Catalyst for the synthesis of isobutanol from syngas and ethanol or propanol

Abstract

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

Description

Background Art

[0001] Isobutanol is considered a better fuel additive for gasoline than ethanol to improve combustion efficiency. It has a relatively higher energy density and lower volatility than ethanol. In addition, it does not easily absorb water from the air, preventing corrosion of the engine and pipes. It also has a higher octane number than ethanol, resulting in less knock in the engine.

[0002] Therefore, methods for producing isobutanol from ethanol and propanol have been sought. Various methods and catalysts for producing isobutanol have been described. For example, US 9,718,754 discloses a homogeneous process for converting alcohol and synthesis gas (synthesis gas) (syngas) into higher alcohols over a carbonylation catalyst containing Ir, Co or Ru. By "synthesis gas" or "synthesis gas" we mean a mixture of CO and H2, and in some cases CO2.

[0003] US 9,346,725 discloses a process for producing higher alcohols from a gas comprising H2, CO, CO2 and lower alcohols, comprising a carbon dioxide and optional alkane removal step. The preferred catalyst consists of copper, zinc oxide and aluminum oxide, optionally promoted with one or more metals selected from alkali metals, alkaline earth metal basic oxides and lanthanide elements.

[0004] US 5,811,602 describes a process in which methanol is reacted with ethanol (and / or propanol) to form isobutanol and higher alcohols in the presence of synthesis gas and light olefins over a noble metal (Pd) supported on a Zn-Mn-Zr mixed oxide containing less than 1.0 mol % of alkali metals.

[0005] US 5,493,064 discloses an alcohol-coupling process in which methanol is reacted with ethanol (and / or propanol) in the presence of synthesis gas to form higher alcohols. The invention is a catalyst comprising Pd and alkali metal exchanged large pore L zeolite, Y zeolite or mordenite.

[0006] Claure, “Assessing C3-C4 alcohol synthesis pathways over a MgAl oxidesupported K / MoS2 catalyst via 13 C2-ethanol and 13C2-ethylene co-feeds”, Journal of Molecular Catalysis A: Chemical, 2016, 423, 224, describing a pathway for the conversion of syngas to C3-C4 alcohols over MgAl oxide-supported K / MoS2 catalysts.

[0007] Walter, "Continuous production of higher alcohols from synthesis gas and ethanol using Cs-modified CuO / ZnO / Al2O3 catalysts", Applied Catalysis A: General, 2019, 585, 117150, describes the continuous production of higher alcohols from synthesis gas and ethanol over Cs-modified CuO / ZnO / Al2O3 catalysts.

[0008] Walter, "Effect of the Addition of Ethanol to Synthesis Gas on the Production of Higher Alcohols over Cs and Ru Modified Cu / ZnO Catalysts", Ind. Eng. Chem. Res. 2015, 54, 1452, reported the addition of ethanol to synthesis gas on Cs- and Ru-Cu / ZnO catalysts to produce higher alcohols.

[0009] Wu, “The mechanism of higher alcohol formation on ZrO2-based catalyst from syngas”, Korean J. Chem. Eng., 2015, 32(3), 406, describes the chain growth mechanism of alcohol synthesis from carbon monoxide and hydrogen over CuZnLaZr catalyst.

[0010] Luk, “Status and prospects in higher alcohols synthesis from syngas”, Chem. Soc. Rev., 2017, 46, 1358, reviews the status of syngas conversion to higher alcohols and describes various catalysts.

[0011] Claure, “Insight into reaction pathways in CO hydrogenation reactions over K / MoS2 supported catalysts via alcohol / olefin co-feed experiments”, Catal. Sci. Technol., 2016, 6, 1957, describes the reaction pathway for the synthesis of higher alcohols from syngas over K / MoS2 supported on mesoporous carbon (C) and mixed MgAl oxide (MMO).

[0012] US 5,703,133 provides a method for preparing iso-alcohols in two stages. In the first stage, synthesis gas is converted into C1-C4 alcohols on Cu-Zn-La-Al oxide promoted by alkali metals. In the second stage, C1-C3 alcohols are converted into iso-alcohols on ZnMnZr oxide doped with alkali metals having noble metals.

[0013] US 7,834,223 discloses a CuMo catalyst, with an optional alkali metal, for converting synthesis gas to alcohols in the presence of methanol and methyl acetate.

[0014] US 8,921,431 discloses a process for converting syngas to mixed alcohols by removing some non-reactive components from the mixed alcohols product and reintroducing a portion of the non-reactive components into a reactor and allowing the syngas to interact with a catalyst in a wet mode.

[0015] US 8,129,436 discloses a process for improving the yield of mixed alcohols for the conversion of synthesis gas to higher alcohols by by-product recycle and removal with a sulfiding Co / Mo catalyst.

[0016] US 2020 / 0039905 describes a method for converting synthesis gas into mixed alcohols using a heterogeneous catalyst in a two-step reaction process.

[0017] Nuan, "Higher alcohol and oxygenate synthesis over cesium-doped CuZnO catalysts", J. Catal., 1989, 116, 195, reported Cs / CuZnO catalysts for converting ethanol and synthesis gas into isobutanol. At 300 ° C, 76 atm, H2 / CO = 0.45 and 193 g / kg-h ethanol and 3260 h -1 The reported isobutanol productivity was 43 g / kg-h at a space velocity of 1.3 Å.

[0018] Hilmen, "Synthesis of higher alcohols on copper catalysts supported on alkali-promoted basic oxides", Appl. Catal. A 1998, 169, 355, discloses a K / CuMgCeO catalyst for reacting ethanol or propanol with synthesis gas to produce isobutanol. x and Cs / Cu / ZnO / Al2O3 catalysts. X The isobutanol productivity over the catalyst was 13.2 g / kg-h at 310°C, 4.5 MPa, 1500 ml / gh and H2 / CO / Ar / C3H7OH=44.5 / 44.5 / 0.1 / 0.5.

[0019] Majocchi, "Synthesis of short chain alcohols over a Cs-promoted Cu-ZnO-Cr2O3 catalyst", Appl. Catal. A, 1998, 166, 393, reported the Cs / CuZnCrO3 catalyst for the conversion of ethanol and synthesis gas into isobutanol. x Catalyst: Under the conditions of 295°C, 75 atm, H2 / CO=1, 139 g / kg-h ethanol and 9000 ml / gh space velocity, only 9 g / kg-h of isobutanol was achieved.

[0020] An, "Isobutanol formation mechanism and method to increase its yieldin low-carbon alcohol synthesis", J.Fuel Chem.Tech., 1994, 22, 63, reported in Cs / ZnCrO x Isobutanol was synthesized from syngas and ethanol or propanol over a catalyst. At 390°C, 100 atm, H2 / CO = 1.9, 160 g / kg-h ethanol and 5000 h -1 Space velocity of 23 g / kg-h of isobutanol was reported. When propanol was used instead of ethanol, the isobutanol productivity increased to 69 g / kg-h.

[0021] However, the performance on the disclosed catalysts is so low that the process has not been commercialized.

[0022] Therefore, there is a need for improved catalysts for reacting syngas with ethanol or propanol to produce propanol or isobutanol.

[0023] Description of the invention

[0024] Alkali or alkaline earth metal doped CuMn oxide catalysts show good performance in the synthesis of propanol and isobutanol in the aldol condensation reaction between synthesis gas and ethanol or propanol. On the catalyst, 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 metal oxide or salt is used to enhance CC coupling in the reaction.

[0025] The alkali metal or alkaline earth metal doped CuMn oxide catalyst may contain 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% to 70% by weight, or 5% to 60% by weight, or 5% to 50% by weight, or 5% to 40% by weight, or 5% to 30% by weight, or 5% to 20% by weight, or 10% to 90% by weight, or 10% to 80% by weight, or 10% to 70% by weight, or 10% to 60% by weight, or 10% to 50% by weight, or 10% to 40% by weight, or 10% to 30% by weight %, 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 % 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%.

[0026] The alkali metal or alkaline earth metal doped CuMn oxide catalyst may contain 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 %. % or 15 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 %.

[0027] By "alkali or alkaline earth metal doped", we mean that the CuMn oxide catalyst contains alkali or alkaline earth metal cations. One or more alkali or alkaline earth metals may be present in the alkali or alkaline earth metal doped CuMn oxide catalyst. The alkali or alkaline earth metal may be incorporated into the catalyst by any suitable method, including but not limited to impregnation and coprecipitation. 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 Cs2O) doped CuMnCr oxide catalyst). When the alkali or alkaline earth metal is coprecipitated with 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 metal or alkaline earth metal may 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 %.

[0028] The alkali metal or alkaline earth metal doped CuMn oxide catalyst may include a catalyst support containing 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 may 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% by weight, or 5% to 90% by weight, or 5% to 80% by weight, or 5% to 70% by weight, or 5% to 60% by weight, or 5% to 50% by weight, or 5% to 40% by weight, or 5% to 30% by weight, or 5% to 25% by weight, or 5% to 20% by weight, or 10% to 95% by weight, or 10% to 90% by weight, or 10% to 80% by weight, or 10% to 150% by weight, or 10% to 20% by weight. 0 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 % 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 %.

[0029] The alkali metal or alkaline earth metal doped CuMn oxide catalyst may be prepared using any suitable method including, but not limited to, co-precipitation followed by impregnation, sol-gel, deposition-precipitation, and incipient wetness impregnation.

[0030] For example, the alkali metal or alkaline earth metal doped CuMn oxide catalyst can be prepared by dissolving the precursor compound of Cu and Mn (and any other metal oxide) in water. Carbonate or hydroxide is dissolved in water separately. Then two solutions are merged and stirred to mix to form a solution of mixed metal carbonate or hydroxide. The slurry is filtered, washed with water, dried and calcined. Finally, alkali metal or alkaline earth metal oxide or salt is impregnated on a solid to generate the catalyst. The alkaline earth metal oxide can also be coprecipitated with Cu, Mn and other metal oxides.

[0031] Suitable Cu and Mn precursor compounds include, but are not limited to, nitrates, acetates, chlorides, and sulfates. Suitable alkali or alkaline earth metal precursors include, but are not limited to, hydroxides, carbonates, bicarbonates, nitrates, acetates, formates, and phosphates.

[0032] The ethanol or propanol conversion reaction can be a continuous process, a semi-continuous process or a batch process.

[0033] The ethanol or propanol conversion can be carried out in any suitable type of reactor, such as fixed bed reactors and fluidized bed reactors.

[0034] 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 syngas.

[0035] The syngas typically has a molar ratio of H2 to CO in the range of 5:1 to 1:5, or in the range of 3:1 to 1:3.

[0036] Suitable reaction conditions include one or more of the following: a temperature in the range of 150°C to 500°C, or 200°C to 450°C, or 250°C to 400°C; a pressure in the range of 0.1 MPa to 30 MPa, or 0.5 MPa to 15 MPa, or 1.0 MPa to 10 MPa; or a gas hourly space velocity in the range of 100 to 500,000, or 1,000 to 200,000, or 2,000 to 100,000 liters of gas per kilogram of catalyst per hour (L / kg-h).

[0037] The alkali or alkaline earth metal doped CuMn oxide catalyst provides good performance in the conversion of ethanol and synthesis gas to propanol and isobutanol, and the conversion of propanol and synthesis gas to isobutanol.

[0038] The conversion of ethanol is 5% to 100%, while the conversion of CO is 5% to 90%. The yields of propanol and isobutanol are 5% to 95%. The propanol and isobutanol productivity is significantly higher than that of the prior art process, for example, increased by 100%.

[0039] The conversion of propanol is between 5% and 100%, while the conversion of CO is between 5% and 90%. The yield of isobutanol is between 5% and 95%. The isobutanol productivity is significantly higher than that of the prior art process, for example, by 150%.

[0040] One aspect of the present invention is a method for producing propanol and / or isobutanol. In one embodiment, the method comprises reacting ethanol or propanol with synthesis gas under reaction conditions in the presence of an alkali metal or alkaline earth metal doped CuMn oxide catalyst to produce propanol and / or isobutanol.

[0041] In some embodiments, the alkali metal or alkaline earth metal 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 %.

[0042] In some embodiments, the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises at least one alkali metal or alkaline earth metal in an amount of 0.1 wt % to 30 wt %.

[0043] In some embodiments, the at least one alkali metal or alkaline earth metal includes at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba.

[0044] In some embodiments, the alkali metal or alkaline earth metal doped CuMn oxide catalyst further comprises one or more additional metal oxides.

[0045] In some embodiments, the additional metal oxide is present in an amount from 0.1 wt % to 95 wt %.

[0046] In some embodiments, the additional metal oxide comprises an oxide of at least one of Zn, Cr, Zr, Al, Si, Ti, Ga, Sn, Y, or a rare earth metal, or a combination thereof.

[0047] In some embodiments, the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnCr oxide catalyst. In some embodiments, the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnZnCr oxide catalyst.

[0048] In some embodiments, the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises a Cs-doped CuMnZnCr oxide catalyst.

[0049] In some embodiments, ethanol is reacted with the syngas and wherein at least one of the following is satisfied: the conversion of ethanol is at least 5%, or the conversion of CO in the syngas is at least 5%.

[0050] In some embodiments, propanol is reacted with the syngas and wherein at least one of the following is satisfied: the conversion of propanol is at least 5%, or the conversion of CO in the syngas is at least 5%.

[0051] In some embodiments, the reaction conditions include one or more of: a temperature in the range of 150°C to 500°C; a pressure in the range of 0.1 MPa to 30 MPa; or a gas hourly space velocity in the range of 100 to 500,000 liters of gas per kilogram of catalyst per hour (L / kg-h).

[0052] In some embodiments, at least one of the following is met: the total amount of ethanol or propanol or both is in the range of 0.1 mol% to 50 mol%, with the balance being synthesis gas; or the synthesis gas has a ratio of H2 to CO in the range of 5:1 to 1:5.

[0053] In some embodiments, the alkali or alkaline earth metal 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 an additional metal oxide.

[0054] In some embodiments, the alkali or alkaline earth metal doped CuMn oxide catalyst comprises an alkali or alkaline earth metal doped CuMnZnCr oxide catalyst containing: 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.

[0055] Another aspect of the present invention is a method for producing propanol or isobutanol. In one embodiment, the method comprises: reacting ethanol or propanol with synthesis gas under reaction conditions in the presence of an alkali metal or alkaline earth metal doped CuMn oxide catalyst to produce propanol or isobutanol; wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises: 0.1 wt % to 90 wt % of C u0.1 wt % to 90 wt % of Mn oxide; 0.1 wt % to 30 wt % of the at least one alkali metal or alkaline earth metal; and 0.1 wt % to 95 wt % of another metal oxide.

[0056] In some embodiments, the alkali or alkaline earth metal 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 includes at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba.

[0057] In some embodiments, the alkali or alkaline earth metal doped CuMn oxide catalyst further comprises 0.1 wt % to 95 wt % of the additional metal oxide, wherein the additional metal oxide comprises an oxide of at least one of Zn, Cr, Zr, Al, Si, Ti, Ga, Sn, Y, or a rare earth metal, or a combination thereof.

[0058] In some embodiments, ethanol is reacted with the syngas and wherein at least one of the following is satisfied: the conversion of ethanol is at least 5%, or the conversion of CO in the syngas is at least 5%.

[0059] In some embodiments, propanol is reacted with the syngas and wherein at least one of the following is satisfied: the conversion of propanol is at least 5%, or the conversion of CO in the syngas is at least 5%.

[0060] In some embodiments, the reaction conditions include one or more of: a temperature in the range of 150°C to 500°C; a pressure in the range of 0.1 MPa to 30 MPa; or a gas hourly space velocity in the range of 100 to 500,000 liters of gas per kilogram of catalyst per hour (L / kg-h).

[0061] In some embodiments, at least one of the following is met: the total amount of ethanol or propanol or both is in the range of 0.1 mol% to 50 mol%, with the balance being synthesis gas; or the synthesis gas has a ratio of H2 to CO in the range of 5:1 to 1:5.

[0062] Example 1

[0063] 3% Cs2O / Cu5Mn4Cr1O was prepared by coprecipitation followed by impregnation of Cs. 14.5 catalyst.

[0064] 28.3 g Cu(NO3)2.2.5H2O, 34.8 g 50% Mn(NO3)2 solution and 9.9 g Cr(NO3)3.9H2O were dissolved in 162 g deionized water in a beaker.

[0065] In a separate beaker, 53.5 g K2CO3 was dissolved in 192 g deionized water.

[0066] The two solutions were pumped with stirring into a third beaker containing 200 g of deionized water at 70° C. The pH of the mixture was maintained at 7.0. After the coprecipitation process was complete, the mixture was stirred for an additional hour.

[0067] Subsequently, the slurry was filtered and washed three times with deionized water.The resulting paste was dried at 120°C for 12 hours and then calcined at 400°C for 4 hours.

[0068] 0.7 g of Cs2CO3 was dissolved in 10.9 g of 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.

[0069] Example 2

[0070] 3% Cs2O / Cu5Mn1Zn3Cr1O was prepared by coprecipitation followed by impregnation of Cs. 11.5 catalyst.

[0071] In a beaker, 28.9 g Cu(NO3)2.2.5H2O, 6.2 g Mn(CH3COO3)2.4H2O, 22.4 g Zn(NO3)2.6H2O and 10.1 g Cr(NO3)3.9H2O were dissolved in 166 g deionized water.

[0072] In a separate beaker, 54.6 g K2CO3 was dissolved in 196 g deionized water.

[0073] The two solutions were pumped with stirring into a third beaker containing 200 g of deionized water at 70° C. The pH of the mixture was maintained at 7.0. After the coprecipitation process was complete, the mixture was stirred for an additional hour.

[0074] Subsequently, the slurry was filtered and washed three times with deionized water.The resulting paste was dried at 120°C for 12 hours and then calcined at 400°C for 4 hours.

[0075] 0.7 g of Cs2CO3 was dissolved in 15 g of 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.

[0076] Example 3

[0077] 3% Cs2O / Cu was prepared by coprecipitation followed by impregnation of Cs 12 Mn1Zn3Cr1O 18.5 catalyst.

[0078] 41.0 g Cu(NO3)2.2.5H2O, 5.3 g 50% Mn(NO3)2 solution, 13.2 g Zn(NO3)2.6H2O and 6.0 g Cr(NO3)3.9H2O were dissolved in 166 g deionized water in a beaker.

[0079] In a separate beaker, 53.8 g K2CO3 was dissolved in 193 g deionized water.

[0080] The two solutions were pumped with stirring into a third beaker containing 200 g of deionized water at 70° C. The pH of the mixture was maintained at 7.0. After the coprecipitation process was complete, the mixture was stirred for an additional hour.

[0081] Subsequently, the slurry was filtered and washed three times with deionized water.The resulting paste was dried at 120°C for 12 hours and then calcined at 400°C for 4 hours.

[0082] 0.7 g of Cs2CO3 was dissolved in 14 g of 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.

[0083] Example 4

[0084] 3% Cs2O / Cu5Mn2Zn2Cr1O was prepared by coprecipitation followed by impregnation of Cs. 12.5 catalyst.

[0085] 28.7 g Cu(NO3)2.2.5H2O, 12.3 g Mn(CH3COO3)2.4H2O, 14.8 g Zn(NO3)2.6H2O and 10.0 g Cr(NO3)3.9H2O were dissolved in 164 g deionized water in a beaker.

[0086] In a separate beaker, 54.3 g K2CO3 was dissolved in 194 g deionized water.

[0087] The two solutions were pumped with stirring into a third beaker containing 200 g of deionized water at 70° C. The pH of the mixture was maintained at 7.0. After the coprecipitation process was complete, the mixture was stirred for an additional hour.

[0088] Subsequently, the slurry was filtered and washed three times with deionized water.The resulting paste was dried at 120°C for 12 hours and then calcined at 400°C for 4 hours.

[0089] 0.7 g of Cs2CO3 was dissolved in 15 g of 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.

[0090] Example 5

[0091] 3% Cs2O / Cu6Mn2Mg3Zr1O was prepared by coprecipitation followed by impregnation of Cs 15 catalyst.

[0092] 31.2 g Cu(NO3)2.2.5H2O, 16.0 g 50% Mn(NO3)2 solution, 17.4 g Mg(NO3)2.6H2O and 8.4 g ZrO(NO3)2.xH2O were dissolved in 179 g deionized water in a beaker.

[0093] In a separate beaker, 56.1 g K2CO3 was dissolved in 201 g deionized water.

[0094] The two solutions were pumped with stirring into a third beaker containing 200 g of deionized water at 70° C. The pH of the mixture was maintained at 7.0. After the coprecipitation process was complete, the mixture was stirred for an additional hour.

[0095] Subsequently, the slurry was filtered and washed three times with deionized water.The resulting paste was dried at 120°C for 12 hours and then calcined at 400°C for 4 hours.

[0096] 0.7 g of Cs2CO3 was dissolved in 8.1 g of 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.

[0097] Example 6

[0098] The catalyst from Example 1 was tested in a tubular reactor at 359°C, 100 atm, 3.0% C3H7OH, 43.5% H2, 43.5% CO, 10% N2, and a gas hourly space velocity of 8000 ml / gh.

[0099] A CO conversion of 20% and a propanol conversion of 35% were obtained. The production rates of methanol, ethanol and isobutanol were 343 g / kg-h, 24 g / kg-h and 174 g / kg-h, respectively.

[0100] Example 7

[0101] The catalyst from Example 2 was tested in a tubular reactor at 310°C, 100 atm, 3.5% C2H5OH, 43.25% H2, 43.25% CO, 10% N2, and a gas hourly space velocity of 4000 ml / gh.

[0102] A CO conversion of 43% and an ethanol conversion of 88% were obtained. The production rates of methanol, propanol and isobutanol were 305 g / kg-h, 74 g / kg-h and 85 g / kg-h, respectively. The total production rate of propanol and isobutanol was 159 g / kg-h.

[0103] Example 8

[0104] The catalyst from Example 2 was tested in a tubular reactor at 340°C, 100 atm, 2.7% C3H7OH, 43.65% H2, 43.65% CO, 10% N2, and a gas hourly space velocity of 4000 ml / gh.

[0105] A CO conversion of 33% and a propanol conversion of 84% were obtained. The production rates of methanol, ethanol and isobutanol were 214 g / kg-h, 9 g / kg-h and 161 g / kg-h, respectively.

[0106] Example 9

[0107] The catalyst from Example 3 was tested in a tubular reactor at 300°C, 100 atm, 3.5% C2H5OH, 43.25% H2, 43.25% CO, 10% N2, and a gas hourly space velocity of 8000 ml / gh.

[0108] A CO conversion of 26% and an ethanol conversion of 62% were obtained. The production rates of methanol, propanol and isobutanol were 670 g / kg-h, 233 g / kg-h and 19 g / kg-h, respectively. The total production rate of propanol and isobutanol was 252 g / kg-h.

[0109] Example 10

[0110] The catalyst from Example 4 was tested in a tubular reactor at 366°C, 100 atm, 3% C3H7OH, 43.5% H2, 43.5% CO, 10% N2, and a gas hourly space velocity of 8000 ml / gh.

[0111] A CO conversion of 23% and a propanol conversion of 89% were obtained. The production rates of methanol, ethanol and isobutanol were 246 g / kg-h, 5 g / kg-h and 378 g / kg-h, respectively.

[0112] Embodiment 11

[0113] The catalyst from Example 5 was tested in a tubular reactor at 337°C, 100 atm, 3.8% C2H5OH, 43.1% H2, 43.1% CO, 10% N2, and a gas hourly space velocity of 8000 ml / gh.

[0114] A CO conversion of 28% and an ethanol conversion of 70% were obtained. The production rates of methanol, propanol and isobutanol were 438 g / kg-h, 129 g / kg-h and 32 g / kg-h, respectively. The total production rate of propanol and isobutanol was 161 g / kg-h.

[0115] The above examples demonstrate that under the described test conditions, the disclosed catalysts can effectively convert ethanol and syngas to propanol and isobutanol and vice versa.

[0116] Although at least one exemplary embodiment has been presented in the foregoing detailed description of the present invention, it should be understood that there are a large number of variations. It should also be understood that the one or more exemplary embodiments are merely examples and are not intended to limit the scope, application or configuration of the present invention in any way. On the contrary, the foregoing detailed description will provide a convenient roadmap for implementing the exemplary embodiments of the present invention to those skilled in the art. It should be understood that, without departing from the scope of the present invention set forth in the appended claims, various changes may be made to the functions and arrangements of the elements described in the exemplary embodiments.

Claims

1. A method for producing propanol and / or isobutanol, comprising: reacting ethanol or propanol with synthesis gas in the presence of an alkali metal or alkaline earth metal doped CuMn oxide catalyst under reaction conditions to produce propanol and / or isobutanol, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises Cu oxide in an amount of 0.1 wt % to 90 wt %, Mn oxide in an amount of 0.1 wt % to 90 wt %, at least one alkali metal or alkaline earth metal in an amount of 0.1 wt % to 30 wt %, and a catalyst support containing one or more additional metal oxides in an amount of 0.1 wt % to 95 wt %; wherein the one or more additional metal oxides comprise oxides of one or more of Zn, Cr, Zr, and combinations thereof; and The reaction conditions include one or more of the following: a temperature in the range of 150°C to 500°C; a pressure in the range of 0.1 MPa to 30 MPa; or a gas hourly space velocity in the range of 100 to 500,000 liters of gas per kilogram of catalyst per hour (L / kg-h).

2. The method of claim 1, wherein the at least one alkali metal or alkaline earth metal comprises at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba.

3. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnCr oxide catalyst.

4. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnZn oxide catalyst.

5. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnZnCr oxide catalyst.

6. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises a Cs-doped CuMnZnCr oxide catalyst.

7. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnZr oxide catalyst.

8. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises a CuMnMgZr oxide catalyst.

9. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises a Cs2O doped CuMnMgZr oxide catalyst.

10. The method according to any one of claims 1 to 2, wherein at least one of the following is satisfied: the total amount of ethanol or propanol or both is in the range of 0.1 mol % to 50 mol %, with the remainder being synthesis gas; or the synthesis gas has a ratio of H2 to CO in the range of 5:1 to 1:

5.

11. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises: 1 wt % to 60 wt % Cu oxide; 1 wt % to 50 wt % of Mn oxide; 1 to 20 wt % of the at least one alkali metal or alkaline earth metal; and 1 wt % to 50 wt % of the one or more additional metal oxides.

12. The method according to any one of claims 1 to 2, wherein the alkali metal or alkaline earth metal doped CuMn oxide catalyst comprises an alkali metal or alkaline earth metal doped CuMnZnCr oxide catalyst containing: 5 to 60 wt % Cu oxide; 5 to 40 wt % of Mn oxide; 2 to 15 wt. % of the at least one alkali metal or alkaline earth metal; 5 to 40 wt % Zn oxide; and 5 to 30 wt. % Cr oxide.