 10 wt% to 80 wt%, or 10 wt% to 70 wt%, or 10 wt% to 60 wt%, or 10 wt% to 50 wt%, or 10 wt% to 40 wt%, or 10 wt% to 30 wt%, or 10 wt% to 25 wt%, or 10 wt% to 20 wt%, or 15 wt% to 95 wt%, or 15 wt% to 90 wt%, or 15 wt% to 80 wt%, or 15 wt% to 70 wt%, or 15 wt% to 60 wt%, or 15 wt% to 50 wt%, or 15 wt% to 40 wt%, or 15 wt% to 30 wt%, or 15 wt% to 25 wt%, or 15 wt% to 20 wt%, or 20 wt% to 95 wt%, or 25 wt% to 95 wt%, or 30 wt% to 95 wt%, or 35 wt% to 95 wt%, or 40 wt% to 95 wt%, or 45 wt% to 95 wt%, or 50 wt% to 95 wt%.

[0028] The alkali or alkaline earth doped CuMn oxide catalyst can be made using any suitable method including, but not limited to co-precipitation followed by impregnation, sol-gel, deposition-precipitation and incipient wetness impregnation.

[0029] For example, the alkali or alkaline earth doped CuMn oxide catalyst can be made by dissolving precursor compounds of Cu and Mn (and any additional metal oxides) in water. A carbonate or hydroxide is separately dissolved in water. The two solutions are then combined and mixed with stirring to form a solution of mixed metal carbonates or hydroxides. The slurry is filtered, washed with water, dried, and calcined. Finally, the alkali or alkaline earth oxide or salt is impregnated on the solid to generate the catalyst. The alkaline earth oxide can also be co-precipitated with the Cu, Mn and other metal oxides.

[0030] Suitable Cu and Mn precursor compounds include, but are not limited to, nitrates, acetates, chlorides, and sulfates. Suitable alkali or alkaline earth precursors include, but are not limited to hydroxides, carbonates, bicarbonates, nitrates, acetates, formates, and phosphates

[0031] The ethanol or propanol conversion reaction can be a continuous process, a semi-continuous process, or a batch process.

[0032] The ethanol or propanol conversion can take place in any suitable type of reactor, such as fixed-bed reactor and fluidized bed reactor.

[0033] The reactor may contain a total amount of ethanol or propanol or both in the range of 0.1 mol% to 50 mol%or 0.5 mol% to 25 mol%, or 2 mol% to 15 mol%, with the balance being synthesis gas.

[0034] The synthesis gas typically has a molar ratio of H.sub.2 to CO in a range of 5:1 to 1:5, or in a range of 3:1 to 1:3.

[0035] Suitable reaction conditions include one or more of: a temperature in a range of 150° C. to 500° C., or 200° C. to 450° C., or 250° C. to 400° C.; a pressure in a range of 0.1 to 30 MPa, or 0.5 to 15 MPa, or 1.0 to 10 MPa; or a gas hourly space velocity in a range of 100 to 500,000, or 1000 to 200,000, or 2000 to 100,000 liters of gas per kg of catalyst per hr (L/kg-h).

[0036] The alkali or alkaline earth doped CuMn oxide catalyst provides good performance in the conversion of ethanol and syngas to propanol and isobutanol, and the conversion of propanol and syngas to isobutanol.

[0037] Conversion of ethanol ranged from 5 to 100%, while conversion of CO ranged from 5 to 90%. The yield of propanol and isobutanol ranged from 5 to 95%. The propanol and isobutanol productivities were significantly higher than that of the prior art processes, for example 100% increase.

[0038] Conversion of propanol ranged from 5 to 100%, while conversion of CO ranged from 5 to 90%. The yield of isobutanol ranged from 5 to 95%. The isobutanol productivities were significantly higher than that of the prior art processes, for example 150% increase.

[0039] One aspect of the invention is a process for the production of propanol and/or isobutanol. In one embodiment, the process comprises reacting ethanol or propanol with synthesis gas in the presence of an alkali or alkaline earth doped CuMn oxide catalyst under reaction conditions to produce propanol and/or isobutanol.

[0040] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises Cu oxide in an amount of 0.1 wt% to 90 wt%, and Mn oxide in an amount of 0.1 wt% to 90 wt%.

[0041] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises at least one alkali or alkaline earth metal in an amount of 0.1 wt% to 30 wt%.

[0042] In some embodiments, the at least one alkali or alkaline earth metal comprises at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba.

[0043] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst further comprises one or more additional metal oxides.

[0044] In some embodiments, the additional metal oxides are present in an amount of 0.1 wt% to 95 wt%.

[0045] In some embodiments, the additional metal oxides comprise oxides of at least one of: Zn, Cr, Zr, Al, Si, Ti, Ga, Sn, Y, or rare earth metals or combination thereof.

[0046] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnCr oxide catalyst. In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnZnCr oxide catalyst.

[0047] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises a Cs doped CuMnZnCr oxide catalyst.

[0048] In some embodiments, the ethanol is reacted with the synthesis gas and wherein at least one of: a conversion of the ethanol is at least 5%, or a conversion of CO in the synthesis gas is at least 5%.

[0049] In some embodiments, the propanol is reacted with the synthesis gas and wherein at least one of: a conversion of the propanol is at least 5%, or a conversion of CO in the synthesis gas is at least 5%.

[0050] In some embodiments, the reaction conditions comprise one or more of: a temperature in a range of 150° C. to 500° C.; a pressure in a range of 0.1 to 30 MPa; or a gas hourly space velocity in a range of 100 to 500,000 liters of gas per kg of catalyst per hr (L/kg-h).

[0051] In some embodiments, at least one of: a total amount of ethanol or propanol or both is in a range of 0.1 mol% to 50 mol% with the balance being synthesis gas; or the synthesis gas has a ratio of H.sub.2 to CO is in a range of 5:1 to 1:5.

[0052] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises: 1 wt% to 60 wt% Cu oxide ; 1 wt% to 50 wt% Mn oxide; 1 wt% to 20 wt% of the at least one alkali or alkaline earth metal; and 1 wt% to 50 wt% of additional metal oxides.

[0053] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst comprises an alkali or alkaline earth doped CuMnZnCr oxide catalyst comprising: 5 wt% to 60 wt% Cu oxide; 5 wt% to 40 wt% Mn oxide; 5 wt% to 40 wt% Zn oxide; 2 wt% to 15 wt% of the at least one alkali or alkaline earth metal; and 5 wt% to 30 wt% Cr oxide.

[0054] Another aspect of the invention is a process for the production of propanol or isobutanol. In one embodiment, the process comprises: reacting ethanol or propanol with synthesis gas in the presence of an alkali or alkaline earth doped CuMn oxide catalyst under reaction conditions to produce propanol or isobutanol; wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises: 0.1 wt% to 90 wt% Cu oxide; 0.1 wt% to 90 wt% Mn oxide; 0.1 wt% to 30 wt% of the at least one alkali or alkaline earth metal; and 0.1 wt% to 95 wt% of additional metal oxides.

[0055] In some embodiments, wherein the alkali or alkaline earth doped CuMn oxide catalyst comprises at least one alkali or alkaline earth metal in an amount of 0.1 wt% to 30 wt%, and wherein the at least one alkali or alkaline earth metal comprises at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba.

[0056] In some embodiments, the alkali or alkaline earth doped CuMn oxide catalyst further comprises 0.1 wt% to 95 wt% of the additional metal oxides, wherein the additional metal oxides comprise oxides of at least one of: Zn, Cr, Zr, Al, Si, Ti, Ga, Sn, Y, or rare earth metals, or combination thereof.

[0057] In some embodiments, the ethanol is reacted with the synthesis gas and wherein at least one of: a conversion of the ethanol is at least 5%, or a conversion of CO in the synthesis gas is at least 5%.

[0058] In some embodiments, the propanol is reacted with the synthesis gas and wherein at least one of: a conversion of the propanol is at least 5%, or a conversion of CO in the synthesis gas is at least 5%.

[0059] In some embodiments, the reaction conditions comprise one or more of: a temperature in a range of 150° C. to 500° C.; a pressure in a range of 0.1 to 30 MPa; or a gas hourly space velocity in a range of 100 to 500,000 liters of gas per kg of catalyst per hr (L/kg-h).

[0060] In some embodiments, at least one of: a total amount of ethanol or propanol or both is in a range of 0.1 mol% to 50 mol% with the balance being synthesis gas; or the synthesis gas has a ratio of H.sub.2 to CO is in a range of 5:1 to 1:5.

Example 1

[0061] 3%Cs.sub.2O/Cu.sub.5Mn.sub.4Cr.sub.1O.sub.14.5 catalyst was prepared with co-precipitation followed by impregnation of Cs.

[0062] 28.3 g Cu(NO.sub.3).sub.2.Math.2.5H.sub.2O, 34.8 g 50% Mn(NO.sub.3).sub.2 solution and 9.9 g Cr(NO.sub.3).sub.3.Math.9H.sub.2O were dissolved in 162 g deionized water in a beaker.

[0063] In a separate beaker, 53.5 g K.sub.2CO.sub.3 was dissolved in 192 g deionized water.

[0064] The two solutions were pumped to a third beaker containing 200 g deionized water at 70° C. with stirring. The pH value of the mixture was kept at 7.0. After the co-precipitation process was complete, the mixture was stirred for an additional one hour.

[0065] Subsequently, the slurry was filtered and washed with deionized water three times. The obtained paste was dried at 120° C. for 12 hours and then calcined at 400° C. for 4 hours.

[0066] 0.7 g Cs.sub.2CO.sub.3 was dissolved in 10.9 g deionized water and impregnated on the mixed oxide. The catalyst was dried at 120° C. for 4 hours and calcined at 350° C. for 4 hours.

Example 2

[0067] 3%Cs.sub.2O/Cu.sub.5Mn.sub.1Zn.sub.3Cr.sub.1O.sub.11.5 catalyst was prepared with co-precipitation followed by impregnation of Cs.

[0068] 28.9 g Cu(NO.sub.3).sub.2.Math.2.5H.sub.2O, 6.2 g Mn(CH.sub.3COO.sub.3).sub.2.Math.4H.sub.2O, 22.4 g Zn(NO.sub.3).sub.2.Math.6H.sub.2O and 10.1 g Cr(NO.sub.3).sub.3 •9H.sub.2O were dissolved in 166 g deionized water in a beaker.

[0069] In a separate beaker, 54.6 g K.sub.2CO.sub.3 was dissolved in 196 g deionized water.

[0070] The two solutions were pumped to a third beaker containing 200 g deionized water at 70° C. with stirring. The pH value of the mixture was kept at 7.0. After the co-precipitation process was complete, the mixture was stirred for an additional one hour.

[0071] Subsequently, the slurry was filtered and washed with deionized water three times. The obtained paste was dried at 120° C. for 12 hours and then calcined at 400° C. for 4 hours.

[0072] 0.7 g Cs.sub.2CO.sub.3 was dissolved in 15 g deionized water and impregnated on the mixed oxide. The catalyst was dried at 120° C. for 4 hours and calcined at 350° C. for 4 hours.

Example 3

[0073] 3%Cs.sub.2O/Cu.sub.12Mn.sub.1Zn.sub.3Cr.sub.1O.sub.18.5 catalyst was prepared with co-precipitation followed by impregnation of Cs.

[0074] 41.0 g Cu(NO.sub.3).sub.2.Math.2.5H.sub.2O, 5.3 g 50% Mn(NO.sub.3).sub.2 solution, 13.2 g Zn(NO.sub.3).sub.2.Math.6H.sub.2O and 6.0 g Cr(NO.sub.3).sub.3.Math.9H.sub.2O were dissolved in 166 g deionized water in a beaker.

[0075] In a separate beaker, 53.8 g K.sub.2CO.sub.3 was dissolved in 193 g deionized water.

[0076] The two solutions were pumped to a third beaker containing 200 g deionized water at 70° C. with stirring. The pH value of the mixture was kept at 7.0. After the co-precipitation process was complete, the mixture was stirred for an additional one hour.

[0077] Subsequently, the slurry was filtered and washed with deionized water three times. The obtained paste was dried at 120° C. for 12 hours and then calcined at 400° C. for 4 hours.

[0078] 0.7 g Cs.sub.2CO.sub.3 was dissolved in 14 g deionized water and impregnated on the mixed oxide. The catalyst was dried at 120° C. for 4 hours and calcined at 350° C. for 4 hours.

Example 4

[0079] 3%Cs.sub.2O/Cu.sub.5Mn.sub.2Zn.sub.2Cr.sub.1O.sub.12.5 catalyst was prepared with co-precipitation followed by impregnation of Cs.

[0080] 28.7 g Cu(NO.sub.3).sub.2.Math.2.5H.sub.2O, 12.3 g Mn(CH.sub.3COO.sub.3).sub.2.Math.4H.sub.2O, 14.8 g Zn(NO.sub.3).sub.2.Math.6H.sub.2O and 10.0 g Cr(NO.sub.3).sub.3.Math.9H.sub.2O were dissolved in 164 g deionized water in a beaker.

[0081] In a separate beaker, 54.3 g K.sub.2CO.sub.3 was dissolved in 194 g deionized water.

[0082] The two solutions were pumped to a third beaker containing 200 g deionized water at 70° C. with stirring. The pH value of the mixture was kept at 7.0. After the co-precipitation process was complete, the mixture was stirred for an additional one hour.

[0083] Subsequently, the slurry was filtered and washed with deionized water three times. The obtained paste was dried at 120° C. for 12 hours and then calcined at 400° C. for 4 hours.

[0084] 0.7 g Cs.sub.2CO.sub.3 was dissolved in 15 g deionized water and impregnated on the mixed oxide. The catalyst was dried at 120° C. for 4 hours and calcined at 350° C. for 4 hours.

Example 5

[0085] 3%Cs.sub.2O/Cu.sub.6Mn.sub.2Mg.sub.3Zr.sub.1O.sub.15 catalyst was prepared with co-precipitation followed by impregnation of Cs.

[0086] 31.2 g Cu(NO.sub.3).sub.2.Math.2.5H.sub.2O, 16.0 g 50% Mn(NO.sub.3).sub.2 solution, 17.4 g Mg(NO.sub.3).sub.2.Math.6H.sub.2O and 8.4 g ZrO(NO.sub.3).sub.2.Math.xH.sub.2O were dissolved in 179 g deionized water in a beaker.

[0087] In a separate beaker, 56.1 g K.sub.2CO.sub.3 was dissolved in 201 g deionized water.

[0088] The two solutions were pumped to a third beaker containing 200 g deionized water at 70° C. with stirring. The pH value of the mixture was kept at 7.0. After the co-precipitation process was complete, the mixture was stirred for an additional one hour.

[0089] Subsequently, the slurry was filtered and washed with deionized water three times. The obtained paste was dried at 120° C. for 12 hours and then calcined at 400° C. for 4 hours.

[0090] 0.7 g Cs.sub.2CO.sub.3 was dissolved in 8.1 g deionized water and impregnated on the mixed oxide. The catalyst was dried at 120° C. for 4 hours and calcined at 350° C. for 4 hours.

Example 6

[0091] The catalyst from Example 1 was tested in a tubular reactor under the conditions of 359° C.,

[0092] 100 atm, 3.0% C.sub.3H.sub.7OH, 43.5% H.sub.2, 43.5%CO, 10% N.sub.2, and gas hourly space velocity of 8,000 ml/g-h.

[0093] 20% CO conversion and 35% propanol conversion were obtained. The productivities of methanol, ethanol and isobutanol were 343, 24 and 174 g/kg-h, respectively.

Example 7

[0094] The catalyst from Example 2 was tested in a tubular reactor under the conditions of 310° C., 100 atm, 3.5% C.sub.2H.sub.5OH, 43.25% H.sub.2, 43.25% CO, 10% N.sub.2, and gas hourly space velocity of 4,000 ml/g-h.

[0095] 43% CO conversion and 88% ethanol conversion were obtained. The productivities of methanol, propanol and isobutanol were 305, 74 and 85 g/kg-h, respectively. The total productivity of propanol and isobutanol was 159 g/kg-h.

Example 8

[0096] The catalyst from Example 2 was tested in a tubular reactor under the conditions of 340° C., 100 atm, 2.7% C.sub.3H.sub.7OH, 43.65% H.sub.2, 43.65%CO, 10% N.sub.2, and gas hourly space velocity of 4,000 ml/g-h.

[0097] 33% CO conversion and 84% propanol conversion were obtained. The productivities of methanol, ethanol and isobutanol were 214, 9 and 161 g/kg-h, respectively.

Example 9

[0098] The catalyst from Example 3 was tested in a tubular reactor under the conditions of 300° C., 100 atm, 3.5% C.sub.2H.sub.5OH, 43.25% H.sub.2, 43.25% CO, 10% N.sub.2, and gas hourly space velocity of 8,000 ml/g-h.

[0099] 26% CO conversion and 62% ethanol conversion were obtained. The productivities of methanol, propanol and isobutanol were 670, 233 and 19 g/kg-h, respectively. The total productivity of propanol and isobutanol was 252 g/kg-h.

Example 10

[0100] The catalyst from Example 4 was tested in a tubular reactor under the conditions of 366° C., 100 atm, 3% C.sub.3H.sub.7OH, 43.5% H.sub.2, 43.5%CO, 10% N.sub.2, and gas hourly space velocity of 8,000 ml/g-h.

[0101] 23% CO conversion and 89% propanol conversion were obtained. The productivities of methanol, ethanol and isobutanol were 246, 5 and 378 g/kg-h, respectively.

Example 11

[0102] The catalyst from Example 5 was tested in a tubular reactor under the conditions of 337° C., 100 atm, 3.8% C.sub.2H.sub.5OH, 43.1% H.sub.2, 43.1% CO, 10% N.sub.2, and gas hourly space velocity of 8,000 ml/g-h.

[0103] 28% CO conversion and 70% ethanol conversion were obtained. The productivities of methanol, propanol and isobutanol were 438, 129 and 32 g/kg-h, respectively. The total productivity of propanol and isobutanol was 161 g/kg-h.

[0104] The above examples indicate that the disclosed catalysts can convert efficiently ethanol and syngas to propanol and isobutanol, and convert propanol and syngas to isobutanol, under the testing conditions.

[0105] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims.