Catalyst for isobutanol synthesis

Abstract

Use of M / M for the production of isobutanol in the propanol-methanol, ethanol-methanol and propanol / ethanol mixture-methanol reactions 2+ M 4+ Oxide catalysts have been developed. The catalysts may also be used in the production of n-butanol in the ethanol-ethanol reaction. M may comprise one or more metals of Groups 3-12 of the Periodic Table. 2+ may comprise divalent magnesium, calcium, strontium, barium, or combinations thereof. 4+ may comprise tetravalent silicon, titanium, zirconium, or combinations thereof. The catalysts, and methods of using the catalysts are described.

Description

Technical Field

[0001] The present invention relates to a catalyst for isobutanol synthesis.

Background Art

[0002]

[0001] Isobutanol is an organic solvent and raw material in the production of isobutyl acetate and isobutyl esters. It may also be directly blended with gasoline or used as an alternative fuel as it is to improve octane number and combustion efficiency. Isobutanol has a relatively high energy density and low volatility compared to ethanol. In addition, since it does not easily absorb water from the air, it prevents or reduces corrosion of engines and pipelines. Isobutanol has many potential uses, but its synthesis is limited. Isobutanol is currently produced by carbonylation of propylene. In this process, propylene is reacted with carbon monoxide and hydrogen to produce butyraldehyde and isobutyraldehyde, which are hydrogenated to n-butanol and isobutanol, and then the butanol is separated. A new alternative technology is biomass fermentation. However, the selectivity of isobutanol in these two homologous processes is low, the productivity is limited, and as a result, the cost of isobutanol is high.

[0003]

[0002] The Guerbet reaction is an alternative process for synthesizing isobutanol from methanol and ethanol / propanol. This reaction is particularly important because it can produce valuable isobutanol from inexpensive mixed alcohols. The Guerbet reaction occurs by a coupling method between alcohols using a multifunctional catalyst having dehydrogenation activity, strong surface basicity, mild acidity, and hydrogenation activity. The reaction is as follows: C2H5OH + CH3OH = C3H7OH + H2O (1) C3H7OH + CH3OH = C4H9OH + H2O (2) C2H5OH + 2CH3OH = C4H9OH + 2H2O (3) As a result, various catalysts and processes for producing isobutanol from methanol, ethanol, and propanol have been explored. For example, U.S. Patent Nos. 5,581,602, 5,707,920, 5,770,541, 5,908,807, 5,939,352, and 6,034,141 describe noble metal-loaded alkali metal-doped ZnMnZr oxide catalysts that convert methanol and ethanol, or methanol, ethanol, and propanol, to isobutanol.

[0004] U.S. Patent No. 5,559,275 discloses a process for converting methanol, ethanol, and propanol to higher branched oxygenates such as isobutanol using a catalyst comprising: a) a mixed oxide support having at least two components selected from the oxides of Zn, Mg, Zr, Mn, Ti, Cr, and La; and b) an active metal selected from Pd, Pt, Ag, Rh, Co, and mixtures thereof.

[0005] Carlini, "Guerbet condensation of methanol with n-propanol to isobutyl alcohol over heterogeneous bifunctional catalysts based on Mg-Al mixed oxides partially substituted by different metal components", Journal of Molecular Catalysis A: Chemical, 2005, 232, 13 describes Mg-Al mixed oxides doped with Pd, Rh, Ni, and Cu for the synthesis of isobutanol from methanol and propanol.

[0006] U.S. Patent Application Publication No. 20190031585 discloses a method for converting ethanol to higher alcohols (e.g., n-butanol) using a Cu-MgO-Al2O3 catalyst having less than 0.25 wt% Cu. The Cu is pseudo-single-atom, small, and highly dispersed on the support.

[0007]

[0007] Gabriels, "Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization", Catalysis Science & Technology, 2015, 5, 3876 summarizes a series of catalysts for the reaction between methanol and ethanol / propanol, including those supported on Al2O3, Ca or Sr hydroxyapatite, hydrotalcite, MgO, Mg(OH)2, Rb-Li exchanged zeolite X, and Na2CO3 / NaX and containing alkali or alkaline earth metals.

Summary of the Invention

Problems to be Solved by the Invention

[0008]

[0008] There remains a need for catalysts for producing isobutanol from methanol, ethanol, and propanol, as well as methods for making and using such catalysts.

Means for Solving the Problems

[0009]

[0009] M / M showing good isobutanol yield in propanol-methanol, ethanol-methanol, and propanol / ethanol mixture-methanol reactions 2+ M 4+Oxide catalysts have been developed. These catalysts also exhibit good n-butanol yields in ethanol-ethanol reactions. Methanol and ethanol can be reacted to form propanol, and this propanol can then be M / M 2+ M 4+ reacted with methanol using an oxide catalyst to form isobutanol. Alternatively, methanol and propanol can be M / M 2+ M 4+ directly reacted using an oxide catalyst to produce isobutanol. A mixture of propanol and ethanol may be reacted with methanol. Also, ethanol can be reacted with ethanol to form n-butanol.

[0010]

[0010] One aspect of the present invention is an alcohol condensation catalyst for the synthesis of isobutanol. In one embodiment, the catalyst is M / M 2+ M 4+ an oxide catalyst. M can include one or more metals of Groups 3-12 of the periodic table. M 2+ can include divalent magnesium, calcium, strontium, barium, or combinations thereof. M 2+ can consist essentially of divalent magnesium, calcium, strontium, barium, or combinations thereof. M 2+ can be selected from the group consisting of divalent magnesium, calcium, strontium, barium, or combinations thereof. M 4+ can include tetravalent silicon, titanium, zirconium, or combinations thereof. M 4+ can consist essentially of tetravalent silicon, titanium, zirconium, or combinations thereof. M 4+ can be selected from the group consisting of tetravalent silicon, titanium, zirconium, or combinations thereof.

DETAILED DESCRIPTION OF THE INVENTION

[0011] In some embodiments, M comprises Cu, Co, Fe, Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au, or combinations thereof. In some embodiments, M is Cu.

[0012] In some embodiments, M is 0.01 wt% to 50 wt%, or 0.01 wt% to 40 wt%, or 0.01 wt% to 30 wt%, or 0.01 wt% to 25 wt%, or 0.01 wt% to 20 wt%, or 0.01 wt% to 15 wt%, or 0.01 wt% to 10 wt%, or 0.1 wt% to 50 wt%, or 0.1 wt% to 40 wt%, or 0.1 wt% to 30 wt%, or 0.1 wt% to 25 wt%, or 0.1 wt% to 20 wt%, or 0.1 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.5 wt% to 50 wt%, or 0.5 wt% to 40 wt%, or 0.5 wt% to 30 wt%, or 0.5 wt% to 25 wt%, or 0.5 wt% to 20 wt%, or 0.5 wt% to 15 wt%, or 0.It is present in the catalyst in an amount of 5 wt% to 10 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 1 wt% to 15 wt%, or 1 wt% to 10 wt%, or 2 wt% to 50 wt%, or 2 wt% to 40 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 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 5 wt% to 15 wt%, or 5 wt% to 10 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 10 wt% to 15 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 50 wt%, or 20 wt% to 40 wt%, or 20 wt% to 30 wt%, or 20 wt% to 25 wt%, or 25 wt% to 50 wt%, or 25 wt% to 40 wt%, or 25 wt% to 30 wt%, or 30 wt% to 50 wt%, or 30 wt% to 40 wt%, or 35 wt% to 50 wt%, or 35 wt% to 40 wt%, or 40 wt% to 50 wt%.

[0013]

[0013] In some embodiments, M 2+O is 1 wt% to 50 wt%, or 1 wt% to 75 wt%, or 1 wt% to 70 wt%, or 1 wt% to 65 wt%, or 1 wt% to 60 wt%, or 2 wt% to 98 wt%, or 2 wt% to 75 wt%, or 2 wt% to 70 wt%, or 2 wt% to 65 wt%, or 2 wt% to 60 wt%, or 5 wt% to 98 wt%, or 5 wt% to 75 wt%, or 5 wt% to 70 wt%, or 5 wt% to 65 wt%, or 5 wt% to 60 wt%, or 10 wt% to 98 wt%, or 10 wt% to 75 wt%, or 10 wt% to 70 wt%, or 10 wt% to 65 wt%, or 10 wt% to 60 wt%, or 15 wt% to 98 wt%, or 15 wt% to 75 wt%, or 15 wt% to 70 wt%, or 15 wt% to 65 wt%, or 15 wt% to 60 wt%, or 20 wt% to 98 wt%, or 20 wt% to 75 wt%, or 20 wt% to 70 wt%, or 20 wt% to 65 wt%, or 20 wt% to 60 wt%, or 25 wt% to 98 wt%, or 25 wt% to 75 wt%, or 25 wt% to 70 wt%, or 25 wt% to 65 wt%, or 25 wt% to 60 wt%, or 30 wt% to 98 wt%, or 30 wt% to 75 wt%, or 30 wt% to 70 wt%, or 30 wt% to 65 wt%, or 30 wt% to 60 wt%, or 35 wt% to 98 wt%, or 35 wt% to 75 wt%, or 35 wt% to 70 wt%, or 35 wt% to 65 wt%, or 35 wt% to 60 wt%, or, 40 wt% to 98 wt%, or 40 wt% to 75 wt%, or 40 wt% to 70 wt%, or 40 wt% to 65 wt%, or 40 wt% to 60 wt%, or 45 wt% to 98 wt%, or 45 wt% to 75 wt%, or 45 wt% to 70 wt%, or 45 wt% to 65 wt%, or 45 wt% to 60 wt%, or 50 wt% to 98 wt%, or 50 wt% to 75 wt%, or 50 wt% to 70 wt%, or 50 wt% to 65 wt%, or 50 wt% to 60 wt%, or 55 wt% to 98 wt%, or 55 wt% to 75 wt%, or 55 wt% to 70 wt%, or 55 wt% to 65 wt%, or 55 wt% to 60 wt% 5 wt% to 98 wt%, or 5 wt% to 75 wt%, or 5 wt% to 70 wt%Or in an amount of 5 wt% to 65 wt%, or 5 wt% to 60 wt%, or 10 wt% to 98 wt%, or 10 wt% to 75 wt%, or 10 wt% to 70 wt%, or 10 wt% to 65 wt%, or 10 wt% to 60 wt%, or 15 wt% to 98 wt%, or 15 wt% to 75 wt%, or 15 wt% to 70 wt%, or 15 wt% to 65 wt%, or 15 wt% to 60 wt%, or 20 wt% to 98 wt%, or 20 wt% to 75 wt%, or 20 wt% to 70 wt%, or 20 wt% to 65 wt%, or 20 wt% to 60 wt%, or 25 wt% to 98 wt%, or 25 wt% to 75 wt%, or 25 wt% to 70 wt%, or 25 wt% to 65 wt%, or 25 wt% to 60 wt%, or 30 wt% to 98 wt%, or 30 wt% to 75 wt%, or 30 wt% to 70 wt%, or 30 wt% to 65 wt%, or 30 wt% to 60 wt%, or 35 wt% to 98 wt%, or 35 wt% to 75 wt%, or 35 wt% to 70 wt%, or 35 wt% to 65 wt%, or 35 wt% to 60 wt%, or, 40 wt% to 98 wt%, or 40 wt% to 75 wt%, or 40 wt% to 70 wt%, or 40 wt% to 65 wt%, or 40 wt% to 60 wt%, or 45 wt% to 98 wt%, or 45 wt% to 75 wt%, or 45 wt% to 70 wt%, or 45 wt% to 65 wt%, or 45 wt% to 60 wt%, or 50 wt% to 98 wt%, or 50 wt% to 75 wt%, or 50 wt% to 70 wt%, or 50 wt% to 65 wt%, or 50 wt% to 60 wt%, or 55 wt% to 98 wt%, or 55 wt% to 75 wt%, or 55 wt% to 70 wt%, or 55 wt% to 65 wt%, or 55 wt% to 60 wt% is present in the catalyst.,

[0014]

[0014] In some embodiments, M 4+O2 is present in the catalyst in an amount of 1 wt% to 98 wt%, or 1 wt% to 75 wt%, or 1 wt% to 70 wt%, or 1 wt% to 65 wt%, or 1 wt% to 60 wt%, or 2 wt% to 98 wt%, or 2 wt% to 75 wt%, or 2 wt% to 70 wt%, or 2 wt% to 65 wt%, or 2 wt% to 60 wt%, or 5 wt% to 98 wt%, or 5 wt% to 75 wt%, or 5 wt% to 70 wt%, or 5 wt% to 65 wt%, or 5 wt% to 60 wt%, or 10 wt% to 98 wt%, or 10 wt% to 75 wt%, or 10 wt% to 70 wt%, or 10 wt% to 65 wt%, or 10 wt% to 60 wt%, or 15 wt% to 98 wt%, or 15 wt% to 75 wt%, or 15 wt% to 70 wt%, or 15 wt% to 65 wt%, or 15 wt% to 60 wt%, or 20 wt% to 98 wt%, or 20 wt% to 75 wt%, or 20 wt% to 70 wt%, or 20 wt% to 65 wt%, or 20 wt% to 60 wt%, or 25 wt% to 98 wt%, or 25 wt% to 75 wt%, or 25 wt% to 70 wt%, or 25 wt% to 65 wt%, or 25 wt% to 60 wt%, or 30 wt% to 98 wt%, or 30 wt% to 75 wt%, or 30 wt% to 70 wt%, or 30 wt% to 65 wt%, or 30 wt% to 60 wt%, or 35 wt% to 98 wt%, or 35 wt% to 75 wt%, or 35 wt% to 70 wt%, or 35 wt% to 65 wt%, or 35 wt% to 60 wt%, or 40 wt% to 98 wt%, or 40 wt% to 75 wt%, or 40 wt% to 70 wt%, or 40 wt% to 65 wt%, or 40 wt% to 60 wt%, or 45 wt% to 98 wt%, or 45 wt% to 75 wt%, or 45 wt% to 70 wt%, or 45 wt% to 65 wt%, or 45 wt% to 60 wt%, or 50 wt% to 98 wt%, or 50 wt% to 75 wt%, or 50 wt% to 70 wt%, or 50 wt% to 65 wt%, or 50 wt% to 60 wt%, or 55 wt% to 98 wt%, or 55 wt% to 75 wt%, or 55 wt% to 70 wt%, or 55 wt% to 65 wt%, or 55 wt% to 60 wt%.

[0015]

[0015] In some embodiments, M 2+ contains divalent magnesium.

[0016] In some embodiments, M 4+ contains silicon.

[0017] In some embodiments, the catalyst further comprises a salt or oxide of a Group 1 metal of the periodic table, or a combination thereof. In some embodiments, the Group 1 metal includes Li, Na, K, Rb, Cs, or a combination thereof. The Group 1 metal may be present in an amount of 0.01 wt% to 10 wt%, or 0.05 wt% to 10 wt%, or 0.1 wt% to 10 wt%, or 0.5 wt% to 10 wt%, or 1 wt% to 10 wt%, or 2 wt% to 10 wt%, or 3 wt% to 10 wt%, or 4 wt% to 10 wt%, or 5 wt% to 10 wt%, or 6 wt% to 10 wt%, or 7 wt% to 10 wt%, or 8 wt% to 10 wt%, or 9 wt% to 10 wt%, or 0.01 wt% to 8 wt%, or 0.01 wt% to 5 wt%, or 0.01 wt% to 2 wt%, or 0.01 wt% to 1 wt%, or 0.01 wt% to 0.5 wt%, or 0.05 wt% to 8 wt%, or 0.05 wt% to 5 wt%, or 0.05 wt% to 2 wt%, or 0.05 wt% to 1 wt%, or 0.05 wt% to 0.5 wt%, or 0.1 wt% to 8 wt%, or 0.1 wt% to 5 wt%, or 0.1 wt% to 2 wt%, or 0.1 wt% to 1 wt%, or 0.1 wt% to 0.5 wt%, or 0.5 wt% to 8 wt%, or 0.5 wt% to 5 wt%, or 0.5 wt% to 2 wt%, or 0.5 wt% to 1 wt%, or 1 wt% to 8 wt%, or 1 wt% to 5 wt%, or 1 wt% to 2 wt%, or 2 wt% to 8 wt%, or 2 wt% to 5 wt%, or 3 wt% to 5 wt%, or 4 wt% to 8 wt%, or 4 wt% to 5 wt%.

[0016]

[0018] Another aspect of the present invention is a method for producing isobutanol or n-butanol. In one embodiment, the method comprises reacting ethanol or propanol with methanol in the presence of an alcohol condensation catalyst under reaction conditions to produce isobutanol, or reacting ethanol with ethanol in the presence of an alcohol condensation catalyst under reaction conditions to produce n-butanol; wherein the alcohol condensation catalyst is M / M 2+ M 4+ oxide catalyst; M includes a metal of Groups 3-12 of the Periodic Table, or a combination thereof; M 2+ includes divalent magnesium, calcium, strontium, barium, or a combination thereof; M 4+ includes tetravalent silicon, titanium, zirconium, or a combination thereof.

[0017]

[0019] M / M 2+ M 4+ The oxide catalyst is as described above.

[0020] In some embodiments, the reaction conditions include: a temperature in the range of 100 °C to 500 °C; or one or more of a pressure in the range of 5 kPa to 30,000 kPa.

[0018]

[0021] M / M 2+ M 4+ The method for producing isobutanol or n-butanol using the oxide catalyst enables good conversion of methanol, ethanol or propanol, as well as good selectivity and productivity of isobutanol or n-butanol.

Example

[0019]

[0022] Example 1

[0023] Mg(NO3)2·6H2O (dissolved in ethanol) was reacted with an aqueous solution of Na2SiO3·9H2O in an autoclave at 170 °C for 24 hours, followed by filtration, washing, drying, and calcination at 450 °C for 4 hours to prepare Mg2SiO4. Cu was impregnated on the surface of Mg2SiO4 by the incipient wetness impregnation method. As a result, a 5% Cu / Mg2SiO4 catalyst with a BET surface area of 203 m 2 / g and a pore volume of 0.21 cm 3 / g was produced.

[0020]

[0024] The catalytic performance test was carried out in a microreactor under the conditions of 289 - 337 °C, 4136856 Pa (600 psi), 11.4% propanol, 22.8% methanol, the balance N2, and GHSV 3000 ml / g-h. The test results are summarized in Table 1. Under these test conditions, the methanol conversion was 28 - 42%, the propanol conversion was 43 - 66%, the isobutanol selectivity was 30 - 46%, and the isobutanol productivity was 154 - 361 g / kg-h.

[0021]

[0025] The above results indicate that the Cu-doped Mg2SiO4 catalyst is a good catalyst for converting propanol and methanol to isobutanol by the Guerbet reaction.

[0022]

[0026] Example 2

[0027] Cu 0.19 Ca 1.81 ZrO4 catalyst was prepared by the conventional coprecipitation method.

[0028] 3.65 g of Cu(NO3)2·2.5H2O, 36.05 g of Ca(NO3)2·4H2O, and 31.41 g of ZrO(NO3)2·xH2O were dissolved in 167 g of deionized water in a beaker.

[0023]

[0029] In another beaker, 52.39 g of K2CO3 was dissolved in 188 g of deionized water.

[0030] Two solutions were pumped into a third beaker containing 200 g of deionized water while stirring at 70 °C. The pH value of the mixture was maintained at 7.0. After the coprecipitation process was completed, the mixture was stirred for an additional 1 hour.

[0024]

[0031] Thereafter, the slurry was filtered and washed three times with deionized water. The obtained paste was dried at 120 °C for 12 hours and calcined at 600 °C for 4 hours.

[0032] 1.00 g of the sample was loaded into a catalyst basket and placed into a stainless steel autoclave together with 29 g of a solution with a 2:1 CH3OH - C3H7OH molar ratio. The autoclave was sealed, filled with ultra-high purity N2 at 15168472 Pa (2200 psi), and purged after 2 hours to obtain a closed system with an N2 headspace. The autoclave was heated to 325 °C at a heating rate of 2 °C / min while stirring, maintained at 325 °C for 15 hours, and then cooled to room temperature. The weights of the liquid, catalyst basket, and autoclave were recorded. The liquid was analyzed by GC to obtain information regarding methanol and propanol conversion rates and isobutanol productivity. A methanol conversion rate of 55%, a propanol conversion rate of 46%, an isobutanol selectivity of 28%, and an isobutanol productivity of 148 g / kg-h were achieved.

[0025]

[0033] Example 3

[0034] 5%Cu / Mg3Si4O 11 was prepared by precipitation followed by impregnation. 25.6 g of Mg(NO3)2·6H2O and 3.81 g of acetic acid were dissolved in 50 ml of deionized water in a 500 ml Nalgene bottle. 37.9 g of Na2SiO3·9H2O was dissolved in 300 ml of deionized water and then rapidly added to the Mg(NO3)2 solution while stirring. The mixture was stirred vigorously for 30 min and then left sealed at room temperature for 4 days. The slurry was then filtered, washed with deionized water, and dried at 120 °C. The dried solid was mixed with 100 ml of H2O in a 200 ml Teflon-lined autoclave and heated at 200 °C for 24 h. The solid was filtered, washed with 500 ml of H2O, dried, and calcined at 500 °C for 4 h.

[0026]

[0035] 8 g of calcined material (Mg3Si4O 11 ) was impregnated with a solution of 0.541 g of Cu(NO3)2·2.5H2O in 2.8 ml of H2O, and the material was calcined at 400 °C for 8 h.

[0027]

[0036] 1.00 g of the sample was loaded into a catalyst basket and placed into a stainless-steel autoclave together with 29 g of a solution with a 2:1 CH3OH - C3H7OH molar ratio. The autoclave was sealed, filled with ultra-high purity N2 at 15168472 Pa (2200 psi), and purged after 2 h to obtain a sealed system with an N2 headspace. The autoclave was heated to 325 °C at a rate of 2 °C / min with stirring, held at 325 °C for 15 h, and then cooled to room temperature. The weights of the liquid, catalyst basket, and autoclave were recorded. The liquid was analyzed by GC to obtain information on methanol and propanol conversion rates and isobutanol productivity. A methanol conversion rate of 55%, a propanol conversion rate of 60%, an isobutanol selectivity of 30%, and an isobutanol productivity of 206 g / kg-h were obtained.

[0028]

[0037] Example 4

[0038] 1.0 g of the 5% Cu / Mg3Si4O sample of Example 3 11 was loaded into a catalyst basket and placed into a stainless-steel autoclave together with 31.3 g of an ethanol solution. The autoclave was sealed, filled with ultra-high purity N2 at 15168472 Pa (2200 psi), and purged after 2 h to obtain a sealed system with an N2 headspace. The autoclave was heated to 325 °C at a rate of 2 °C / min with stirring, held at 325 °C for 15 h, and then cooled to room temperature. The weights of the liquid, catalyst basket, and autoclave were recorded. The liquid was analyzed by GC to obtain information on ethanol conversion rate and n-butanol productivity. An ethanol conversion rate of 72%, an n-butanol selectivity of 22%, and an n-butanol productivity of 263 g / kg-h were obtained.

[0029]

[0039]

[0030]

Table 1

[0031]

[0040] In the above detailed description of the present invention, at least one representative embodiment has been presented, but it should be understood that there are a vast number of variations. It should also be understood that one or more representative embodiments are merely examples and are not intended to limit the scope, applicability, or configuration of the present invention in any way. Rather, the above detailed description provides a convenient guide for those skilled in the art to implement representative embodiments of the present invention. It is understood that various changes can be made to the functions and arrangements of the elements described in a representative embodiment without departing from the scope of the present invention as set forth in the appended claims.

Claims

1. An alcohol condensation catalyst for the synthesis of isobutanol, comprising: M / M ２＋ M ４＋ comprising an oxide catalyst; wherein M comprises a metal of Groups 3-12 of the Periodic Table, or a combination thereof; M ２＋ comprises divalent magnesium, calcium, strontium, barium, or a combination thereof; M ４＋ contains tetravalent silicon, titanium, zirconium, or a combination thereof; However, M ２＋ when M is magnesium, M ４＋ is not titanium or zirconium, catalyst.

2. The catalyst according to claim 1, wherein M comprises Cu, Co, Fe, Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au, or a combination thereof.

3. The catalyst according to claim 1 or 2, wherein M comprises Cu.

4. The catalyst according to any one of claims 1 to 3, wherein M is present in an amount of 0.01 wt% to 50 wt%.

5. M ２＋ The catalyst according to any one of claims 1 to 4, wherein M contains divalent magnesium.

6. M ２＋ The catalyst according to any one of claims 1 to 5, wherein O is present in an amount of 1 wt% to 98 wt%.

7. M ４＋ The catalyst according to any one of claims 1 to 6, wherein M contains silicon.

8. M ４＋ O ２ The catalyst according to any one of claims 1 to 7, wherein M is present in an amount of 1 wt% to 98 wt%.

9. The catalyst according to any one of claims 1 to 8, further comprising a salt or oxide of a metal of Group 1 of the Periodic Table, or a combination thereof.

10. The catalyst according to claim 9, wherein the Group 1 metal comprises Li, Na, K, Rb, Cs, or a combination thereof.

11. The catalyst according to claim 9, wherein the Group 1 metal is present in an amount of 0.01 wt% to 10 wt%.

12. A method for producing isobutanol, comprising: reacting ethanol or propanol with methanol in the presence of an alcohol condensation catalyst under reaction conditions to produce isobutanol; The alcohol condensation catalyst is M / M ２＋ M ４＋ and includes an oxide catalyst; wherein M comprises a metal of Groups 3-12 of the Periodic Table, or a combination thereof; M ２＋ comprises divalent magnesium, calcium, strontium, barium, or combinations thereof; M ４＋ comprises tetravalent silicon, titanium, zirconium, or a combination thereof, method.

13. The reaction conditions are: a temperature in the range of 100°C to 500°C; or a pressure in the range of 5 kPa to 30,000 kPa The method according to claim 12, comprising one or more of the above.

14. The catalyst according to claim 12 or 13, wherein M comprises Cu, Co, Fe, Ni, Ru, Rh, Pd, Ir, Pt, Ag, Au, or a combination thereof.

15. The catalyst according to any one of claims 12 to 14, wherein M is present in an amount of 0.01 wt% to 50 wt%.

16. M ２＋ The catalyst according to any one of claims 12 to 15, wherein O is present in an amount of 1 wt% to 98 wt%.

17. M ４＋ O ２ The catalyst according to any one of claims 12 to 16, wherein M and O are present in an amount of 1 wt% to 98 wt%.

18. The catalyst according to any one of claims 12 to 17, further comprising a salt or oxide of a metal of Group 1 of the Periodic Table, or a combination thereof.

19. The catalyst according to claim 18, wherein the Group 1 metal is present in an amount of 0.01 wt% to 10 wt%.

Images