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WO2024194205A1 - Process for producing 2-propanol - Google Patents

Process for producing 2-propanol Download PDF

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Publication number
WO2024194205A1
WO2024194205A1 PCT/EP2024/057042 EP2024057042W WO2024194205A1 WO 2024194205 A1 WO2024194205 A1 WO 2024194205A1 EP 2024057042 W EP2024057042 W EP 2024057042W WO 2024194205 A1 WO2024194205 A1 WO 2024194205A1
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catalysts
range
metals
gas stream
support material
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PCT/EP2024/057042
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French (fr)
Inventor
Gonzalo PRIETO GONZALES
Raquel PELAEZ FERNANDEZ
Adrian RIELVES LUQUE
Eva ANDRES MARCOS
Andrei-Nicolae PARVULESCU
Nils Bottke
Michael Ludwig Lejkowski
Philipp Gruene
Irina YARULINA
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/22—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
    • B01J29/67—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions

Definitions

  • the present invention relates to a process for producing 2-propanol by converting a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof, wherein the oxygenate preferably is dimethyl ether.
  • 2-propanol is an important commodity chemical which finds applications as solvent, precursor for the production of polymers such as polyacrylates and polyolefins, denaturing agent for ethanol (ethyl alcohol), component in cosmetics and as disinfectant, among other.
  • 2-propanol can be used as a precursor for the production of propylene via dehydration thereof, but it can also be produced from propylene which is currently done largely. According to common methods, 2-propanol can be produced by an indirect hydration process which involves esterification and hydrolysis reactions in concentrated sulfuric acid. Further, 2-propanol can be produced by a direct propylene hydration with either liquid or solid acid catalysts. Gehrmann and Tenhumberg disclose a study on the “Production and Use of Sustainable C2-C4 Alcohols - An Industrial Perspective” in Chemie Ingenieurtechnik, Volume 92, 2020, pages 1444-1458. In said publication, an overview is provided on these methods for 2-propanol production.
  • 2-propanol can also be produced from acetone, via hydrogenation of the carbonyl group, as described, e.g. in documents US 6930213 B1 , US 7041857 B1 , US 2013/0035517 A1 and ON 112403510 A.
  • EP 2590922 B1 relates to a process for the preparation of ethanol and higher alcohols.
  • said process particularly comprises the steps of providing an alcohol synthesis gas comprising carbon monoxide and hydrogen; adding methanol; converting the resulting synthesis gas mixture in presence of one or more catalysts to ethanol and/or higher alcohols.
  • a potassium carbonate promoted catalyst containing metallic copper, zinc oxide and aluminum oxide is disclosed.
  • ON 104892361 A relates to a method for catalytically converting methanol to propanol.
  • said method is particularly characterized in that methanol is used as a raw material, and a composite of two or more elements containing iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium supported by molecular sieve is used.
  • EP 2173694 B1 relates to a method of producing C2-C4 alcohols, the method particularly comprising introducing syngas into a first reaction zone with a first catalyst and thereby producing methanol; introducing said syngas and methanol into a second reaction zone comprising at least a second catalyst and converting it to ethanol, 1 -propanol and 1 -butanol.
  • a first reaction zone with a first catalyst and thereby producing methanol
  • introducing said syngas and methanol into a second reaction zone comprising at least a second catalyst and converting it to ethanol, 1 -propanol and 1 -butanol.
  • C1 platform compounds such as methanol, dimethyl ether and CO, are an interesting alternative as a carbon source for 2-propanol production.
  • Synthesis gas is a mixture composed of carbon monoxide (CO), hydrogen (H2) and, in some cases, also carbon dioxide (CO2) as main components.
  • Synthesis gas streams might additionally comprise other gases such as nitrogen (N2), helium (He), argon (Ar), water steam (H2O), or light hydrocarbons such as methane (CH4), ethane (C2H6), propane (CsHs), which do not alter the reactivity of the major components to a significant extent.
  • Syngas can be obtained from a wide array of carbonaceous sources, for example, by steam reforming or partial oxidation of natural or shale gas, gasification of coal, gasification and/or reforming of biomass, hydrogenation of carbon dioxide, by waste gasification, for instance of municipal waste, or the co-electrolysis of CO2 and water, among other.
  • Methanol can be obtained directly from synthesis gas by the catalytic process known as methanol synthesis.
  • methanol synthesis An overview of existing catalysts and processes for the direct production of methanol from synthesis gas is presented in J. P. Lange, "Methanol synthesis: a short review of technology improvements", Catalysis Today, Volume 64, Issues 1-2, 2001 , pages 3-8.
  • Dimethyl ether can also be produced from synthesis gas by combining the methanol synthesis and subsequent methanol dehydration, either in two consecutive reaction steps, or in a single conversion step, as described e.g. in A. Schafer et al. US 9295978 B2, and Saravanan et al. “Recent progress for direct synthesis of dimethyl ether from syngas on the heterogeneous bifunctional hybrid catalysts”, Applied Catalysis B: Environmental, Volume 217, 2017, pages 494-522. Both methanol and its derivative DME are formally C1 compounds which may be obtained from syngas.
  • WO 2022/144480 A1 discloses a process for the production of acetone by contacting a gas mixture comprising at least synthesis gas, with a multicomponent catalyst.
  • the present invention relates to a process for producing 2-propanol, the process comprising
  • the one or more carbonylation catalysts C1 are chemically different from the one or more ketonization catalysts C2.
  • the one or more carbonylation catalysts C1 are chemically different from the one or more catalysts C3.
  • the one or more ketonization catalysts C2 are chemically different from the one or more catalysts C3.
  • the one or more carbonylation catalysts C1 are chemically different from the one or more ketonization catalysts C2, wherein the one or more carbonylation catalysts C1 are chemically different from the one or more catalysts C3, and wherein the one or more ketonization catalysts C2 are chemically different from the one or more catalysts C3.
  • R1 comprises one or more of the one or more carbonylation catalysts C1
  • R2 comprises one or more of the one or more catalysts C3
  • R1 or R2 comprises one or more of the one or more ketonization catalysts C2.
  • R1 comprises one or more of the one or more carbonylation catalysts C1
  • R2 comprises one or more of the one or more ketonization catalysts C2
  • R3 comprises one or more of the one or more catalysts C3.
  • the one or more carbonylation catalysts C1 are solid.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 .
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1
  • the one or more metals M1 are selected from the group consisting of Ag, Ga, Pd, Cu, In, Sn, Ir, Pt, Rh, Co, Re, Zn, and mixtures of two or more thereof, more preferably from the group consisting of Ag, Ga, Pd, and mixtures of two or more thereof, wherein the one or more metals M1 more preferably are Ag.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1
  • the one or more metals M1 are supported on the support material S1 at a loading in the range of from 0.001 to 50 weight-%, more preferably from 0.01 to 40 weight-%, more preferably from 0.1 to 30 weight-%, more preferably from 1 to 20 weight-%, more preferably from 4 to 17 weight-%, more preferably from 7 to 13 weight-%, more preferably from 9 to 11 weight-%, calculated as sum of the one or more metals M1 as elements and based on the sum of the weights of the one or more metals M1 as elements and the support material S1 .
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1
  • the support material S1 comprises, more preferably consists of, one or more of a zeolitic material and a metal oxide, more preferably a zeolitic material.
  • the support material S1 comprises, more preferably consists of, one or more of a zeolitic material and a metal oxide
  • the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises, more preferably consists of, a zeolitic material, wherein the zeolitic material more preferably comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of a metal, calculated as element and based on the sum of the weights of the metal and the zeolitic material, wherein the zeolitic material more preferably is free of a metal, wherein the metal is selected from the group consisting of groups 3 to 12 of the periodic table of elements.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material comprises SiO2 and AI2O3 in its framework structure, and wherein the zeolitic material more preferably has a SIC>2 : AI2O3 molar ratio in the range of from 3:1 to 100:1 , more preferably in the range of from 5:1 to 40:1 , more preferably in the range of from 8:1 to 30:1 , more preferably in the range of from 14:1 to 26:1 , more preferably in the range of from 17:1 to 23:1 .
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M 1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , wherein the support material S1 comprises, preferably consists of, one or more of a zeolitic material
  • the support material S1 comprises, preferably consists of, one or more of a zeolitic material
  • each of the one or more carbonylation catalysts C1 independently from one another, has an atomic ratio of the one or more metals M 1 , calculated as sum of the molar amounts of the one or more metals M 1 as elements, to Al comprised in the framework structure of the zeolitic material, calculated as molar amount of Al as element, in the range of 0.2:1 to 1.0:1 , more preferably in the range of 0.5:1 to 0.7:1.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material has a framework structure comprising rings with 8 T- atoms, preferably rings with 8 T-atoms and rings with 10 or 12 T-atoms, more preferably rings with 8 T-atoms and rings with 12 T-atoms.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material has a framework structure type selected from the group consisting of ABW, AEN, AFR, AFV, APC, APD, ATN, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BIK, BRE, CAS, CDO, CFG, CSV, CZP, DAC, DDR, EAB, EEI, EON, EPI, ESV, ETL, EZT, FER, HEU, IHW, IRN, ITE, ITW
  • the zeolitic material has the MOR-type framework structure type
  • the zeolitic material is selected from the group consisting of Mordenite, [Ga-Si-O]- MOR, Maricopaite, Ca-Q, LZ-211 , Na-D, RMA-1 , including mixtures of two or more thereof, wherein more preferably the zeolitic material having a MOR-type framework structure comprises, more preferably consists of, Mordenite.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material is in the H-form or in the NFU-form, preferably in the H-form.
  • the one or more carbonylation catalysts 01 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S1 , wherein the one or more carbonylation catalysts 01 more preferably are free of Zn.
  • the one or more carbonylation catalysts 01 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S1 , wherein the one or more carbonylation catalysts 01 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
  • the one or more ketonization catalysts C2 are solid.
  • each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2.
  • each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more of ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, more preferably from the group consisting of ceria, zirconia, ceria-zirconia, and mixtures of two or more thereof, wherein each of the one or more ketonization catalysts more preferably are c
  • each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2, it is preferred that the one or more metals M2 are selected from the group consisting of Pd, Pt, Ag, Fe, Ru, Os, Co, Rh, Ir, N I, Cu, Au, and mixtures of two or more thereof, more preferably from the group consisting of Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M2 more preferably are Pd.
  • each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2, it is preferred that each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, wherein each of the one or more ketonization catalysts C2 independently from one another more preferably comprises, more preferably consists, of the one or more metals M2, the support material S2 and the zeolitic material.
  • each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material
  • the one or more metals M2 are supported on the support material S2 at a loading in the range of from 0.01 to 0.50 weight-%, preferably from 0.02 to 0.20 weight-%, more preferably from 0.03 to 0.12 weight-%, more preferably from 0.04 to 0.09 weight-%, more preferably from 0.05 to 0.07 weight-%, calculated as sum of the one or more metals M2 as elements and based on the sum of the weights of the one or more metals M2, the support material S2 and the zeolitic material.
  • each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material
  • the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, and wherein the zeolitic material preferably has a SiC>2 : AI2O3 molar ratio in the range of from 1 :1 to 200:1 , more preferably in the range of from 5:1 to 100:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 15:1 to 25:1 , more preferably in the range of from 18:1 to 22:1.
  • each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material
  • the zeolitic material has a framework structure comprising rings with 10 T-atoms, wherein the rings comprised in the framework structure are more preferably selected from the group consisting of rings with equal to or less than 10 T-atoms.
  • each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material
  • the zeolitic material has a framework structure type selected from the group consisting of CSV, DAC, ETV, EUO, EWO, FER, HEU, IMF, ITH, LAU, -LIT, MEL, MFI, MFS, MTT, MWW, NES, -PAR, PCR, PTY, PWW, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TON, TUN, -WEN, and mixed structures composed of two or more thereof, more preferably selected from the group consisting of FER, MFI, MWW, and mixed structures composed of two or more thereof, wherein the zeolitic material more preferably has the FER-type framework structure type.
  • the zeolitic material has the FER-type framework structure type
  • the zeolitic material is selected from the group consisting of Ferrierite, [Ga-Si-O]-FER, [Si- O]-FER, FU-9, ISI-6, NU-23, Sr-D, ZSM-35, and [B-Si-O]-FER, including mixtures of two or more thereof, more preferably from the group consisting of Ferrierite, FU-9, ISI-6, NU-23, and ZSM-35, including mixtures of two or more thereof, wherein more preferably the zeolitic material having a FER-type framework structure comprises, more preferably consists of, Ferrierite.
  • each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material
  • the zeolitic material is in the Flform .
  • each of the one or more ketonization catalysts 02 independently from one another comprises a zeolitic material
  • each of the one or more ketonization catalysts 02 independently from one another has a mass ratio of the zeolitic material, calculated as weight of the zeolitic material, to the one or more metals M2 and the support material S2, calculated as sum of the weights of the one or more metals M2 as elements and the support material S2, in the range of from 1 :200 to 1 :1 , more preferably in the range of from 1 :100 to 1 :2, more preferably in the range of from 1 :20 to 1 :5, more preferably in the range of from 1 :12 to 1 :7.
  • each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2, it is preferred that the support material S2 comprises, more preferably consists of, a metal oxide.
  • the support material S2 comprises, more preferably consists of, a metal oxide
  • the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, more preferably from the group consisting of ceria, zirconia, ceria-zirconia, and mixtures of two or more thereof, wherein the metal oxide more preferably is ceria-zirconia.
  • the metal oxide comprises, preferably consists of, ceria-zirconia
  • the ceria-zirconia has a Ce:Zr molar ratio in the range of from 1 :1 to 5:1 , more preferably in the range of from 1.5:1 to 2.5:1 , more preferably in the range of from 1.7:1 to 2.3:1 , more preferably in the range of from 1.9:1 to 2.1 :1.
  • the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Zn.
  • the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
  • the one or more catalysts C3 are solid.
  • the one or more metals M3 are selected from the group consisting of Ag, Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M3 more preferably are Ag, a mixture of Ag and Pt, or a mixture of Ag and Pd, wherein the one or more metals M3 more preferably are Ag.
  • each of the one or more catalysts C3 further comprise one or more co-cata- lyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, wherein each of the one or more catalysts C3 preferably displays an atomic ratio of the one or more metals M3, calculated as elements, to the one or more co-catalyst metals, calculated as elements, of less than 10:1 .
  • the one or more metals M3 comprise, more preferably consists of, a mixture of Ag and Pt, wherein each of the one or more catalysts C3 more preferably display an atomic ratio of Ag, calculated as element, to Pt, calculated as element, in the range of from 5:1 to 50:1 , more preferably in the range of from 10:1 to 28:1 , more preferably in the range of from 15:1 to 23:1 , more preferably in the range of from 18:1 to 20:1.
  • each of the one or more catalysts C3 further comprise one or more co-cata- lyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, it is preferred according to a first alternative that the one or more metals M3 comprise, preferably consist of, Pd and wherein the one or more co-catalyst metals comprise, more preferably consist of, In, wherein the one or more catalysts C3 preferably display an atomic ratio of Pd, calculated as element, to In, calculated as element, in the range of from 1 :2 to 10:1 , more preferably in the range of from 1 :
  • each of the one or more catalysts C3 further comprise one or more co-cata- lyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, it is preferred according to a second alternative that the one or more metals M3 comprise, preferably consist of, Pt and wherein the one or more co-catalyst metals comprise, preferably consist of, Sn, wherein the one or more catalysts C3 preferably display an atomic ratio of Pt, calculated as element, to Sn, calculated as element, in the range of from 0.05:1 to 5:1 , more preferably in the range of from 0.1
  • the one or more metals M3 are supported on the support material S3 at a loading in the range of from 0.2 to 50.0 weight-%, more preferably in the range of from 1 .0 to 40 weight-%, more preferably in the range of from 1.5 to 30 weight-%, more preferably in the range of from 2.0 to 20 weight-%, more preferably in the range of from 2.5 to 10 weight-%, more preferably in the range of from 3.0 to 5.0 weight-%, calculated as sum of the one or more metals M3 as elements and based on the sum of the weights of the one or more metals M3 and the support material S3.
  • the support material S3 comprises, preferably consists of, one or more of a transitional alumina, a-alumina, silica, titania, carbon, and silicon carbide, preferably one or more of a-alumina, silica, carbon and silicon carbide, wherein the support material S3 more preferably comprises, more preferably consists of, a-alumina or silica, more preferably a-alu- mina.
  • the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of y-alumina, wherein the one or more catalysts C3 are more preferably free of y-alumina.
  • the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Ni, calculated as element and based on the sum of the weights of the Ni, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Ni.
  • the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Mo, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Mo, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Mo.
  • the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Zn, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Zn.
  • the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, more preferably of one or more of Cu and Pd, calculated as sum of the weights of one or more of Pd and Cu, respectively, as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
  • each of the one or more carbonylation catalysts C1 , the one or more keton- ization catalysts C2, and the one or more catalysts C3, independently from one another is comprised in a packed-bed.
  • the gas stream prepared according to (II) has a molar ratio of CO to H2 in the range of from 0.1 :1 to 10:1 , more preferably in the range of from 0.2:1 to 5:1 , more preferably in the range of from 0.3:1 to 2.5:1 , more preferably in the range of from 0.4:1 to 1.3:1 , more preferably in the range of from 0.5:1 to 1.1 :1.
  • the gas stream prepared according to (II) has a molar ratio of CO to the oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, in the range of from 1 :1 to 100:1 , more preferably in the range of from 2:1 to 80:1 , more preferably in the range of from 5:1 to 60:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 20:1 to 47:1.
  • the gas stream prepared according to (II) has a molar ratio of H2 to oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, in the range of from 10:1 to 100:1 , more preferably in the range of from 20:1 to 80:1 , more preferably in the range of from 30:1 to 60:1 , more preferably in the range of from 40:1 to 50:1 , more preferably in the range of from 43:1 to 47:1.
  • the gas stream prepared according to (II) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof.
  • the gas stream prepared according to (II) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof
  • the gas stream prepared according to (ii) has a molar ratio of CO to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 50:1 , more preferably in the range of from 1 :1 to 20:1 , more preferably in the range of from 2:1 to 10:1 , more preferably in the range of from 3:1 to 7:1 , more preferably in the range of from 4:1 to 6:1 .
  • the gas stream prepared according to (ii) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof
  • the gas stream prepared according to (ii) has a molar ratio of H2 to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 500: 1 , more preferably in the range of from 1 :1 to 200:1 , more preferably in the range of from 2:1 to 100:1 , more preferably in the range of from 3:1 to 50:1 , more preferably in the range of from 4:1 to 25:1.
  • the gas stream prepared according to (ii) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof
  • the gas stream prepared according to (ii) has a molar ratio of the oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :50 to 50:1 , more preferably in the range of from 1 :25 to 20:1 , more preferably in the range of from 1 :20 to 10:1 , more preferably in the range of from 1 :15 to 1 :1 , more preferably in the range of from 1 :10 to 1 :5.
  • the gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C2-C6)alkene, more preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 vol- ume-% of a (C2-C6)alkene, preferably of one or more of ethylene, propylene, and butylene, more preferably of propylene.
  • the gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C3-C6)ketone, more preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 vol- ume-% of a (C3-C6)ketone, preferably of acetone.
  • the gas stream prepared according to (ii) is obtained from biosyngas.
  • the reactor comprises an inlet end and an outlet end, and an axial length extending from the inlet end to the outlet end.
  • the reactor has a volume in the range of from 50 to 1000 I, preferably in the range of from 250 to 400 I, more preferably in the range of from 300 to 330 I.
  • contacting according to (iii) comprises heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 to a temperature in the range of from 100 to 400 °C, more preferably in the range of from 150 to 400 °C, more preferably in the range of from 200 to 350 °C, more preferably in the range of from 240 to 310 °C, more preferably in the range of from 260 to 290 °C, more preferably in the range of from 270 to 280 °C.
  • the gas stream prepared according to (ii) is contacted according to (iii) with the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 at a pressure in the range of from 1 to 200 bar(abs), more preferably in the range of from 5 to 150 bar(abs), more preferably in the range of from 5 to 35 bar(abs), more preferably in the range of from 10 to 30 bar(abs), more preferably in the range of from 12 to 28 bar(abs), more preferably in the range of from 16 to 24 bar(abs), more preferably in the range of from 18 to 22 bar(abs), more preferably in the range of from 19 to 21 bar(abs).
  • the gas stream prepared according to (ii) is fed into the reactor according to (iii) with a gas hourly space velocity in the range of from 10 to 1000 IT 1 , more preferably in the range of from 100 to 300 IT 1 , more preferably in the range of from 150 to 250 IT 1 , more preferably in the range of from 190 to 210 IT 1 , more preferably in the range of from 194 to 203 IT 1 .
  • the process further comprises a heat treatment after (ii) and prior to (iii), wherein the heat treatment more preferably comprises
  • the process further comprises a heat treatment after (ii) and prior to (iii), wherein the heat treatment more preferably comprises (a.1 ) and (a.2)
  • heating according to (a.2) is performed for a period in the range of from 1 to 5 h, more preferably in the range of from 2 to 4 h.
  • the process further comprises a catalyst activation after (ii) or after the heat treatment according to any one of the embodiments disclosed herein, and prior to (iii), wherein the catalyst activation comprises
  • the gas stream is fed according to (b.1) into the reactor has a volume ratio of H2 to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases in the range of from 0.1 :1 to 1 :1 , more preferably in the range of from 0.3:1 to 0.5:1.
  • heating according to (b.2) is performed for a period in the range of from 1 to 5 h, more preferably in the range of from 2 to 4 h.
  • the process is a continuous process or a batch process, more preferably a continuous process.
  • process further comprises prior to (i)
  • Suitable catalysts are disclosed for example in J. P. Lange, "Methanol synthesis: a short review of technology improvements", Catalysis Today, Volume 64, Issues 1-2, 2001 , pages 3-8, US9295978B2, and Saravanan et al. “Recent progress for direct synthesis of dimethyl ether from syngas on the heterogeneous bifunctional hybrid catalysts”, Applied Catalysis B: Environmental, Volume 217, 2017, pages 494-522.
  • the gas stream comprises H2 in an amount in the range of from 25 to 95 vol.-%, more preferably of from 50 to 92 vol.-%, more preferably of from 60 to 90 vol.-%, and more preferably of from 60 to 75 vol.-%.
  • the gas stream comprises CO2 in an amount of equal to or less than 60 vol.-%, more preferably of equal to or less than 50 vol.-%, more preferably of equal to or less than 40 vol.-%, more preferably of equal to or less than 30 vol.-%, more preferably of equal to or less than 25 vol.-%, and more preferably of equal to or less than 22, wherein more preferably the gas stream comprises CO2 in an amount in the range of froml to 22 vol.-%, more preferably in the range of from 5 to 21 vol.-%, more preferably in the range of from 10 to 20 vol.-%, and more preferably in the range of from 15 to 19 vol.-%.
  • the gas stream further comprises CO, more preferably in an amount in the range from 0.5 to 40 vol.-%, more preferably in the range of from 1 to 33 vol.-%, more preferably in the range of from 2 to 20 vol.-%, more preferably in the range of from 3 to 10 vol.-%, and more preferably in the range of from 5 to 8 vol.-%.
  • the gas stream further comprises one or more inert gases, more preferably in an amount in the range of from 0.1 to 40 vol.-%, more preferably in the range of from 0.5 to 30 vol.-%, more preferably in the range of from 1 to 20 vol.-%, and more preferably in the range of from 2 to 15 vol.-%.
  • the gas stream further comprises one or more inert gases
  • the one or more inert gases are selected from the group consisting of He, Ar, Ne, CH4, N2, and mixtures of two or more thereof, more preferably from the group consisting of Ar, CH4, N2, and mixtures of two or more thereof, wherein the one or more inert gases more preferably are CH4 and N2.
  • contacting according to (B) is conducted at a temperature in the range of from 200 to 400 °C, more preferably in the range of from 250 to 350 °C, and more preferably in the range of from 270 to 330 °C.
  • contacting according to (B) is conducted at a pressure of 100 bar(abs) or less, more preferably in the range of from 50 to 95 bar(abs), more preferably in the range of from 60 to 90 bar(abs), and more preferably in the range of from 70 to 80 bar(abs).
  • contacting according to (B) is conducted in a continuous mode, more preferably in a recycle mode, after separation of the high boiling products dimethylether and methanol.
  • contacting according to (B) is conducted in a continuous mode, more preferably in a recycle mode, after separation of the high boiling products dimethylether and methanol, it is preferred that contacting according to (B) is conducted in a continuous mode at a gas hourly space velocity in the range of from 500 to 24,000 IT 1 , more preferably in the range of from 1000 to 8000 IT 1 , and more preferably in the range of from 2000 to 6000 IT 1 .
  • process further comprises after (iii)
  • the product gas stream obtained according to (iii) further comprises one or more of methyl acetate and acetone.
  • three catalysts are used, i.e. a carbonylation catalyst, a ketonization catalyst and a further catalyst.
  • the carbonylation and ketonization catalysts are defined with respect to their purpose, indicating that the respective catalyst is suitable for its specific purpose being catalyzing a carbonylation reaction or a ketonization reaction.
  • Said catalysts can be identical to each other or differ in their physical or chemical nature.
  • carbonylation as used in the context of the present invention is understood to mean a reaction in which a carboxylic compound, that is a carboxylic acid or a carboxylic ester, is formed from an alcohol compound or an ether compound, and carbon monoxide.
  • a carbonylation catalyst according to the present invention is the catalyst which catalyses this type of reaction.
  • ketonization as used in the context of the present invention is understood to mean a reaction in which a ketone-type compound, also together with carbon dioxide and water, is produced by condensation of two carboxylic compounds or by self-condensation of a single carboxylic compound.
  • a ketonization catalyst according to the present invention is the catalyst which catalyzes this type of reaction.
  • the term “chemically different” with respect to a catalyst being chemically different to another catalyst indicates that the former catalyst has one or more chemical features distinguishing it from the latter.
  • Said one or more chemical features include any chemical features with respect to the nature of elements comprised by said catalysts, the molar composition of elements comprised by said catalysts, the electronic structure of the bonds between the elements comprised by said catalysts, and the spatial arrangement of the elements comprised by said catalysts.
  • the electronic structure of bonds relates to the type of bond particularly including covalent bonds, ionic bonds, metallic bonds and coordinate covalent bonds.
  • the term “chemically different” with respect to a catalyst being chemically different to another catalyst indicates that the former catalyst differs from the latter in the chemical composition.
  • inert gas or “inert gases” for a plurality, is understood to mean a compound which, under a specific set of operational conditions of the inventive process, or under a specific set of operational conditions of catalyst preparation and activation therefor, does not undergo chemical transformation and it does not modify to any significant extent the reactivity of other compounds, concomitantly present.
  • gaseous compounds selected from the list of nitrogen (N2), helium (He), argon (Ar), and light alkanes such as methane (CH4), ethane (C2H6), propane (CsHs), and any mixtures thereof, are considered inert gases.
  • the unit bar(abs) refers to an absolute pressure of 10 5 Pa and the unit angstrom refers to a length of 10’ 10 m.
  • each reaction zone Rk independently from one another comprises one or more catalysts selected from the group consisting of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3; wherein, if m is equal to or greater than 2, each reaction zone Rk+i is arranged downstream of the reaction zone Rk.
  • R1 or R2 comprises one or more of the one or more ketonization catalysts C2.
  • R1 comprises one or more of the one or more carbonylation catalysts C1
  • R2 comprises one or more of the one or more ketonization catalysts C2
  • R3 comprises one or more of the one or more catalysts C3.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 .
  • the one or more metals M1 are selected from the group consisting of Ag, Ga, Pd, Cu, In, Sn, Ir, Pt, Rh, Co, Re, Zn, and mixtures of two or more thereof, preferably from the group consisting of Ag, Ga, Pd, and mixtures of two or more thereof, wherein the one or more metals M1 more preferably are Ag.
  • the support material S1 comprises, preferably consists of, one or more of a zeolitic material and a metal oxide, preferably a zeolitic material.
  • the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises, preferably consists of, a zeolitic material, wherein the zeolitic material preferably comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight- %, of a metal, calculated as element and based on the sum of the weights of the metal and the zeolitic material, wherein the zeolitic material more preferably is free of a metal, wherein the metal is selected from the group consisting of groups 3 to 12 of the periodic table of elements.
  • the zeolitic material comprises SiC>2 and AI2O3 in its framework structure
  • the zeolitic material preferably has a SiO 2 : AI2O3 molar ratio in the range of from 3:1 to 100:1 , more preferably in the range of from 5:1 to 40:1 , more preferably in the range of from 8:1 to 30:1 , more preferably in the range of from 14:1 to 26:1 , more preferably in the range of from 17:1 to 23:1.
  • each of the one or more carbonylation catalysts C1 independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , wherein the support material S1 comprises, preferably consists of, one or more of a zeolitic material, wherein the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, wherein each of the one or more carbonylation catalysts C1 , independently from one another, has an atomic ratio of the one or more metals M 1 , calculated as sum of the molar amounts of the one or more metals M1 as elements, to Al comprised in the framework structure of the zeolitic material, calculated as molar amount of Al as element, in the range of 0.2:1 to 1.0:1 , more preferably in the range of 0.5:1 to 0.7:1.
  • the zeolitic material has a framework structure comprising rings with 8 T-atoms, preferably rings with 8 T-atoms and rings with 10 or 12 T-atoms, more preferably rings with 8 T-atoms and rings with 12 T-at- oms.
  • zeolitic material has a framework structure type selected from the group consisting of ABW, AEN, AFR, AFV, APC, APD, ATN, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BIK, BRE, CAS, CDO, CFG, CSV, CZP, DAC, DDR, EAB, EEI, EON, EPI, ESV, ETL, EZT, FER, HEU, IHW, IRN, ITE, ITW, JBW, JNT, JSN, JSW, LEV, MAZ, MFS, MOR, MRT, MTF, NSI, OWE, PAR, PCR, PCS, PSI, PTY, PWW, RRO, RTE, RTH, RWR, SAS, SFO, STI, UEI, UFI, VET, YUG, ZON, ACO, AEI, AFN, A
  • the zeolitic material has the MOR-type framework structure type and wherein the zeolitic material is selected from the group consisting of Mordenite, [Ga-Si-O]-MOR, Maricopaite, Ca-Q, LZ-211 , Na-D, RMA-1 , including mixtures of two or more thereof, wherein more preferably the zeolitic material having a MOR- type framework structure comprises, more preferably consists of, Mordenite.
  • the zeolitic material is in the H- form or in the NH4-form, preferably in the H-form.
  • any one of embodiments 1 to 25 wherein the one or more carbonylation catalysts C1 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S1 , wherein the one or more carbonylation catalysts C1 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
  • the one or more ketonization catalysts C2 are solid.
  • each of the one or more ketonization catalysts C2 independently from one another comprises, preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2.
  • the one or more metals M2 are selected from the group consisting of Pd, Pt, Ag, Fe, Ru, Os, Co, Rh, Ir, Ni, Cu, Au, and mixtures of two or more thereof, preferably from the group consisting of Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M2 more preferably are Pd.
  • each of the one or more ketonization catalysts C2 independently from one another further comprises a zeolitic material, wherein each of the one or more ketonization catalysts C2 independently from one another preferably comprises, more preferably consists, of the one or more metals M2, the support material S2 and the zeolitic material.
  • the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, and wherein the zeolitic material preferably has a SIC>2 : AI2O3 molar ratio in the range of from 1 :1 to 200:1 , more preferably in the range of from 5:1 to 100:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 15:1 to 25:1 , more preferably in the range of from 18:1 to 22:1.
  • the zeolitic material has a framework structure type selected from the group consisting of CSV, DAC, ETV, EUO, EWO, FER, HEU, IMF, ITH, LAU, -LIT, MEL, MFI, MFS, MTT, MWW, NES, -PAR, PCR, PTY, PWW, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TON, TUN, -WEN, and mixed structures composed of two or more thereof, preferably selected from the group consisting of FER, MFI, MWW, and mixed structures composed of two or more thereof, wherein the zeolitic material more preferably has the FER-type framework structure type.
  • the zeolitic material has the FER-type framework structure type and wherein the zeolitic material is selected from the group consisting of Ferrierite, [Ga-Si-O]-FER, [Si-O]-FER, FU-9, ISI-6, NU-23, Sr-D, ZSM-35, and [B-Si-O]- FER, including mixtures of two or more thereof, more preferably from the group consisting of Ferrierite, FU-9, ISI-6, NU-23, and ZSM-35, including mixtures of two or more thereof, wherein more preferably the zeolitic material having a FER-type framework structure comprises, more preferably consists of, Ferrierite.
  • each of the one or more keton- ization catalysts C2 independently from one another has a mass ratio of the zeolitic material, calculated as weight of the zeolitic material, to the one or more metals M2 and the support material S2, calculated as sum of the weights of the one or more metals M2 as elements and the support material S2, in the range of from 1 :200 to 1 :1 , preferably in the range of from 1 :100 to 1 :2, more preferably in the range of from 1 :20 to 1 :5, more preferably in the range of from 1 :12 to 1 :7.
  • the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, preferably from the group consisting of ceria, zirconia, ceriazirconia, and mixtures of two or more thereof, wherein the metal oxide more preferably is ceria-zirconia.
  • each of the one or more keton- ization catalysts C2 independently from one another comprises, preferably consists of, one or more of ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, preferably from the group consisting of ceria, zirconia, ceria-zirconia, and mixtures of two or more thereof, wherein each of the one or more ketonization catalysts more preferably are ceria-zirconia.
  • any one of embodiments 1 to 41 wherein the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Zn.
  • the one or more metals M3 are selected from the group consisting of Ag, Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M3 more preferably are Ag, a mixture of Ag and Pt, or a mixture of Ag and Pd, wherein the one or more metals M3 more preferably are Ag.
  • each of the one or more catalysts C3 further comprise one or more co-catalyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, wherein each of the one or more catalysts C3 preferably displays an atomic ratio of the one or more metals M3, calculated as elements, to the one or more co-catalyst metals, calculated as elements, of less than 10:1.
  • the one or more metals M3 comprise, preferably consist of, Pd and wherein the one or more co-catalyst metals comprise, preferably consist of, In, wherein the one or more catalysts C3 preferably display an atomic ratio of Pd, calculated as element, to In, calculated as element, in the range of from 1 :2 to 10:1 , preferably in the range of from 1 :1 to 3:1 , more preferably in the range of from 1.5:1 to 2.5:1 , more preferably in the range of from 1 .9:1 to 2.1 :1.
  • the support material S3 comprises, preferably consists of, one or more of a transitional alumina, a-alumina, silica, titania, carbon, and silicon carbide, preferably one or more of a-alumina, silica, carbon and silicon carbide, wherein the support material S3 more preferably comprises, more preferably consists of, a-alumina or silica, more preferably a-alumina.
  • any one of embodiments 1 to 54 wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Zn, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Zn.
  • any one of embodiments 1 to 55 wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as sum of the weights of one or more of Pd and Cu, respectively, as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
  • the gas stream prepared according to (ii) has a molar ratio of CO to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 50:1 , preferably in the range of from 1 :1 to 20:1 , more preferably in the range of from 2:1 to 10:1 , more preferably in the range of from 3:1 to 7:1 , more preferably in the range of from 4:1 to 6:1.
  • gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C2-C6)alkene, preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-% of a (C2-C6)alkene, preferably of one or more of ethylene, propylene, and butylene, more preferably of propylene.
  • gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C3-C6)ketone, preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-% of a (C3-C6)ketone, preferably of acetone.
  • contacting according to (iii) comprises heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 to a temperature in the range of from 100 to 400 °C, preferably in the range of from 150 to 400 °C, more preferably in the range of from 200 to 350 °C, more preferably in the range of from 240 to 310 °C, more preferably in the range of from 260 to 290 °C, more preferably in the range of from 270 to 280 °C.
  • the gas stream comprises H2 in an amount in the range of from 25 to 95 vol.-%, preferably of from 50 to 92 vol.-%, more preferably of from 60 to 90 vol.-%, and more preferably of from 60 to 75 vol.-%.
  • the gas stream comprises CO2 in an amount of equal to or less than 60 vol.-%, preferably of equal to or less than 50 vol.-%, more preferably of equal to or less than 40 vol.-%, more preferably of equal to or less than 30 vol.-%, more preferably of equal to or less than 25 vol.-%, and more preferably of equal to or less than 22, wherein more preferably the gas stream comprises CO2 in an amount in the range of froml to 22 vol.-%, more preferably in the range of from 5 to 21 vol.-%, more preferably in the range of from 10 to 20 vol.-%, and more preferably in the range of from 15 to 19 vol.-%.
  • the gas stream further comprises CO, preferably in an amount in the range from 0.5 to 40 voL-%, more preferably in the range of from 1 to 33 voL-%, more preferably in the range of from 2 to 20 voL-%, more preferably in the range of from 3 to 10 voL-%, and more preferably in the range of from 5 to 8 voL-%.
  • the gas stream further comprises one or more inert gases, preferably in an amount in the range of from 0.1 to 40 vol.-%, more preferably in the range of from 0.5 to 30 vol.-%, more preferably in the range of from 1 to 20 vol.-%, and more preferably in the range of from 2 to 15 vol.-%.
  • the present invention is further illustrated by the following reference examples, examples and comparative examples.
  • the macroscopic particle size of the catalyst was determined using calibrated Retsch stainless steel sieves.
  • XRD Powder X-Ray Diffraction
  • the measurement range used was 3.5° to 90.0° (2theta), with a step of 0.020° (2theta) and a measurement time of 35 seconds per step. Measurements were performed at 298 K, while the sample, mounted as a fine powder in a sample holder with a sample area of 79 mm 2 or 804 mm 2 , was rotated at 0.5 revolutions per second around the axis perpendicular to the irradiated sample surface.
  • compositions were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) using a Varian 715-ES spectrometer.
  • the samples were previously dissolved in a mixture of nitric acid (HNO3) and hydrochloric acid (HCI), in a 1 :3 ratio (HNO3:HCI), at 333 K for 20 h.
  • HNO3:HCI hydrochloric acid
  • disaggregation was not possible and therefore analyses were performed by Energy Dispersive X-ray spectroscopy (EDS) in a Field Emission Scanning Electron microscope, FESEM (ZEISS, ULTRA 55), equipped with a X-Max 80 - Oxford Instruments EDS detector.
  • EDS Energy Dispersive X-ray spectroscopy
  • the powdered sample was dispersed over a double-faced carbon adhesive mounted on a SEM pin stub. Elemental quantification was based on the EDS signal for photon emission K lines for elements with atomic number below 15 (Z ⁇ 15), photon emission M lines for elements with atomic number greater than 50 (Z > 50), and photon emission L lines for the remaining elements.
  • the obtained material was then dried at 100 °C for 2 h in an oven. Then, the solid was transferred into a ceramic crucible and subjected to a further drying step at 110 °C for 4 h, followed by calcination under stagnant air atmosphere by heating to 500 °C (heating ramp of 3 °C/min), followed by an isothermal step at 500 °C for 3 h and cooling down to room temperature in a convectionless muffle furnace.
  • the silver loading was 9.4 weight- % (corresponding to an atomic ratio Ag/AI of 0.6).
  • the catalyst Prior to catalytic experiments, the catalyst was subjected to activation treatments. 2.0 g of Ag-H- MOR, previously sieved to obtain particles having a size in the range 0.2-0.4 mm, were loaded as a packed bed in a stainless steel reactor (316 L, 7.8 mm internal diameter) and subjected to a first thermal treatment under nitrogen flow (50 mL/min) by heating to 500 °C (heating ramp of 3 °C/min from room temperature) followed by an isothermal step at 500 °C for 3 hours and cooling down to room temperature.
  • a first thermal treatment under nitrogen flow 50 mL/min
  • 500 °C heating ramp of 3 °C/min from room temperature
  • an isothermal step at 500 °C for 3 hours and cooling down to room temperature.
  • a gas mixture of DME/CO/H2/Ar in molar ratios 1/45/45/9 was fed to the inlet of the reactor and the reactor was pressurized to 20 bar pressure by means of a membrane back-pressure regulating valve (Swagelok) located downstream of the reactor.
  • the flow rate of the DME/CO/H2/Ar stream was adjusted to obtain approximately 900 IT 1 gas space velocity (GHSV) and the reactor temperature was increased to 275 °C following a heating ramp of 3 °C/min and it was kept constant at 275 °C for 20 hours and finally cooled down to room temperature. After these activation treatments, the catalyst was recovered and then used as carbonylation catalyst.
  • FER zeolite (SiO2/AhO3 molar ratio of 26.4) was synthetized in its aluminosilicate form.
  • a synthesis gel was prepared by mixing 0.79 g of pseudo-boehmite (CATAPAL, Sasol Materials, 72 % AI2O3), 10.6 g of trans- 1 ,4-diaminecyclohexane (TDACH, Sigma Aldrich, 98 %), 25.3 g of colloidal silica (Sigma Aldrich, LUDOX AS40, 40 % suspension in water) and deionized water.
  • the mixture was kept under stirring at 377 rpm at room temperature while evaporating the amount of water needed to reach a molar gel composition of 1 SiO2 : 0.033 AI2O3 : 0.48 TDACH : 5 H2O.
  • 3.54 g of HF Sigma Aldrich, 48 % in water was added to the gel, reaching a final molar gel composition of 1 SiO2 : 0.033 AI2O3 : 0.48 TDACH : 0.5 HF : 5 H2O.
  • the gel obtained was kept under stirring at room temperature for 30 minutes and it was then transferred to 2 stainless steel autoclaves provided with PTFE in-liners of 35 ml volume.
  • the autoclaves were introduced in a pre-heated oven and kept at 150 °C for 15 days for zeolite crystallization.
  • the solid obtained was recovered by filtration, washed with deionized water, dried at 100 °C in an oven, and calcined in a tubular packed-bed reactor at 550 °C (heating rate 1 °C/min) for 10 hours, under synthetic air flow (approximately 80 ml/min).
  • CeO2-ZrO2 (Ce:Zr molar ratio of approximately 2:1 ) was synthetized by submitting a commercial cerium (IV)-zirconium (IV) mixed oxide (Sigma-Aldrich, 99 %) to a thermal treatment under stagnant air atmosphere in a muffle furnace. The sample was heated from room temperature to 600 °C (heating rate of 3 °C/min), followed by an isothermal step at 600 °C for 4 hours and cooling down to room temperature. Next, palladium was incorporated by impregnation. 21 mg of palladium acetylacetonate (Pd(acac)2, Sigma Aldrich, 99 %), were dissolved in 125 mL of acetone.
  • Pd(acac)2 palladium acetylacetonate
  • H-FER and Pd/CeO2-ZrO2 powders were mixed in a 1 :7.5 mass ratio and the resulting composite material was ground thoroughly in a mortar with a pestle to produce the H-FER- Pd/CeO2-ZrC>2 catalyst.
  • the Pd loading on the H-FER-Pd/CeO2-ZrO2 catalyst was 0.065 weight- 0 //o.
  • the impregnated solid was dried in a quartz tubular reactor under nitrogen flow (approximately 80 mL/min) at 70 °C for 10 hours, followed by a calcination treatment to decompose the silver precursor, in the same reactor, under the same nitrogen flow, by heating from 70 °C to 450 °C (heating rate of 1 °C/min), followed by an isothermal stage at 450 °C for 4 hours.
  • Alpha-alumina (a-ALOs) was synthesized by direct calcination of a gamma-alumina (Y-AI2O3).
  • Gamma-AhOs spheres (SASOL, Alumina Spheres 1 .8/210) were crushed and sieved. Then par- tides in the size range of 0.4-0.6 mm were calcined in a muffle furnace under stagnant air applying a heating ramp of 3 °C/min from room temperature to 1140 °C, followed by an isothermal dwell stage at 1140 °C for 4 hours and cooling down to room temperature.
  • a-ALOs prepared according to Reference Example 8 were suspended in the metal salts solution and the suspension was stirred for 15 minutes.
  • the solvent was removed under vacuum (50-100 mbar) using a rotary evaporator at 60 °C.
  • the obtained material was then dried in air at 60 °C for 2 h.
  • the dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 350 °C (heating rate of 2 °C/min), followed by an isothermal step at 350 °C for 4 h under nitrogen flow (200 mL/min).
  • the solvent was removed under vacuum (50-100 mbar) using a rotary evaporator at 60 °C.
  • the obtained material was dried at 60 °C in air for 2 h.
  • the dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 550 °C (heating rate of 2 °C/min), followed by an isothermal step at 550 °C for 4 h under synthetic air flow (200 mL/min).
  • the dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 350 °C (heating rate of 2 °C/min), followed by an isothermal step at 350 °C for 4 h under nitrogen flow (200 mL/min).
  • Silver oxalate (Ag2C2C>4) was used as silver precursor.
  • Ag2C2C>4 To synthesize Ag2C2C>4, 5.0 g of silver nitrate (AgNOs, Sigma Aldrich, > 99.0%) and 7.0 g of oxalic acid dihydrate (HO2CCO2H-2H2O, Sigma Aldrich, > 99.0 %) were dissolved in 100 mL of M illiQ water and the mixture was stirred for 15 minutes. The solid precipitated was recovered by filtration and washed with 1 L of MilliQ water. The filter containing the Ag2C2O4 material was dried overnight at 80 °C and the solid recovered and kept under a protective Ar atmosphere until use.
  • AgNOs silver nitrate
  • HO2CCO2H-2H2O oxalic acid dihydrate
  • the dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 350 °C (heating rate of 2 °C/min), followed by an isothermal step at 350 °C for 4 h under nitrogen flow (200 mL/min).
  • Ni-Mo-ZnOx/y-AhOs catalyst was synthesized as described in Example 1 of CN 101927168 A.
  • a first step 2.4 g of aluminium oxide, produced by calcination of a pseudo-boehmite powder (DISPERAL HP14, Sasol Materials, Germany) at 550 °C in a muffle furnace without convection in an air atmosphere.
  • the resulting support material was dried in a round-bottom multi-necked flask at a temperature of 200 °C under dynamic vacuum provided by a vacuubrand-MZ-2C-NT membrane pump for 4 hours.
  • the material obtained was subjected to a drying treatment in a packed-bed tubular reactor under nitrogen flow (200 ml/min) at 70 °C for 10 hours, followed by a calcination treatment in the same reactor, and under the same nitrogen flow, by heating from 70 °C to 350 °C (heating rate of 2 K/min) and an isothermal stage at 350 °C lasting 3 hours.
  • a 316 L stainless steel tubular reactor was used having 7.8 mm internal diameter, equipped with an external coiled heating element of 600 W power, controlled by a PID controller, and a type K thermocouple coated with a 316 L stainless steel sheath inserted axially in the catalyst bed.
  • Catalyst samples were press-conformed as pellets, the pellets disaggregated in a mortar with a pestle and particles in the size range of 200 to 400 pm recovered by means of sieving.
  • the catalyst particles were diluted with silicon carbide granules (SiC, Fisher Chemical, mean granule size about 696 pm) previously sieved to retain particles in the size range 600 - 800 pm, in order to increase the overall thermal conductivity of the packed beds in the reactor.
  • the SiC-diluted catalysts were loaded into the tubular reactor in the form of either a single packed-bed (loading scheme I according to Figure 1 a)), two (loading scheme II according to Figure 1 b)) or three (loading scheme III according to Figure 1 c)) axially arranged, consecutive packed beds as shown in Figure 1.
  • Individual packed beds were spaced by quartz wool blocks (3 mm thickness, axially). The overall volume of the packed beds was about 6 mL.
  • catalysts Prior to the catalytic testing, catalysts were subjected to an in situ activation treatment, i.e. in the tubular reactor itself.
  • This activation treatment consisted of two steps. In a first step, the reactor was heated from room temperature to 325 °C (with a temperature ramp of 3 °C/min) under N2 (Abello-Linde, 99.999 %) flow of approximately 50 mL/min, followed by an isothermal step at 325 °C for 3 hours, and cooling to room temperature.
  • the reactor was heated from room temperature to 250 °C (with a temperature ramp of 3 °C/min) under a mixed flow of H2 (Abello- Linde, 99.999 %, 20 mL/min) and N2 (Abello-Linde, 99.999 %, 50 mL/min), followed by an isothermal step at 250 °C for 3 hours, and cooling to room temperature.
  • H2 Abello- Linde, 99.999 %, 20 mL/min
  • N2 Abello-Linde, 99.999 %, 50 mL/min
  • a gas stream containing DME/CO/Fh/Ar in molar ratios 1/45/45/9 was fed from pressurized cylinders into the reactor and the reactor was pressurized to the desired operation pressure by means of a membrane back-pressure regulating valve (Swagelok) located downstream of the reactor.
  • the flow rate of the DME/CO/Fh/Ar stream was adjusted to obtain the desired gas space velocity (GHSV) and the reactor temperature was increased to the selected operation temperature following a heating ramp of 3 °C/min.
  • the outlet stream from the tubular reactor was depressurized at the pressure control valve and periodically analyzed in an Agilent 7890 gas chromatograph located on-line, downstream of the reactor, and equipped with two analysis channels.
  • a first channel is equipped with a packed column HayeSep R 80/100 (6 ft), a capillary column HP- PLOT-Q 30m (20 pm film thickness) and a capillary column molecular sieve HP-PLOT 5A 30m (12 pm film thickness) and two TCD detectors for the analysis of permanent gases and carbon dioxide.
  • a second analysis channel is equipped with a capillary column DB 1-MS (60 m) and a FID detector for the analysis of organic hydrocarbon and oxygenated compounds.
  • examples 13.1-13.4 which are according to the present invention, lead to a process with high selectivity to C3 oxygenate products, and particularly 2-pronanol.
  • Comparative Examples 13.5-13.7 which are not according to the present invention, the selectivity to 2-propanol is essentially null.
  • the results illustrate the technical effect of high selectivity to 2-propanol for a process in accordance with the present invention.
  • Figure 1 shows schematic drawings for different configurations of catalyst packed-beds in a tubular reactor, wherein in a) a single packed bed loading scheme I is shown, in b) a two packed beds loading scheme II, and in c) a three packed beds loading scheme III, wherein the arrows indicate the direction of the gas flow through the reactor.

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Abstract

The present invention relates to a process for producing 2-propanol, the process comprising (i) providing a reactor comprising one or more carbonylation catalysts C1, one or more ketonization catalysts C2, and one or more catalysts C3, wherein each of the one or more catalysts C3 independently from one another comprise one or more metals M3 and a support material S3, wherein the one or more metals M3 are supported on the support material S3, and wherein the one or more metals M3 are selected from the group consisting of Cu, Ag, Au, Pd, Pt, and mix tures of two or more thereof; (ii) preparing a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof; (iii) feeding the gas stream into the reactor and contacting the gas stream with the one or more carbonylation catalysts C1, the one or more ketonization catalysts C2, and the one or more catalysts C3, obtaining a product gas stream.

Description

Process for producing 2-propanol
TECHNICAL FIELD
The present invention relates to a process for producing 2-propanol by converting a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof, wherein the oxygenate preferably is dimethyl ether.
INTRODUCTION
2-propanol (isopropanol) is an important commodity chemical which finds applications as solvent, precursor for the production of polymers such as polyacrylates and polyolefins, denaturing agent for ethanol (ethyl alcohol), component in cosmetics and as disinfectant, among other.
2-propanol can be used as a precursor for the production of propylene via dehydration thereof, but it can also be produced from propylene which is currently done largely. According to common methods, 2-propanol can be produced by an indirect hydration process which involves esterification and hydrolysis reactions in concentrated sulfuric acid. Further, 2-propanol can be produced by a direct propylene hydration with either liquid or solid acid catalysts. Gehrmann and Tenhumberg disclose a study on the “Production and Use of Sustainable C2-C4 Alcohols - An Industrial Perspective” in Chemie Ingenieur Technik, Volume 92, 2020, pages 1444-1458. In said publication, an overview is provided on these methods for 2-propanol production. Alternatively, 2-propanol can also be produced from acetone, via hydrogenation of the carbonyl group, as described, e.g. in documents US 6930213 B1 , US 7041857 B1 , US 2013/0035517 A1 and ON 112403510 A.
EP 2590922 B1 relates to a process for the preparation of ethanol and higher alcohols. According to claim 1 , said process particularly comprises the steps of providing an alcohol synthesis gas comprising carbon monoxide and hydrogen; adding methanol; converting the resulting synthesis gas mixture in presence of one or more catalysts to ethanol and/or higher alcohols. In the examples, a potassium carbonate promoted catalyst containing metallic copper, zinc oxide and aluminum oxide is disclosed.
ON 104892361 A relates to a method for catalytically converting methanol to propanol. According to claim 1 , said method is particularly characterized in that methanol is used as a raw material, and a composite of two or more elements containing iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium supported by molecular sieve is used.
EP 2173694 B1 relates to a method of producing C2-C4 alcohols, the method particularly comprising introducing syngas into a first reaction zone with a first catalyst and thereby producing methanol; introducing said syngas and methanol into a second reaction zone comprising at least a second catalyst and converting it to ethanol, 1 -propanol and 1 -butanol. There is an increasing interest for processes for the production of isopropanol from alternative carbon sources, so that its production is decoupled from the availability of resources with a high demand and or high carbon footprint, such as propylene. Generally, monocarbonated (C1) platform compounds, such as methanol, dimethyl ether and CO, are an interesting alternative as a carbon source for 2-propanol production.
Synthesis gas, commonly abbreviated as "syngas", is a mixture composed of carbon monoxide (CO), hydrogen (H2) and, in some cases, also carbon dioxide (CO2) as main components. Synthesis gas streams might additionally comprise other gases such as nitrogen (N2), helium (He), argon (Ar), water steam (H2O), or light hydrocarbons such as methane (CH4), ethane (C2H6), propane (CsHs), which do not alter the reactivity of the major components to a significant extent. Syngas can be obtained from a wide array of carbonaceous sources, for example, by steam reforming or partial oxidation of natural or shale gas, gasification of coal, gasification and/or reforming of biomass, hydrogenation of carbon dioxide, by waste gasification, for instance of municipal waste, or the co-electrolysis of CO2 and water, among other.
Methanol can be obtained directly from synthesis gas by the catalytic process known as methanol synthesis. An overview of existing catalysts and processes for the direct production of methanol from synthesis gas is presented in J. P. Lange, "Methanol synthesis: a short review of technology improvements", Catalysis Today, Volume 64, Issues 1-2, 2001 , pages 3-8.
Dimethyl ether (DME), can also be produced from synthesis gas by combining the methanol synthesis and subsequent methanol dehydration, either in two consecutive reaction steps, or in a single conversion step, as described e.g. in A. Schafer et al. US 9295978 B2, and Saravanan et al. “Recent progress for direct synthesis of dimethyl ether from syngas on the heterogeneous bifunctional hybrid catalysts”, Applied Catalysis B: Environmental, Volume 217, 2017, pages 494-522. Both methanol and its derivative DME are formally C1 compounds which may be obtained from syngas.
Furthermore, WO 2022/144480 A1 discloses a process for the production of acetone by contacting a gas mixture comprising at least synthesis gas, with a multicomponent catalyst.
It was an object of the present invention to provide an improved process for producing 2-propa- nol, which particularly allows for a facile reaction control, and especially allows for using a reduced number of reactors. In particular, it was an object to provide a process for producing 2- propanol from readily accessible starting materials.
DETAILED DESCRIPTION Thus, it has surprisingly been found that a process for producing 2-propanol can be provided, wherein synthesis gas and an oxygenate are used as starting materials, and wherein the production of 2-propanol can be achieved in one reactor. Further, the oxygenate can also be produced from syngas. Further, it has been found that the inventive process does not require use of a solvent, and therefore product recovery does not entail its separation from a diluted liquid mixture. Yet another technical benefit is attained since the inventive process employs only solid, inorganic catalysts. Thus, it has been found that an improved process can be provided which can be operated in continuous mode and especially as gas-solid catalytic process. Thereby, catalyst handling and separation from the mixture of reactants and products can be simplified.
Therefore, the present invention relates to a process for producing 2-propanol, the process comprising
(i) providing a reactor comprising one or more carbonylation catalysts C1 , one or more ke- tonization catalysts C2, and one or more catalysts C3, wherein the one or more catalysts C3 independently from one another comprise one or more metals M3 and a support material S3, wherein the one or more metals M3 are supported on the support material S3, and wherein the one or more metals M3 are selected from the group consisting of Cu, Ag, Au, Pd, Pt, and mixtures of two or more thereof;
(ii) preparing a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof, wherein the oxygenate preferably is dimethyl ether;
(Hi) feeding the gas stream prepared according to (ii) into the reactor provided according to (i) and contacting the gas stream with the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, obtaining a product gas stream comprising 2-propanol.
It is preferred that the one or more carbonylation catalysts C1 are chemically different from the one or more ketonization catalysts C2.
It is preferred that the one or more carbonylation catalysts C1 are chemically different from the one or more catalysts C3.
It is preferred that the one or more ketonization catalysts C2 are chemically different from the one or more catalysts C3.
It is particularly preferred that the one or more carbonylation catalysts C1 are chemically different from the one or more ketonization catalysts C2, wherein the one or more carbonylation catalysts C1 are chemically different from the one or more catalysts C3, and wherein the one or more ketonization catalysts C2 are chemically different from the one or more catalysts C3.
It is preferred that the reactor provided according to (i) comprises m reaction zones Rk, with k = 1 , 2, 3,..., m, wherein each reaction zone Rk independently from one another comprises one or more catalysts selected from the group consisting of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, wherein, if m is equal to or greater than 2, each reaction zone Rk+i is arranged downstream of the reaction zone Rk.
In the case where the reactor provided according to (i) comprises m reaction zones Rk, with k = 1 , 2, 3,..., m, wherein each reaction zone Rk independently from one another comprises one or more catalysts selected from the group consisting of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, wherein, if m is equal to or greater than 2, each reaction zone Rk+i is arranged downstream of the reaction zone Rk, it is preferred according to a first alternative that m = 1.
Further in the case where the reactor provided according to (i) comprises m reaction zones Rk, with k = 1 , 2, 3,..., m, wherein each reaction zone Rk independently from one another comprises one or more catalysts selected from the group consisting of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, wherein, if m is equal to or greater than 2, each reaction zone Rk+i is arranged downstream of the reaction zone Rk, it is preferred according to a second alternative that m = 2 and wherein Ri comprises one or more of the one or more carbonylation catalysts C1 , and wherein R2 comprises one or more of the one or more catalysts C3.
In the case where m = 2 and wherein R1 comprises one or more of the one or more carbonylation catalysts C1 , and wherein R2 comprises one or more of the one or more catalysts C3, it is preferred that R1 or R2 comprises one or more of the one or more ketonization catalysts C2.
Further in the case where the reactor provided according to (i) comprises m reaction zones Rk, with k = 1 , 2, 3,..., m, wherein each reaction zone Rk independently from one another comprises one or more catalysts selected from the group consisting of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, wherein, if m is equal to or greater than 2, each reaction zone Rk+1 is arranged downstream of the reaction zone Rk, it is preferred according to a second alternative that m = 3, and wherein R3 is downstream of R2 and R2 is downstream of R1.
In the case where m = 3, and wherein R3 is downstream of R2 and R2 is downstream of R1, it is preferred that R1 comprises one or more of the one or more carbonylation catalysts C1 , wherein R2 comprises one or more of the one or more ketonization catalysts C2, and wherein R3 comprises one or more of the one or more catalysts C3.
It is preferred that the one or more carbonylation catalysts C1 are solid.
According to a first alternative, it is preferred that each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 . In the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , it is preferred that the one or more metals M1 are selected from the group consisting of Ag, Ga, Pd, Cu, In, Sn, Ir, Pt, Rh, Co, Re, Zn, and mixtures of two or more thereof, more preferably from the group consisting of Ag, Ga, Pd, and mixtures of two or more thereof, wherein the one or more metals M1 more preferably are Ag.
Further in the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , it is preferred that the one or more metals M1 are supported on the support material S1 at a loading in the range of from 0.001 to 50 weight-%, more preferably from 0.01 to 40 weight-%, more preferably from 0.1 to 30 weight-%, more preferably from 1 to 20 weight-%, more preferably from 4 to 17 weight-%, more preferably from 7 to 13 weight-%, more preferably from 9 to 11 weight-%, calculated as sum of the one or more metals M1 as elements and based on the sum of the weights of the one or more metals M1 as elements and the support material S1 .
Further in the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , it is preferred that the support material S1 comprises, more preferably consists of, one or more of a zeolitic material and a metal oxide, more preferably a zeolitic material.
In the case where the support material S1 comprises, more preferably consists of, one or more of a zeolitic material and a metal oxide, it is preferred that the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof.
According to a second alternative, it is preferred that each of the one or more carbonylation catalysts C1 , independently from one another, comprises, more preferably consists of, a zeolitic material, wherein the zeolitic material more preferably comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of a metal, calculated as element and based on the sum of the weights of the metal and the zeolitic material, wherein the zeolitic material more preferably is free of a metal, wherein the metal is selected from the group consisting of groups 3 to 12 of the periodic table of elements.
In the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material comprises SiO2 and AI2O3 in its framework structure, and wherein the zeolitic material more preferably has a SIC>2 : AI2O3 molar ratio in the range of from 3:1 to 100:1 , more preferably in the range of from 5:1 to 40:1 , more preferably in the range of from 8:1 to 30:1 , more preferably in the range of from 14:1 to 26:1 , more preferably in the range of from 17:1 to 23:1 .
In the case where the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, and wherein each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M 1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , wherein the support material S1 comprises, preferably consists of, one or more of a zeolitic material, it is preferred that each of the one or more carbonylation catalysts C1 , independently from one another, has an atomic ratio of the one or more metals M 1 , calculated as sum of the molar amounts of the one or more metals M 1 as elements, to Al comprised in the framework structure of the zeolitic material, calculated as molar amount of Al as element, in the range of 0.2:1 to 1.0:1 , more preferably in the range of 0.5:1 to 0.7:1.
Further in the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material has a framework structure comprising rings with 8 T- atoms, preferably rings with 8 T-atoms and rings with 10 or 12 T-atoms, more preferably rings with 8 T-atoms and rings with 12 T-atoms.
Further in the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material has a framework structure type selected from the group consisting of ABW, AEN, AFR, AFV, APC, APD, ATN, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BIK, BRE, CAS, CDO, CFG, CSV, CZP, DAC, DDR, EAB, EEI, EON, EPI, ESV, ETL, EZT, FER, HEU, IHW, IRN, ITE, ITW, JBW, JNT, JSN, JSW, LEV, MAZ, MFS, MOR, MRT, MTF, NSI, OWE, PAR, PCR, PCS, PSI, PTY, PWW, RRO, RTE, RTH, RWR, SAS, SFO, STI, UEI, UFI, VET, YUG, ZON, ACO, AEI, AFN, AFS, AFT, AFX, AFY, ANA, BOZ, BPH, CGS, CHA, CLO, DFO, DFT, EDI, ERI, ETR, ETV, GIS, GME, GOO, IFU, IFW, IFY, IWW, JOZ, KFI, LIT, LOV, LTA, LTF, LYJ, LTL, MEL, MER, MON, MOZ, MWF, NAB, NAT, NPT, OBW, OFF, OSO, PAU, PHI, POR, PUN, PWN, RHO, RSN, RWY, SAT, SAV, SBE, SBN, SBS, SBT, SFV, SFW, SIV, SOR, SOS, STW, SWY, SYT, SZR, THO, TSC, TUN, UOE, USO, UOV, VNI, VSV, WEI, WEN, YFI, and mixed structures composed of two or more thereof, more preferably selected from the group consisting of MOR, ETL, FER, CHA, SZR, and mixed structures composed of two or more thereof, wherein the zeolitic material more preferably has the MOR-type framework structure type.
In the case where the zeolitic material has the MOR-type framework structure type, it is preferred that the zeolitic material is selected from the group consisting of Mordenite, [Ga-Si-O]- MOR, Maricopaite, Ca-Q, LZ-211 , Na-D, RMA-1 , including mixtures of two or more thereof, wherein more preferably the zeolitic material having a MOR-type framework structure comprises, more preferably consists of, Mordenite.
Further in the case where each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , as defined for the first alternative, or where each of the one or more carbonylation catalysts C1 , independently from one another, comprises, optionally consists of, a zeolitic material, as defined for the second alternative, it is preferred that the zeolitic material is in the H-form or in the NFU-form, preferably in the H-form.
It is preferred that the one or more carbonylation catalysts 01 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S1 , wherein the one or more carbonylation catalysts 01 more preferably are free of Zn.
It is preferred that the one or more carbonylation catalysts 01 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S1 , wherein the one or more carbonylation catalysts 01 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
It is preferred that the one or more ketonization catalysts C2 are solid.
It is preferred that each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2. Alternatively, it is preferred that each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more of ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, more preferably from the group consisting of ceria, zirconia, ceria-zirconia, and mixtures of two or more thereof, wherein each of the one or more ketonization catalysts more preferably are ceria-zirconia. In the case where each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2, it is preferred that the one or more metals M2 are selected from the group consisting of Pd, Pt, Ag, Fe, Ru, Os, Co, Rh, Ir, N I, Cu, Au, and mixtures of two or more thereof, more preferably from the group consisting of Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M2 more preferably are Pd.
Further in the case where each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2, it is preferred that each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, wherein each of the one or more ketonization catalysts C2 independently from one another more preferably comprises, more preferably consists, of the one or more metals M2, the support material S2 and the zeolitic material.
In the case where each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, it is preferred that the one or more metals M2 are supported on the support material S2 at a loading in the range of from 0.01 to 0.50 weight-%, preferably from 0.02 to 0.20 weight-%, more preferably from 0.03 to 0.12 weight-%, more preferably from 0.04 to 0.09 weight-%, more preferably from 0.05 to 0.07 weight-%, calculated as sum of the one or more metals M2 as elements and based on the sum of the weights of the one or more metals M2, the support material S2 and the zeolitic material.
Further in the case where each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, it is preferred that the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, and wherein the zeolitic material preferably has a SiC>2 : AI2O3 molar ratio in the range of from 1 :1 to 200:1 , more preferably in the range of from 5:1 to 100:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 15:1 to 25:1 , more preferably in the range of from 18:1 to 22:1.
Further in the case where each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, it is preferred that the zeolitic material has a framework structure comprising rings with 10 T-atoms, wherein the rings comprised in the framework structure are more preferably selected from the group consisting of rings with equal to or less than 10 T-atoms.
Further in the case where each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, it is preferred that the zeolitic material has a framework structure type selected from the group consisting of CSV, DAC, ETV, EUO, EWO, FER, HEU, IMF, ITH, LAU, -LIT, MEL, MFI, MFS, MTT, MWW, NES, -PAR, PCR, PTY, PWW, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TON, TUN, -WEN, and mixed structures composed of two or more thereof, more preferably selected from the group consisting of FER, MFI, MWW, and mixed structures composed of two or more thereof, wherein the zeolitic material more preferably has the FER-type framework structure type.
In the case where the zeolitic material has the FER-type framework structure type, it is preferred that the zeolitic material is selected from the group consisting of Ferrierite, [Ga-Si-O]-FER, [Si- O]-FER, FU-9, ISI-6, NU-23, Sr-D, ZSM-35, and [B-Si-O]-FER, including mixtures of two or more thereof, more preferably from the group consisting of Ferrierite, FU-9, ISI-6, NU-23, and ZSM-35, including mixtures of two or more thereof, wherein more preferably the zeolitic material having a FER-type framework structure comprises, more preferably consists of, Ferrierite.
Further in the case where each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material, it is preferred that the zeolitic material is in the Flform .
Further in the case where each of the one or more ketonization catalysts 02 independently from one another comprises a zeolitic material, it is preferred that each of the one or more ketonization catalysts 02 independently from one another has a mass ratio of the zeolitic material, calculated as weight of the zeolitic material, to the one or more metals M2 and the support material S2, calculated as sum of the weights of the one or more metals M2 as elements and the support material S2, in the range of from 1 :200 to 1 :1 , more preferably in the range of from 1 :100 to 1 :2, more preferably in the range of from 1 :20 to 1 :5, more preferably in the range of from 1 :12 to 1 :7.
Further in the case where each of the one or more ketonization catalysts C2 independently from one another comprises, more preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2, it is preferred that the support material S2 comprises, more preferably consists of, a metal oxide.
In the case where the support material S2 comprises, more preferably consists of, a metal oxide, it is preferred that the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, more preferably from the group consisting of ceria, zirconia, ceria-zirconia, and mixtures of two or more thereof, wherein the metal oxide more preferably is ceria-zirconia.
In the case where the metal oxide comprises, preferably consists of, ceria-zirconia, it is preferred that the ceria-zirconia has a Ce:Zr molar ratio in the range of from 1 :1 to 5:1 , more preferably in the range of from 1.5:1 to 2.5:1 , more preferably in the range of from 1.7:1 to 2.3:1 , more preferably in the range of from 1.9:1 to 2.1 :1. It is preferred that the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Zn.
It is preferred that the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
It is preferred that the one or more catalysts C3 are solid.
It is preferred that the one or more metals M3 are selected from the group consisting of Ag, Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M3 more preferably are Ag, a mixture of Ag and Pt, or a mixture of Ag and Pd, wherein the one or more metals M3 more preferably are Ag.
It is preferred that each of the one or more catalysts C3 further comprise one or more co-cata- lyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, wherein each of the one or more catalysts C3 preferably displays an atomic ratio of the one or more metals M3, calculated as elements, to the one or more co-catalyst metals, calculated as elements, of less than 10:1 .
It is preferred that the one or more metals M3 comprise, more preferably consists of, a mixture of Ag and Pt, wherein each of the one or more catalysts C3 more preferably display an atomic ratio of Ag, calculated as element, to Pt, calculated as element, in the range of from 5:1 to 50:1 , more preferably in the range of from 10:1 to 28:1 , more preferably in the range of from 15:1 to 23:1 , more preferably in the range of from 18:1 to 20:1.
In the case where each of the one or more catalysts C3 further comprise one or more co-cata- lyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, it is preferred according to a first alternative that the one or more metals M3 comprise, preferably consist of, Pd and wherein the one or more co-catalyst metals comprise, more preferably consist of, In, wherein the one or more catalysts C3 preferably display an atomic ratio of Pd, calculated as element, to In, calculated as element, in the range of from 1 :2 to 10:1 , more preferably in the range of from 1 :1 to 3:1 , more preferably in the range of from 1.5:1 to 2.5:1 , more preferably in the range of from 1.9:1 to 2.1 :1.
In the case where each of the one or more catalysts C3 further comprise one or more co-cata- lyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, it is preferred according to a second alternative that the one or more metals M3 comprise, preferably consist of, Pt and wherein the one or more co-catalyst metals comprise, preferably consist of, Sn, wherein the one or more catalysts C3 preferably display an atomic ratio of Pt, calculated as element, to Sn, calculated as element, in the range of from 0.05:1 to 5:1 , more preferably in the range of from 0.1 :1 to 2:1 , more preferably in the range of from 0.2:1 to 1.0:1 , more preferably in the range of from 0.5:1 to 0.7:1.
It is preferred that the one or more metals M3 are supported on the support material S3 at a loading in the range of from 0.2 to 50.0 weight-%, more preferably in the range of from 1 .0 to 40 weight-%, more preferably in the range of from 1.5 to 30 weight-%, more preferably in the range of from 2.0 to 20 weight-%, more preferably in the range of from 2.5 to 10 weight-%, more preferably in the range of from 3.0 to 5.0 weight-%, calculated as sum of the one or more metals M3 as elements and based on the sum of the weights of the one or more metals M3 and the support material S3.
It is preferred that the support material S3 comprises, preferably consists of, one or more of a transitional alumina, a-alumina, silica, titania, carbon, and silicon carbide, preferably one or more of a-alumina, silica, carbon and silicon carbide, wherein the support material S3 more preferably comprises, more preferably consists of, a-alumina or silica, more preferably a-alu- mina.
It is preferred that the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of y-alumina, wherein the one or more catalysts C3 are more preferably free of y-alumina.
It is preferred that the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Ni, calculated as element and based on the sum of the weights of the Ni, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Ni.
It is preferred that the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Mo, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Mo, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Mo. It is preferred that the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Zn, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Zn.
It is preferred that the one or more catalysts C3 comprise from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, more preferably of one or more of Cu and Pd, calculated as sum of the weights of one or more of Pd and Cu, respectively, as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
It is preferred that each of the one or more carbonylation catalysts C1 , the one or more keton- ization catalysts C2, and the one or more catalysts C3, independently from one another is comprised in a packed-bed.
It is preferred that the gas stream prepared according to (II) has a molar ratio of CO to H2 in the range of from 0.1 :1 to 10:1 , more preferably in the range of from 0.2:1 to 5:1 , more preferably in the range of from 0.3:1 to 2.5:1 , more preferably in the range of from 0.4:1 to 1.3:1 , more preferably in the range of from 0.5:1 to 1.1 :1.
It is preferred that the gas stream prepared according to (II) has a molar ratio of CO to the oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, in the range of from 1 :1 to 100:1 , more preferably in the range of from 2:1 to 80:1 , more preferably in the range of from 5:1 to 60:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 20:1 to 47:1.
It is preferred that the gas stream prepared according to (II) has a molar ratio of H2 to oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, in the range of from 10:1 to 100:1 , more preferably in the range of from 20:1 to 80:1 , more preferably in the range of from 30:1 to 60:1 , more preferably in the range of from 40:1 to 50:1 , more preferably in the range of from 43:1 to 47:1.
It is preferred that the gas stream prepared according to (II) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof.
In the case where the gas stream prepared according to (II) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof, it is preferred that the gas stream prepared according to (ii) has a molar ratio of CO to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 50:1 , more preferably in the range of from 1 :1 to 20:1 , more preferably in the range of from 2:1 to 10:1 , more preferably in the range of from 3:1 to 7:1 , more preferably in the range of from 4:1 to 6:1 .
Further in the case where the gas stream prepared according to (ii) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof, it is preferred that the gas stream prepared according to (ii) has a molar ratio of H2 to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 500: 1 , more preferably in the range of from 1 :1 to 200:1 , more preferably in the range of from 2:1 to 100:1 , more preferably in the range of from 3:1 to 50:1 , more preferably in the range of from 4:1 to 25:1.
Further in the case where the gas stream prepared according to (ii) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof, it is preferred that the gas stream prepared according to (ii) has a molar ratio of the oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :50 to 50:1 , more preferably in the range of from 1 :25 to 20:1 , more preferably in the range of from 1 :20 to 10:1 , more preferably in the range of from 1 :15 to 1 :1 , more preferably in the range of from 1 :10 to 1 :5.
It is preferred that the gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C2-C6)alkene, more preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 vol- ume-% of a (C2-C6)alkene, preferably of one or more of ethylene, propylene, and butylene, more preferably of propylene.
It is preferred that the gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C3-C6)ketone, more preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 vol- ume-% of a (C3-C6)ketone, preferably of acetone.
It is preferred that the gas stream prepared according to (ii) is obtained from biosyngas.
It is preferred that the reactor comprises an inlet end and an outlet end, and an axial length extending from the inlet end to the outlet end.
It is preferred that the reactor has a volume in the range of from 50 to 1000 I, preferably in the range of from 250 to 400 I, more preferably in the range of from 300 to 330 I.
It is preferred that contacting according to (iii) comprises heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 to a temperature in the range of from 100 to 400 °C, more preferably in the range of from 150 to 400 °C, more preferably in the range of from 200 to 350 °C, more preferably in the range of from 240 to 310 °C, more preferably in the range of from 260 to 290 °C, more preferably in the range of from 270 to 280 °C.
It is preferred that the gas stream prepared according to (ii) is contacted according to (iii) with the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 at a pressure in the range of from 1 to 200 bar(abs), more preferably in the range of from 5 to 150 bar(abs), more preferably in the range of from 5 to 35 bar(abs), more preferably in the range of from 10 to 30 bar(abs), more preferably in the range of from 12 to 28 bar(abs), more preferably in the range of from 16 to 24 bar(abs), more preferably in the range of from 18 to 22 bar(abs), more preferably in the range of from 19 to 21 bar(abs).
It is preferred that the gas stream prepared according to (ii) is fed into the reactor according to (iii) with a gas hourly space velocity in the range of from 10 to 1000 IT1 , more preferably in the range of from 100 to 300 IT1 , more preferably in the range of from 150 to 250 IT1 , more preferably in the range of from 190 to 210 IT1 , more preferably in the range of from 194 to 203 IT1.
It is preferred that the process further comprises a heat treatment after (ii) and prior to (iii), wherein the heat treatment more preferably comprises
(a.1 ) feeding a gas stream comprising, preferably consisting of, one or more inert gases selected from the group consisting of Ar, N2, and mixtures of two or more thereof, preferably N2, into the reactor provided according to (i);
(a.2) heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) to a temperature in the range of from 250 to 400 °C, preferably in the range of from 300 to 350 °C.
In the case where the process further comprises a heat treatment after (ii) and prior to (iii), wherein the heat treatment more preferably comprises (a.1 ) and (a.2), it is preferred that heating according to (a.2) is performed for a period in the range of from 1 to 5 h, more preferably in the range of from 2 to 4 h.
It is preferred that the process further comprises a catalyst activation after (ii) or after the heat treatment according to any one of the embodiments disclosed herein, and prior to (iii), wherein the catalyst activation comprises
(b.1 ) feeding a gas stream comprising, preferably consisting of, H2 and one or more inert gases selected from the group consisting of Ar, N2, and mixtures of two or more thereof, preferably N2, into the reactor provided according to (i);
(b.2) heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) to a temperature in the range of from 175 to 325 °C, preferably in the range of from 225 to 275 °C. (b.3) contacting the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) with the gas stream fed into the reactor according to (b.1).
In the case where the process further comprises a catalyst activation after (ii) or after the heat treatment according to any one of the embodiments disclosed herein, and prior to (iii), it is preferred that the gas stream is fed according to (b.1) into the reactor has a volume ratio of H2 to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases in the range of from 0.1 :1 to 1 :1 , more preferably in the range of from 0.3:1 to 0.5:1.
Further in the case where the process further comprises a catalyst activation after (ii) or after the heat treatment according to any one of the embodiments disclosed herein, and prior to (iii), it is preferred that heating according to (b.2) is performed for a period in the range of from 1 to 5 h, more preferably in the range of from 2 to 4 h.
It is preferred that the process is a continuous process or a batch process, more preferably a continuous process.
It is preferred that the process further comprises prior to (i)
(A) preparing a gas stream comprising H2, CO, and optionally CO2;
(B) contacting the gas stream prepared according to (A) with a catalyst, for obtaining a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof.
Suitable catalysts are disclosed for example in J. P. Lange, "Methanol synthesis: a short review of technology improvements", Catalysis Today, Volume 64, Issues 1-2, 2001 , pages 3-8, US9295978B2, and Saravanan et al. “Recent progress for direct synthesis of dimethyl ether from syngas on the heterogeneous bifunctional hybrid catalysts”, Applied Catalysis B: Environmental, Volume 217, 2017, pages 494-522.
In the case where the process further comprises (A) and (B) prior to (i), it is preferred that according to (A) the gas stream comprises H2 in an amount in the range of from 25 to 95 vol.-%, more preferably of from 50 to 92 vol.-%, more preferably of from 60 to 90 vol.-%, and more preferably of from 60 to 75 vol.-%.
Further in the case where the process further comprises (A) and (B) prior to (i), it is preferred that according to (A) the gas stream comprises CO2 in an amount of equal to or less than 60 vol.-%, more preferably of equal to or less than 50 vol.-%, more preferably of equal to or less than 40 vol.-%, more preferably of equal to or less than 30 vol.-%, more preferably of equal to or less than 25 vol.-%, and more preferably of equal to or less than 22, wherein more preferably the gas stream comprises CO2 in an amount in the range of froml to 22 vol.-%, more preferably in the range of from 5 to 21 vol.-%, more preferably in the range of from 10 to 20 vol.-%, and more preferably in the range of from 15 to 19 vol.-%. Further in the case where the process further comprises (A) and (B) prior to (i), it is preferred that according to (A) the gas stream further comprises CO, more preferably in an amount in the range from 0.5 to 40 vol.-%, more preferably in the range of from 1 to 33 vol.-%, more preferably in the range of from 2 to 20 vol.-%, more preferably in the range of from 3 to 10 vol.-%, and more preferably in the range of from 5 to 8 vol.-%.
Further in the case where the process further comprises (A) and (B) prior to (i), it is preferred that according to (A) the gas stream further comprises one or more inert gases, more preferably in an amount in the range of from 0.1 to 40 vol.-%, more preferably in the range of from 0.5 to 30 vol.-%, more preferably in the range of from 1 to 20 vol.-%, and more preferably in the range of from 2 to 15 vol.-%.
In the case where according to (A) the gas stream further comprises one or more inert gases, it is preferred that the one or more inert gases are selected from the group consisting of He, Ar, Ne, CH4, N2, and mixtures of two or more thereof, more preferably from the group consisting of Ar, CH4, N2, and mixtures of two or more thereof, wherein the one or more inert gases more preferably are CH4 and N2.
Further in the case where the process further comprises (A) and (B) prior to (i), it is preferred that contacting according to (B) is conducted at a temperature in the range of from 200 to 400 °C, more preferably in the range of from 250 to 350 °C, and more preferably in the range of from 270 to 330 °C.
Further in the case where the process further comprises (A) and (B) prior to (i), it is preferred that contacting according to (B) is conducted at a pressure of 100 bar(abs) or less, more preferably in the range of from 50 to 95 bar(abs), more preferably in the range of from 60 to 90 bar(abs), and more preferably in the range of from 70 to 80 bar(abs).
Further in the case where the process further comprises (A) and (B) prior to (i), it is preferred that contacting according to (B) is conducted in a continuous mode, more preferably in a recycle mode, after separation of the high boiling products dimethylether and methanol.
In the case where contacting according to (B) is conducted in a continuous mode, more preferably in a recycle mode, after separation of the high boiling products dimethylether and methanol, it is preferred that contacting according to (B) is conducted in a continuous mode at a gas hourly space velocity in the range of from 500 to 24,000 IT1 , more preferably in the range of from 1000 to 8000 IT1 , and more preferably in the range of from 2000 to 6000 IT1.
It is preferred that the process further comprises after (iii)
(iv) recovering 2-propanol from the product gas stream obtained according to (iii). It is preferred that the process is for the production of 2-propanol and one or more of methyl acetate and acetone.
It is preferred that the product gas stream obtained according to (iii) further comprises one or more of methyl acetate and acetone.
In the process of the present invention, three catalysts are used, i.e. a carbonylation catalyst, a ketonization catalyst and a further catalyst. The carbonylation and ketonization catalysts are defined with respect to their purpose, indicating that the respective catalyst is suitable for its specific purpose being catalyzing a carbonylation reaction or a ketonization reaction. Said catalysts can be identical to each other or differ in their physical or chemical nature.
The term "carbonylation" as used in the context of the present invention is understood to mean a reaction in which a carboxylic compound, that is a carboxylic acid or a carboxylic ester, is formed from an alcohol compound or an ether compound, and carbon monoxide. A carbonylation catalyst according to the present invention is the catalyst which catalyses this type of reaction.
The term "ketonization" as used in the context of the present invention is understood to mean a reaction in which a ketone-type compound, also together with carbon dioxide and water, is produced by condensation of two carboxylic compounds or by self-condensation of a single carboxylic compound. A ketonization catalyst according to the present invention is the catalyst which catalyzes this type of reaction.
In the context of the present invention the term “chemically different” with respect to a catalyst being chemically different to another catalyst indicates that the former catalyst has one or more chemical features distinguishing it from the latter. Said one or more chemical features include any chemical features with respect to the nature of elements comprised by said catalysts, the molar composition of elements comprised by said catalysts, the electronic structure of the bonds between the elements comprised by said catalysts, and the spatial arrangement of the elements comprised by said catalysts. In this connection the electronic structure of bonds relates to the type of bond particularly including covalent bonds, ionic bonds, metallic bonds and coordinate covalent bonds. Preferably, the term “chemically different” with respect to a catalyst being chemically different to another catalyst indicates that the former catalyst differs from the latter in the chemical composition.
In the context of the present invention, the term "inert gas", or “inert gases” for a plurality, is understood to mean a compound which, under a specific set of operational conditions of the inventive process, or under a specific set of operational conditions of catalyst preparation and activation therefor, does not undergo chemical transformation and it does not modify to any significant extent the reactivity of other compounds, concomitantly present. In the context of the present invention, gaseous compounds selected from the list of nitrogen (N2), helium (He), argon (Ar), and light alkanes such as methane (CH4), ethane (C2H6), propane (CsHs), and any mixtures thereof, are considered inert gases.
The unit bar(abs) refers to an absolute pressure of 105 Pa and the unit angstrom refers to a length of 10’10 m.
The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The process of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1 , 2, 3, and 4". Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.
1 . A process for producing 2-propanol, the process comprising
(i) providing a reactor comprising one or more carbonylation catalysts C1 , one or more ketonization catalysts C2, and one or more catalysts C3, wherein the one or more catalysts C3 independently from one another comprise one or more metals M3 and a support material S3, wherein the one or more metals M3 are supported on the support material S3, and wherein the one or more metals M3 are selected from the group consisting of Cu, Ag, Au, Pd, Pt, and mixtures of two or more thereof;
(ii) preparing a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof, wherein the oxygenate preferably is dimethyl ether;
(iii) feeding the gas stream prepared according to (ii) into the reactor provided according to (i) and contacting the gas stream with the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, obtaining a product gas stream comprising 2-propanol.
2. The process of embodiment 1 , wherein the one or more carbonylation catalysts C1 are chemically different from the one or more ketonization catalysts C2.
3. The process of embodiment 1 or 2, wherein the one or more carbonylation catalysts C1 are chemically different from the one or more catalysts C3.
4. The process of any one of embodiments 1 to 3, wherein the one or more ketonization catalysts C2 are chemically different from the one or more catalysts C3.
5. The process of any one of embodiments 1 to 4, wherein the one or more carbonylation catalysts C1 are chemically different from the one or more ketonization catalysts C2, wherein the one or more carbonylation catalysts C1 are chemically different from the one or more catalysts C3, and wherein the one or more ketonization catalysts C2 are chemically different from the one or more catalysts C3.
6. The process of any one of embodiments 1 to 5, wherein the reactor provided according to (i) comprises m reaction zones Rk, with k = 1 , 2, 3,..., m, wherein each reaction zone Rk independently from one another comprises one or more catalysts selected from the group consisting of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3; wherein, if m is equal to or greater than 2, each reaction zone Rk+i is arranged downstream of the reaction zone Rk.
7. The process of embodiment 6, wherein m = 1.
8. The process of embodiment 6, wherein m = 2 and wherein Ri comprises one or more of the one or more carbonylation catalysts C1 , and wherein R2 comprises one or more of the one or more catalysts C3.
9. The process of embodiment 8, wherein R1 or R2 comprises one or more of the one or more ketonization catalysts C2.
10. The process of embodiment 6, wherein m = 3, and wherein R3 is downstream of R2 and R2 is downstream of R1.
11 . The process of embodiment 10, wherein R1 comprises one or more of the one or more carbonylation catalysts C1 , wherein R2 comprises one or more of the one or more ketonization catalysts C2, and wherein R3 comprises one or more of the one or more catalysts C3.
12. The process of any one of embodiments 1 to 11 , wherein the one or more carbonylation catalysts C1 are solid.
13. The process of any one of embodiments 1 to 12, wherein each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 .
14. The process of embodiment 13, wherein the one or more metals M1 are selected from the group consisting of Ag, Ga, Pd, Cu, In, Sn, Ir, Pt, Rh, Co, Re, Zn, and mixtures of two or more thereof, preferably from the group consisting of Ag, Ga, Pd, and mixtures of two or more thereof, wherein the one or more metals M1 more preferably are Ag. The process of embodiment 13 or 14, wherein the one or more metals M 1 are supported on the support material S1 at a loading in the range of from 0.001 to 50 weight-%, preferably from 0.01 to 40 weight-%, more preferably from 0.1 to 30 weight-%, more preferably from 1 to 20 weight-%, more preferably from 4 to 17 weight-%, more preferably from 7 to 13 weight-%, more preferably from 9 to 11 weight-%, calculated as sum of the one or more metals M1 as elements and based on the sum of the weights of the one or more metals M1 as elements and the support material S1 . The process of any one of embodiments 13 to 15, wherein the support material S1 comprises, preferably consists of, one or more of a zeolitic material and a metal oxide, preferably a zeolitic material. The process of embodiment 16, wherein the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof. The process of any one of embodiments 1 to 12, wherein each of the one or more carbonylation catalysts C1 , independently from one another, comprises, preferably consists of, a zeolitic material, wherein the zeolitic material preferably comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight- %, of a metal, calculated as element and based on the sum of the weights of the metal and the zeolitic material, wherein the zeolitic material more preferably is free of a metal, wherein the metal is selected from the group consisting of groups 3 to 12 of the periodic table of elements. The process of any one of embodiments 16 to 18, wherein the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, and wherein the zeolitic material preferably has a SiO2 : AI2O3 molar ratio in the range of from 3:1 to 100:1 , more preferably in the range of from 5:1 to 40:1 , more preferably in the range of from 8:1 to 30:1 , more preferably in the range of from 14:1 to 26:1 , more preferably in the range of from 17:1 to 23:1. The process of embodiment 19, wherein each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 , wherein the support material S1 comprises, preferably consists of, one or more of a zeolitic material, wherein the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, wherein each of the one or more carbonylation catalysts C1 , independently from one another, has an atomic ratio of the one or more metals M 1 , calculated as sum of the molar amounts of the one or more metals M1 as elements, to Al comprised in the framework structure of the zeolitic material, calculated as molar amount of Al as element, in the range of 0.2:1 to 1.0:1 , more preferably in the range of 0.5:1 to 0.7:1. The process of any one of embodiments 16 to 20, wherein the zeolitic material has a framework structure comprising rings with 8 T-atoms, preferably rings with 8 T-atoms and rings with 10 or 12 T-atoms, more preferably rings with 8 T-atoms and rings with 12 T-at- oms. The process of any one of embodiments 16 to 21 , wherein the zeolitic material has a framework structure type selected from the group consisting of ABW, AEN, AFR, AFV, APC, APD, ATN, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BIK, BRE, CAS, CDO, CFG, CSV, CZP, DAC, DDR, EAB, EEI, EON, EPI, ESV, ETL, EZT, FER, HEU, IHW, IRN, ITE, ITW, JBW, JNT, JSN, JSW, LEV, MAZ, MFS, MOR, MRT, MTF, NSI, OWE, PAR, PCR, PCS, PSI, PTY, PWW, RRO, RTE, RTH, RWR, SAS, SFO, STI, UEI, UFI, VET, YUG, ZON, ACO, AEI, AFN, AFS, AFT, AFX, AFY, ANA, BOZ, BPH, CGS, CHA, CLO, DFO, DFT, EDI, ERI, ETR, ETV, GIS, GME, GOO, IFU, IFW, IFY, IWW, JOZ, KFI, LIT, LOV, LTA, LTF, LYJ, LTL, MEL, MER, MON, MOZ, MWF, NAB, NAT, NPT, OBW, OFF, OSO, PAU, PHI, POR, PUN, PWN, RHO, RSN, RWY, SAT, SAV, SBE, SBN, SBS, SBT, SFV, SFW, SIV, SOR, SOS, STW, SWY, SYT, SZR, THO, TSC, TUN, UOE, USO, UOV, VNI, VSV, WEI, WEN, YFI, and mixed structures composed of two or more thereof, preferably selected from the group consisting of MOR, ETL, FER, CHA, SZR, and mixed structures composed of two or more thereof, wherein the zeolitic material more preferably has the MOR-type framework structure type. The process of embodiment 22, wherein the zeolitic material has the MOR-type framework structure type and wherein the zeolitic material is selected from the group consisting of Mordenite, [Ga-Si-O]-MOR, Maricopaite, Ca-Q, LZ-211 , Na-D, RMA-1 , including mixtures of two or more thereof, wherein more preferably the zeolitic material having a MOR- type framework structure comprises, more preferably consists of, Mordenite. The process of any one of embodiments 16 to 23, wherein the zeolitic material is in the H- form or in the NH4-form, preferably in the H-form. The process of any one of embodiments 1 to 24, wherein the one or more carbonylation catalysts C1 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S1 , wherein the one or more carbonylation catalysts C1 more preferably are free of Zn. The process of any one of embodiments 1 to 25, wherein the one or more carbonylation catalysts C1 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S1 , wherein the one or more carbonylation catalysts C1 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd. 27. The process of any one of embodiments 1 to 26, wherein the one or more ketonization catalysts C2 are solid.
28. The process of any one of embodiments 1 to 27, wherein each of the one or more ketonization catalysts C2 independently from one another comprises, preferably consists of, one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2.
29. The process of embodiment 28, wherein the one or more metals M2 are selected from the group consisting of Pd, Pt, Ag, Fe, Ru, Os, Co, Rh, Ir, Ni, Cu, Au, and mixtures of two or more thereof, preferably from the group consisting of Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M2 more preferably are Pd.
30. The process of embodiment 28 or 29, wherein each of the one or more ketonization catalysts C2 independently from one another further comprises a zeolitic material, wherein each of the one or more ketonization catalysts C2 independently from one another preferably comprises, more preferably consists, of the one or more metals M2, the support material S2 and the zeolitic material.
31 . The process of embodiment 30, wherein the one or more metals M2 are supported on the support material S2 at a loading in the range of from 0.01 to 0.50 weight-%, preferably from 0.02 to 0.20 weight-%, more preferably from 0.03 to 0.12 weight-%, more preferably from 0.04 to 0.09 weight-%, more preferably from 0.05 to 0.07 weight-%, calculated as sum of the one or more metals M2 as elements and based on the sum of the weights of the one or more metals M2, the support material S2 and the zeolitic material.
32. The process of embodiment 30 or 31 , wherein the zeolitic material comprises SiC>2 and AI2O3 in its framework structure, and wherein the zeolitic material preferably has a SIC>2 : AI2O3 molar ratio in the range of from 1 :1 to 200:1 , more preferably in the range of from 5:1 to 100:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 15:1 to 25:1 , more preferably in the range of from 18:1 to 22:1.
33. The process of any one of embodiments 30 to 32, wherein the zeolitic material has a framework structure comprising rings with 10 T-atoms, wherein the rings comprised in the framework structure are preferably selected from the group consisting of rings with equal to or less than 10 T-atoms.
34. The process of any one of embodiments 30 to 33, wherein the zeolitic material has a framework structure type selected from the group consisting of CSV, DAC, ETV, EUO, EWO, FER, HEU, IMF, ITH, LAU, -LIT, MEL, MFI, MFS, MTT, MWW, NES, -PAR, PCR, PTY, PWW, RRO, SFF, SFG, STF, STI, STW, -SVR, SZR, TER, TON, TUN, -WEN, and mixed structures composed of two or more thereof, preferably selected from the group consisting of FER, MFI, MWW, and mixed structures composed of two or more thereof, wherein the zeolitic material more preferably has the FER-type framework structure type.
35. The process of embodiment 34, wherein the zeolitic material has the FER-type framework structure type and wherein the zeolitic material is selected from the group consisting of Ferrierite, [Ga-Si-O]-FER, [Si-O]-FER, FU-9, ISI-6, NU-23, Sr-D, ZSM-35, and [B-Si-O]- FER, including mixtures of two or more thereof, more preferably from the group consisting of Ferrierite, FU-9, ISI-6, NU-23, and ZSM-35, including mixtures of two or more thereof, wherein more preferably the zeolitic material having a FER-type framework structure comprises, more preferably consists of, Ferrierite.
36. The process of any one of embodiments 30 to 35, wherein the zeolitic material is in the Flform .
37. The process of any one of embodiments 30 to 36, wherein each of the one or more keton- ization catalysts C2 independently from one another has a mass ratio of the zeolitic material, calculated as weight of the zeolitic material, to the one or more metals M2 and the support material S2, calculated as sum of the weights of the one or more metals M2 as elements and the support material S2, in the range of from 1 :200 to 1 :1 , preferably in the range of from 1 :100 to 1 :2, more preferably in the range of from 1 :20 to 1 :5, more preferably in the range of from 1 :12 to 1 :7.
38. The process of any one of embodiments 28 to 37, wherein the support material S2 comprises, preferably consists of, a metal oxide.
39. The process of embodiment 38, wherein the metal oxide is selected from the group consisting of alumina, silica, ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, preferably from the group consisting of ceria, zirconia, ceriazirconia, and mixtures of two or more thereof, wherein the metal oxide more preferably is ceria-zirconia.
40. The process of embodiment 39, wherein the ceria-zirconia has a Ce:Zr molar ratio in the range of from 1 :1 to 5:1 , preferably in the range of from 1.5:1 to 2.5:1 , more preferably in the range of from 1.7:1 to 2.3:1 , more preferably in the range of from 1.9:1 to 2.1 :1.
41 . The process of any one of embodiments 1 to 27, wherein each of the one or more keton- ization catalysts C2 independently from one another comprises, preferably consists of, one or more of ceria, zirconia, ceria-zirconia, yttria, titania, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, manganese oxide, zinc oxide, gallium oxide, indium oxide, tin oxide, bismuth oxide, a lanthanide oxide, and mixtures of two or more thereof, preferably from the group consisting of ceria, zirconia, ceria-zirconia, and mixtures of two or more thereof, wherein each of the one or more ketonization catalysts more preferably are ceria-zirconia.
42. The process of any one of embodiments 1 to 41 , wherein the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Zn and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Zn.
43. The process of any one of embodiments 1 to 42, wherein the one or more ketonization catalysts C2 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, and the support material S2, wherein the one or more ketonization catalysts C2 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
44. The process of any one of embodiments 1 to 43, wherein the one or more catalysts C3 are solid.
45. The process of any one of embodiments 1 to 44, wherein the one or more metals M3 are selected from the group consisting of Ag, Pd, Pt, and mixtures of two or more thereof, wherein the one or more metals M3 more preferably are Ag, a mixture of Ag and Pt, or a mixture of Ag and Pd, wherein the one or more metals M3 more preferably are Ag.
46. The process of any one of embodiments 1 to 45, wherein each of the one or more catalysts C3 further comprise one or more co-catalyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, more preferably selected from the group consisting of In, Sn, wherein the one or more co-catalyst metals are supported on the support material S3 in addition to the one or more metals M3, wherein each of the one or more catalysts C3 preferably displays an atomic ratio of the one or more metals M3, calculated as elements, to the one or more co-catalyst metals, calculated as elements, of less than 10:1.
47. The process of any one of embodiments 1 to 46, wherein the one or more metals M3 comprise, preferably consists of, a mixture of Ag and Pt, wherein each of the one or more catalysts C3 preferably display an atomic ratio of Ag, calculated as element, to Pt, calculated as element, in the range of from 5:1 to 50:1 , preferably in the range of from 10:1 to 28:1 , more preferably in the range of from 15:1 to 23:1 , more preferably in the range of from 18:1 to 20:1. 48. The process of embodiment 46, wherein the one or more metals M3 comprise, preferably consist of, Pd and wherein the one or more co-catalyst metals comprise, preferably consist of, In, wherein the one or more catalysts C3 preferably display an atomic ratio of Pd, calculated as element, to In, calculated as element, in the range of from 1 :2 to 10:1 , preferably in the range of from 1 :1 to 3:1 , more preferably in the range of from 1.5:1 to 2.5:1 , more preferably in the range of from 1 .9:1 to 2.1 :1.
49. The process of embodiment 46, wherein the one or more metals M3 comprise, preferably consist of, Pt and wherein the one or more co-catalyst metals comprise, preferably consist of, Sn, wherein the one or more catalysts C3 preferably display an atomic ratio of Pt, calculated as element, to Sn, calculated as element, in the range of from 0.05:1 to 5:1 , preferably in the range of from 0.1 :1 to 2:1 , more preferably in the range of from 0.2:1 to 1.0:1 , more preferably in the range of from 0.5:1 to 0.7:1.
50. The process of any one of embodiments 1 to 49, wherein the one or more metals M3 are supported on the support material S3 at a loading in the range of from 0.2 to 50.0 weight- %, preferably in the range of from 1 .0 to 40 weight-%, more preferably in the range of from 1 .5 to 30 weight-%, more preferably in the range of from 2.0 to 20 weight-%, more preferably in the range of from 2.5 to 10 weight-%, more preferably in the range of from 3.0 to 5.0 weight-%, calculated as sum of the one or more metals M3 as elements and based on the sum of the weights of the one or more metals M3 and the support material S3.
51 . The process of any one of embodiments 1 to 50, wherein the support material S3 comprises, preferably consists of, one or more of a transitional alumina, a-alumina, silica, titania, carbon, and silicon carbide, preferably one or more of a-alumina, silica, carbon and silicon carbide, wherein the support material S3 more preferably comprises, more preferably consists of, a-alumina or silica, more preferably a-alumina.
52. The process of any one of embodiments 1 to 51 , wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of y-alumina, wherein the one or more catalysts C3 are more preferably free of y-alumina.
53. The process of any one of embodiments 1 to 52, wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Ni, calculated as element and based on the sum of the weights of the Ni, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Ni.
54. The process of any one of embodiments 1 to 53, wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Mo, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Mo, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Mo.
55. The process of any one of embodiments 1 to 54, wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Zn, calculated as element and based on the sum of the weights of Mo and based on the sum of the weights of the Zn, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Zn.
56. The process of any one of embodiments 1 to 55, wherein the one or more catalysts C3 comprise from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cu and Pd, preferably of one or more of Cu and Pd, calculated as sum of the weights of one or more of Pd and Cu, respectively, as elements and based on the sum of the weights of one or more of Cu and Pd, respectively, the one or more metals M3 and the support material S3, wherein the one or more catalysts C3 more preferably are free of Cu and Pd, preferably of one or more of Cu and Pd.
57. The process of any one of embodiments 1 to 56, wherein each of the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, independently from one another is comprised in a packed-bed.
58. The process of any one of embodiments 1 to 57, wherein the gas stream prepared according to (II) has a molar ratio of CO to H2 in the range of from 0.1 :1 to 10:1 , preferably in the range of from 0.2:1 to 5:1 , more preferably in the range of from 0.3:1 to 2.5:1 , more preferably in the range of from 0.4:1 to 1.3:1 , more preferably in the range of from 0.5:1 to 1.1 :1.
59. The process of any one of embodiments 1 to 58, wherein the gas stream prepared according to (ii) has a molar ratio of CO to the oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, in the range of from 1 :1 to 100:1 , preferably in the range of from 2:1 to 80:1 , more preferably in the range of from 5:1 to 60:1 , more preferably in the range of from 10:1 to 50:1 , more preferably in the range of from 20:1 to 47:1.
60. The process of any one of embodiments 1 to 59, wherein the gas stream prepared according to (ii) has a molar ratio of H2 to oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, in the range of from 10:1 to 100:1 , preferably in the range of from 20:1 to 80:1 , more preferably in the range of from 30:1 to 60:1 , more preferably in the range of from 40:1 to 50:1 , more preferably in the range of from 43:1 to 47:1.
61 . The process of any one of embodiments 1 to 60, wherein the gas stream prepared according to (ii) further comprises one or more inert gases selected from the group consisting of Ar, N2, He, (C1-C3)alkanes, and mixtures of two or more thereof. 62. The process of embodiment 61 , wherein the gas stream prepared according to (ii) has a molar ratio of CO to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 50:1 , preferably in the range of from 1 :1 to 20:1 , more preferably in the range of from 2:1 to 10:1 , more preferably in the range of from 3:1 to 7:1 , more preferably in the range of from 4:1 to 6:1.
63. The process of embodiment 61 or 62, wherein the gas stream prepared according to (ii) has a molar ratio of H2 to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :2 to 500:1 , preferably in the range of from 1 :1 to 200:1 , more preferably in the range of from 2:1 to 100:1 , more preferably in the range of from 3:1 to 50:1 , more preferably in the range of from 4:1 to 25:1.
64. The process of any one of embodiments 61 to 63, wherein the gas stream prepared according to (ii) has a molar ratio of the oxygenate, calculated as sum of molar amounts of methanol and dimethyl ether, to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases, in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :25 to 20: 1 , more preferably in the range of from 1 :20 to 10: 1 , more preferably in the range of from 1 :15 to 1 :1 , more preferably in the range of from 1 :10 to 1 :5.
65. The process of any one of embodiments 1 to 64, wherein the gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C2-C6)alkene, preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-% of a (C2-C6)alkene, preferably of one or more of ethylene, propylene, and butylene, more preferably of propylene.
66. The process of any one of embodiments 1 to 65, wherein the gas stream prepared according to (ii) comprises from 0 to 1 volume-% of a (C3-C6)ketone, preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-% of a (C3-C6)ketone, preferably of acetone.
67. The process of any one of embodiments 1 to 66, wherein the gas stream prepared according to (ii) is obtained from biosyngas.
68. The process of any one of embodiments 1 to 67, wherein the reactor comprises an inlet end and an outlet end, and an axial length extending from the inlet end to the outlet end.
69. The process of embodiment 68, wherein the reactor has a volume in the range of from 50 to 1000 I, preferably in the range of from 250 to 400 I, more preferably in the range of from 300 to 330 I.
70. The process of any one of embodiments 1 to 69, wherein contacting according to (iii) comprises heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 to a temperature in the range of from 100 to 400 °C, preferably in the range of from 150 to 400 °C, more preferably in the range of from 200 to 350 °C, more preferably in the range of from 240 to 310 °C, more preferably in the range of from 260 to 290 °C, more preferably in the range of from 270 to 280 °C.
71 . The process of any one of embodiments 1 to 70, wherein the gas stream prepared according to (ii) is contacted according to (iii) with the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 at a pressure in the range of from 1 to 200 bar(abs), preferably in the range of from 5 to 150 bar(abs), more preferably in the range of from 5 to 35 bar(abs), more preferably in the range of from 10 to 30 bar(abs), more preferably in the range of from 12 to 28 bar(abs), more preferably in the range of from 16 to 24 bar(abs), more preferably in the range of from 18 to 22 bar(abs), more preferably in the range of from 19 to 21 bar(abs).
72. The process of any one of embodiments 1 to 71 , wherein the gas stream prepared according to (ii) is fed into the reactor according to (iii) with a gas hourly space velocity in the range of from 10 to 1000 IT1 , preferably in the range of from 100 to 300 IT1 , more preferably in the range of from 150 to 250 IT1 , more preferably in the range of from 190 to 210 IT1 , more preferably in the range of from 194 to 203 IT1.
73. The process of any one of embodiments 1 to 72, wherein the process further comprises a heat treatment after (ii) and prior to (iii), wherein the heat treatment preferably comprises (a.1) feeding a gas stream comprising, preferably consisting of, one or more inert gases selected from the group consisting of Ar, N2, and mixtures of two or more thereof, preferably N2, into the reactor provided according to (i);
(a.2) heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) to a temperature in the range of from 250 to 400 °C, preferably in the range of from 300 to 350 °C.
74. The process of embodiment 73, wherein heating according to (a.2) is performed for a period in the range of from 1 to 5 h, preferably in the range of from 2 to 4 h.
75. The process of any one of embodiments 1 to 74, wherein the process further comprises a catalyst activation after (ii) or after the heat treatment according to embodiment 73 or 74, and prior to (iii), wherein the catalyst activation comprises
(b.1) feeding a gas stream comprising, preferably consisting of, H2 and one or more inert gases selected from the group consisting of Ar, N2, and mixtures of two or more thereof, preferably N2, into the reactor provided according to (i);
(b.2) heating the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) to a temperature in the range of from 175 to 325 °C, preferably in the range of from 225 to 275 °C; (b.3) contacting the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) with the gas stream fed into the reactor according to (b.1 ).
76. The process of embodiment 75, wherein the gas stream is fed according to (b.1 ) into the reactor has a volume ratio of H2 to the one or more inert gases, calculated as sum of the molar amounts of the one or more inert gases in the range of from 0.1 :1 to 1 :1 , preferably in the range of from 0.3:1 to 0.5:1.
77. The process of embodiment 75 or 76, wherein heating according to (b.2) is performed for a period in the range of from 1 to 5 h, preferably in the range of from 2 to 4 h.
78. The process of any one of embodiments 1 to 77, wherein the process is a continuous process or a batch process, preferably a continuous process.
79. The process of any one of embodiments 1 to 78 further comprising prior to (i)
(A) preparing a gas stream comprising H2, CO, and optionally CO2;
(B) contacting the gas stream prepared according to (A) with a catalyst, for obtaining a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof.
80. The process of embodiment 79, wherein according to (A) the gas stream comprises H2 in an amount in the range of from 25 to 95 vol.-%, preferably of from 50 to 92 vol.-%, more preferably of from 60 to 90 vol.-%, and more preferably of from 60 to 75 vol.-%.
81 . The process of embodiment 79 or 80, wherein according to (A) the gas stream comprises CO2 in an amount of equal to or less than 60 vol.-%, preferably of equal to or less than 50 vol.-%, more preferably of equal to or less than 40 vol.-%, more preferably of equal to or less than 30 vol.-%, more preferably of equal to or less than 25 vol.-%, and more preferably of equal to or less than 22, wherein more preferably the gas stream comprises CO2 in an amount in the range of froml to 22 vol.-%, more preferably in the range of from 5 to 21 vol.-%, more preferably in the range of from 10 to 20 vol.-%, and more preferably in the range of from 15 to 19 vol.-%.
82. The process of any one of embodiments 79 to 81 , wherein according to (A) the gas stream further comprises CO, preferably in an amount in the range from 0.5 to 40 voL-%, more preferably in the range of from 1 to 33 voL-%, more preferably in the range of from 2 to 20 voL-%, more preferably in the range of from 3 to 10 voL-%, and more preferably in the range of from 5 to 8 voL-%.
83. The process of any one of embodiments 79 to 82, wherein according to (A) the gas stream further comprises one or more inert gases, preferably in an amount in the range of from 0.1 to 40 vol.-%, more preferably in the range of from 0.5 to 30 vol.-%, more preferably in the range of from 1 to 20 vol.-%, and more preferably in the range of from 2 to 15 vol.-%.
84. The process of embodiment 83, wherein the one or more inert gases are selected from the group consisting of He, Ar, Ne, CH4, N2, and mixtures of two or more thereof, preferably from the group consisting of Ar, CH4, N2, and mixtures of two or more thereof, wherein the one or more inert gases more preferably are CH4 and N2.
85. The process of any one of embodiments 79 to 84, wherein contacting according to (B) is conducted at a temperature in the range of from 200 to 400 °C, preferably in the range of from 250 to 350 °C, and more preferably in the range of from 270 to 330 °C.
86. The process of any one of embodiments 79 to 85, wherein contacting according to (B) is conducted at a pressure of 100 bar(abs) or less, preferably in the range of from 50 to 95 bar(abs), more preferably in the range of from 60 to 90 bar(abs), and more preferably in the range of from 70 to 80 bar(abs).
87. The process of any one of embodiments 79 to 86, wherein contacting according to (B) is conducted in a continuous mode, preferably in a recycle mode, after separation of the high boiling products dimethylether and methanol.
88. The process of embodiment 87, wherein contacting according to (B) is conducted in a continuous mode at a gas hourly space velocity in the range of from 500 to 24,000 IT1 , preferably in the range of from 1000 to 8000 IT1 , and more preferably in the range of from 2000 to 6000 IT1.
89. The process of any one of embodiments 1 to 88, further comprising after (iii)
(iv) recovering 2-propanol from the product gas stream obtained according to (iii).
90. The process of any one of embodiments 1 to 89, being for the production of 2-propanol and one or more of methyl acetate and acetone.
91 . The process of any one of embodiments 1 to 90, wherein the product gas stream obtained according to (iii) further comprises one or more of methyl acetate and acetone.
The present invention is further illustrated by the following reference examples, examples and comparative examples.
EXAMPLES Reference Exampie 1 : Determination of particle size
The macroscopic particle size of the catalyst was determined using calibrated Retsch stainless steel sieves.
Reference Example 2: Determination of crystalline structure via XRD
The crystalline structure of a sample was determined by Powder X-Ray Diffraction (XRD). Experimentally, the measurements have been carried out in Bragg-Brentano geometry using a PANalytical CUBIX diffractometer equipped with a PANalytical X'Celerator detector. Cu Ka X- ray radiation (Lambdal = 1.5406 angstrom, Lambda2 = 1.5444 angstrom, I2/I1 = 0.5) generated in a copper metal anode source operated at a voltage of 45 kV and a current of 40 mA has been employed. The goniometer arm length is 200 mm, and a variable divergence slit with an irradiated sample area of 5 mm was used. The measurement range used was 3.5° to 90.0° (2theta), with a step of 0.020° (2theta) and a measurement time of 35 seconds per step. Measurements were performed at 298 K, while the sample, mounted as a fine powder in a sample holder with a sample area of 79 mm2 or 804 mm2, was rotated at 0.5 revolutions per second around the axis perpendicular to the irradiated sample surface.
Reference Example 3: Determination of chemical composition
Chemical compositions were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) using a Varian 715-ES spectrometer. The samples were previously dissolved in a mixture of nitric acid (HNO3) and hydrochloric acid (HCI), in a 1 :3 ratio (HNO3:HCI), at 333 K for 20 h. For materials based on a-ALOs, disaggregation was not possible and therefore analyses were performed by Energy Dispersive X-ray spectroscopy (EDS) in a Field Emission Scanning Electron microscope, FESEM (ZEISS, ULTRA 55), equipped with a X-Max 80 - Oxford Instruments EDS detector. The powdered sample was dispersed over a double-faced carbon adhesive mounted on a SEM pin stub. Elemental quantification was based on the EDS signal for photon emission K lines for elements with atomic number below 15 (Z < 15), photon emission M lines for elements with atomic number greater than 50 (Z > 50), and photon emission L lines for the remaining elements.
Reference Example 4: Determination of specific surface area
Specific surface areas and pore volumes were determined by N2 physisorption. N2 physisorption isotherms were recorded at 77 K using a ASAP 2420 or ASAP 2020 Micrometrics. Prior to the measurements, samples were dried in situ at 473 to 573 K under vacuum (10-3 mbar) for 12 h (10 K min-1). The Brunauer-Emmett-Teller (BET) method was used to determine surface areas from the 0.05 to 0.30 P/Po regime of the recorded isotherms. Pore volumes were determined from the adsorbed N2 volume detected at equilibrium point P/Po of 0.95 from the adsorption branch of the isotherm. Reference Exam pie 5: Preparation of Ag-H-MOR as carbonylation catalyst
7.65 g of mordenite zeolite in its ammonium form (NH4-MOR, purchased from Zeolyst International, SiO2/AI2O3 molar ratio of 20), were suspended in 45 mL of deionized water (conductivity < 1 pS/cm). Separately, 1.00 g of silver nitrate (AgNOs, Sigma Aldrich, > 99 %) was dissolved in 4 mL of deionized water. The AgNOs solution was added to the NH4-MOR suspension and stirred at room temperature for 30 min. The solvent was evaporated under vacuum (50-100 mbar) at 50 °C using a rotary evaporator. The obtained material was then dried at 100 °C for 2 h in an oven. Then, the solid was transferred into a ceramic crucible and subjected to a further drying step at 110 °C for 4 h, followed by calcination under stagnant air atmosphere by heating to 500 °C (heating ramp of 3 °C/min), followed by an isothermal step at 500 °C for 3 h and cooling down to room temperature in a convectionless muffle furnace. The silver loading was 9.4 weight- % (corresponding to an atomic ratio Ag/AI of 0.6).
Prior to catalytic experiments, the catalyst was subjected to activation treatments. 2.0 g of Ag-H- MOR, previously sieved to obtain particles having a size in the range 0.2-0.4 mm, were loaded as a packed bed in a stainless steel reactor (316 L, 7.8 mm internal diameter) and subjected to a first thermal treatment under nitrogen flow (50 mL/min) by heating to 500 °C (heating ramp of 3 °C/min from room temperature) followed by an isothermal step at 500 °C for 3 hours and cooling down to room temperature. In a second step, a gas mixture of DME/CO/H2/Ar in molar ratios 1/45/45/9 was fed to the inlet of the reactor and the reactor was pressurized to 20 bar pressure by means of a membrane back-pressure regulating valve (Swagelok) located downstream of the reactor. Next, the flow rate of the DME/CO/H2/Ar stream was adjusted to obtain approximately 900 IT1 gas space velocity (GHSV) and the reactor temperature was increased to 275 °C following a heating ramp of 3 °C/min and it was kept constant at 275 °C for 20 hours and finally cooled down to room temperature. After these activation treatments, the catalyst was recovered and then used as carbonylation catalyst.
Reference Example 6: Preparation of H-FER-Pd/CeC -ZrC as ketonization catalyst
FER zeolite (SiO2/AhO3 molar ratio of 26.4) was synthetized in its aluminosilicate form. First, a synthesis gel was prepared by mixing 0.79 g of pseudo-boehmite (CATAPAL, Sasol Materials, 72 % AI2O3), 10.6 g of trans- 1 ,4-diaminecyclohexane (TDACH, Sigma Aldrich, 98 %), 25.3 g of colloidal silica (Sigma Aldrich, LUDOX AS40, 40 % suspension in water) and deionized water. The mixture was kept under stirring at 377 rpm at room temperature while evaporating the amount of water needed to reach a molar gel composition of 1 SiO2 : 0.033 AI2O3 : 0.48 TDACH : 5 H2O. Once the amount of water had been adjusted, 3.54 g of HF (Sigma Aldrich, 48 % in water) was added to the gel, reaching a final molar gel composition of 1 SiO2 : 0.033 AI2O3 : 0.48 TDACH : 0.5 HF : 5 H2O. The gel obtained was kept under stirring at room temperature for 30 minutes and it was then transferred to 2 stainless steel autoclaves provided with PTFE in-liners of 35 ml volume. The autoclaves were introduced in a pre-heated oven and kept at 150 °C for 15 days for zeolite crystallization. The solid obtained was recovered by filtration, washed with deionized water, dried at 100 °C in an oven, and calcined in a tubular packed-bed reactor at 550 °C (heating rate 1 °C/min) for 10 hours, under synthetic air flow (approximately 80 ml/min).
Separately, CeO2-ZrO2 (Ce:Zr molar ratio of approximately 2:1 ) was synthetized by submitting a commercial cerium (IV)-zirconium (IV) mixed oxide (Sigma-Aldrich, 99 %) to a thermal treatment under stagnant air atmosphere in a muffle furnace. The sample was heated from room temperature to 600 °C (heating rate of 3 °C/min), followed by an isothermal step at 600 °C for 4 hours and cooling down to room temperature. Next, palladium was incorporated by impregnation. 21 mg of palladium acetylacetonate (Pd(acac)2, Sigma Aldrich, 99 %), were dissolved in 125 mL of acetone. 10.0 g of CeO2-ZrO2 were suspended in the Pd(acac)2 solution and the mixture was stirred at room temperature for 20 minutes. The solvent was removed in a rotary evaporator under vacuum (50-100 mbar) at 30 °C. The solid recovered was dried at 60 °C under air and subsequently submitted to a thermal treatment in a muffle furnace under stagnant air atmosphere. The thermal treatment consisted of an isothermal drying step at 110 °C for 4 hours, followed by a heating step up to 600 °C (heating rate of 1 °C/min) and an isothermal step at 600 °C for 4 hours. After that, the solid was cooled down to room temperature.
Finally, the H-FER and Pd/CeO2-ZrO2 powders were mixed in a 1 :7.5 mass ratio and the resulting composite material was ground thoroughly in a mortar with a pestle to produce the H-FER- Pd/CeO2-ZrC>2 catalyst. The Pd loading on the H-FER-Pd/CeO2-ZrO2 catalyst was 0.065 weight- 0 //o.
Reference Example 7: Preparation of a Ag/SiCh catalyst
Ag/SiC>2 (nominal loading: 5 wt.-% Ag based on Ag/SiC>2 catalyst) was synthesized by incipient wetness impregnation. 0.85 g of silver nitrate (AgNOs, Sigma Aldrich, > 99.0 %) were dissolved in 10 mL of a 0.1 M HNO3 aqueous solution. Separately, 9.23 g of SIC>2 (SiliCycle, SiliaSphere PC 60A, SBET=756 m2/g, total pore volume=0.93 cm3/g) were dried in a flask at 120-150 °C under dynamic vacuum (30 mbar) for at least 3 h. Next, 7.73 mL of the silver nitrate solution were brought in contact with the dry solid under static vacuum and magnetic stirring at room temperature, allowing the solution to infiltrate into the pores of the silica support. The amount of solution applied in the impregnation step was set to 90 % of the total pore volume of the SIC>2 support material. The impregnated solid was dried in a quartz tubular reactor under nitrogen flow (approximately 80 mL/min) at 70 °C for 10 hours, followed by a calcination treatment to decompose the silver precursor, in the same reactor, under the same nitrogen flow, by heating from 70 °C to 450 °C (heating rate of 1 °C/min), followed by an isothermal stage at 450 °C for 4 hours.
Reference Example 8: Preparation of a-AfeOa
Alpha-alumina (a-ALOs) was synthesized by direct calcination of a gamma-alumina (Y-AI2O3). Gamma-AhOs spheres (SASOL, Alumina Spheres 1 .8/210) were crushed and sieved. Then par- tides in the size range of 0.4-0.6 mm were calcined in a muffle furnace under stagnant air applying a heating ramp of 3 °C/min from room temperature to 1140 °C, followed by an isothermal dwell stage at 1140 °C for 4 hours and cooling down to room temperature.
Reference Example 9: Preparation of a Pd-ln/a-AfeOa catalyst
Pd-ln/a-AhOs (nominal overall metals loading=5 wt.-% based on Pd-ln/a-AhOs catalyst; atomic ratio of Pd:ln=2:1 ) was synthesized by wet impregnation in one step. 298 mg of palladium^ I) nitrate dihydrate (Pd(NC>3)2-2H2O, Sigma Aldrich, about 40 % Pd basis) and 226 mg of indium(lll) nitrate hydrate (ln(NC>3)3-5H2O, Sigma Aldrich, 99.9 %) were dissolved in 80 mL of a 0.9 M HNO3 aqueous solution. 3.5 g of a-ALOs prepared according to Reference Example 8 were suspended in the metal salts solution and the suspension was stirred for 15 minutes. The solvent was removed under vacuum (50-100 mbar) using a rotary evaporator at 60 °C. The obtained material was then dried in air at 60 °C for 2 h. The dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 350 °C (heating rate of 2 °C/min), followed by an isothermal step at 350 °C for 4 h under nitrogen flow (200 mL/min).
Reference Example 10: Preparation of a Pt-Sn/a-AfeOa catalyst
Pt-Sn/a-AhOs (nominal overall metals loading: 2 wt.-% based on Pt-Sn/a-AhOs catalyst; atomic ratio of Pt:Sn=0.6:1 ) was synthesized by wet impregnation in two steps. First, 117 mg of tin(IV) chloride hydrate (SnC SFhO, Alfa Aesar, 98 %), were dissolved in 30 mL of deionized water. 4.09 g of a-AhOs prepared according to Reference Example 8 were suspended in the SnCU solution and the suspension stirred for 15 minutes. Then, the solvent was removed under vacuum (50-100 mbar) using a rotary evaporator at 60 °C. The obtained material was dried at 60 °C in air for 2 h. The dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 550 °C (heating rate of 2 °C/min), followed by an isothermal step at 550 °C for 4 h under synthetic air flow (200 mL/min). In a second step, 79 mg of tetraammine platinum(ll) nitrate (Pt(NH4)4(NOs)2, Sigma Aldrich, 99.995 %) were dissolved in 30 mL of deionized water. The Sn/a-AhOs material was suspended in the Pt(NH4)4(NO3)2 solution and the suspension stirred for 15 minutes. The solvent was removed under vacuum (50-100 mbar) using a rotary evaporator at 60 °C. The obtained material was dried at 60 °C for 2 h. The dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 350 °C (heating rate of 2 °C/min), followed by an isothermal step at 350 °C for 4 h under nitrogen flow (200 mL/min).
Reference Example 11 : Preparation of a Ag-Pt/a-AfeOa catalyst
Ag-Pt/a-AhOs (nominal overall metals loading: 5.5 wt.-% based on Ag-Pt/a-AhOs catalyst; atomic ratio of Ag:Pt=19:1 ) was synthesized by wet impregnation in one step. Silver oxalate (Ag2C2C>4) was used as silver precursor. To synthesize Ag2C2C>4, 5.0 g of silver nitrate (AgNOs, Sigma Aldrich, > 99.0%) and 7.0 g of oxalic acid dihydrate (HO2CCO2H-2H2O, Sigma Aldrich, > 99.0 %) were dissolved in 100 mL of M illiQ water and the mixture was stirred for 15 minutes. The solid precipitated was recovered by filtration and washed with 1 L of MilliQ water. The filter containing the Ag2C2O4 material was dried overnight at 80 °C and the solid recovered and kept under a protective Ar atmosphere until use. Next, 257 mg of Ag2C2O4 were dissolved in a mixture of 25 mL of MilliQ and approximately 150 mg of ethylene diamine (Sigma Aldrich, 99%). 36 mg of tetraammine platinum(ll) nitrate (Pt(NH4)4(NO3)2, Sigma Aldrich, 99.995%) were added to the solution and the mixed metal solution was stirred for 10 minutes. 3.5 g of a-ALOs were suspended in the metal salts solution and the suspension stirred for 15 minutes. The solvent was evaporated under vacuum (50-100 mbar) using a rotary evaporator at 70 °C. The obtained material was then dried in air at 60 °C for 2 h. The dry solid was transferred to a tubular quartz reactor and subjected to further drying (70 °C for 4 h) and subsequent calcination by heating to 350 °C (heating rate of 2 °C/min), followed by an isothermal step at 350 °C for 4 h under nitrogen flow (200 mL/min).
Reference Example 12: Preparation of a Ni-Mo-Znx/y-AhOa catalyst
A Ni-Mo-ZnOx/y-AhOs catalyst was synthesized as described in Example 1 of CN 101927168 A.
In a first step, 2.4 g of aluminium oxide, produced by calcination of a pseudo-boehmite powder (DISPERAL HP14, Sasol Materials, Germany) at 550 °C in a muffle furnace without convection in an air atmosphere. The resulting support material was dried in a round-bottom multi-necked flask at a temperature of 200 °C under dynamic vacuum provided by a vacuubrand-MZ-2C-NT membrane pump for 4 hours.
3.53 g of nickel nitrate hexahydrate, Ni(NO3)2-6H2O (Merck, 99.999 %), 0.131 g of ammonium heptamolybdate tetrahydrate, (NH4)eMo7O24-4H2O (SUPELCO) and 0.324 g of zinc nitrate hexahydrate, Zn(NO3)2-6H2O (Alfa Aesar, 99 %), were dissolved in deionized water and the total volume of the solution adjusted to 5 ml. 1.48 ml of the metal precursors solution was brought in contact with the previously dried aluminium oxide, at room temperature and under static vacuum, allowing the solution to infiltrate into the pores of the AI2O3 support. The material obtained was subjected to a drying treatment in a packed-bed tubular reactor under nitrogen flow (200 ml/min) at 70 °C for 10 hours, followed by a calcination treatment in the same reactor, and under the same nitrogen flow, by heating from 70 °C to 350 °C (heating rate of 2 K/min) and an isothermal stage at 350 °C lasting 3 hours.
Example 13: Catalytic testing
A 316 L stainless steel tubular reactor was used having 7.8 mm internal diameter, equipped with an external coiled heating element of 600 W power, controlled by a PID controller, and a type K thermocouple coated with a 316 L stainless steel sheath inserted axially in the catalyst bed. Catalyst samples were press-conformed as pellets, the pellets disaggregated in a mortar with a pestle and particles in the size range of 200 to 400 pm recovered by means of sieving. The catalyst particles were diluted with silicon carbide granules (SiC, Fisher Chemical, mean granule size about 696 pm) previously sieved to retain particles in the size range 600 - 800 pm, in order to increase the overall thermal conductivity of the packed beds in the reactor.
Finally, the SiC-diluted catalysts were loaded into the tubular reactor in the form of either a single packed-bed (loading scheme I according to Figure 1 a)), two (loading scheme II according to Figure 1 b)) or three (loading scheme III according to Figure 1 c)) axially arranged, consecutive packed beds as shown in Figure 1. Individual packed beds were spaced by quartz wool blocks (3 mm thickness, axially). The overall volume of the packed beds was about 6 mL.
Examples 13.1 , 13.2, 13.3, and 13.4 as well as Comparative Examples 13.5, 13.6 and 13.7 were prepared using the catalysts according to the reference examples described hereinabove. The specific loadings are described in Table 1 below.
Table 1 :
Loadings of catalysts for Examples 13.1 , 13.2, 13.3, and 13.4 as well as Comparative Examples 13.5, 13.6 and 13.7.
Figure imgf000038_0001
Prior to the catalytic testing, catalysts were subjected to an in situ activation treatment, i.e. in the tubular reactor itself. This activation treatment consisted of two steps. In a first step, the reactor was heated from room temperature to 325 °C (with a temperature ramp of 3 °C/min) under N2 (Abello-Linde, 99.999 %) flow of approximately 50 mL/min, followed by an isothermal step at 325 °C for 3 hours, and cooling to room temperature. Next, the reactor was heated from room temperature to 250 °C (with a temperature ramp of 3 °C/min) under a mixed flow of H2 (Abello- Linde, 99.999 %, 20 mL/min) and N2 (Abello-Linde, 99.999 %, 50 mL/min), followed by an isothermal step at 250 °C for 3 hours, and cooling to room temperature.
After activation, the catalytic conversion experiment was started. To this end, a gas stream containing DME/CO/Fh/Ar in molar ratios 1/45/45/9 was fed from pressurized cylinders into the reactor and the reactor was pressurized to the desired operation pressure by means of a membrane back-pressure regulating valve (Swagelok) located downstream of the reactor. Next, the flow rate of the DME/CO/Fh/Ar stream was adjusted to obtain the desired gas space velocity (GHSV) and the reactor temperature was increased to the selected operation temperature following a heating ramp of 3 °C/min. The outlet stream from the tubular reactor, was depressurized at the pressure control valve and periodically analyzed in an Agilent 7890 gas chromatograph located on-line, downstream of the reactor, and equipped with two analysis channels. A first channel is equipped with a packed column HayeSep R 80/100 (6 ft), a capillary column HP- PLOT-Q 30m (20 pm film thickness) and a capillary column molecular sieve HP-PLOT 5A 30m (12 pm film thickness) and two TCD detectors for the analysis of permanent gases and carbon dioxide. A second analysis channel is equipped with a capillary column DB 1-MS (60 m) and a FID detector for the analysis of organic hydrocarbon and oxygenated compounds.
The results for the catalytic testing for Examples 13.1 , 13.2, 13.3, and 13.4 as well as Comparative Examples 13.5, 13.6 and 13.7 are shown in Table 2 below.
Table 2:
Results for the catalytic testing
Figure imgf000039_0001
(1 ) Dimethyl ether conversion;
(2) 2-propanol production rate = [W2-propanoi]/[MCat], wherein W2-propanoi is the mass flow rate of 2- propanol produced and Mcat is the lumped mass of all catalysts in the reactor;
(3) Selectivity among organic products, on a carbon molar basis; the selectivity to each organic reaction product "i" (Si) is calculated by the following equation: Si=[Nj!outlet*Ci]/[^Njjoutlet*Cj]* 1 00, where Ni, outlet is the molar flux of product "i" in the reactor outlet stream (mol IT1), Ci is the number of carbon atoms in the molecular structure of product "I" and the sum in the denominator extends to all organic products "j".
As can be deduced from the results presented in Table 2, examples 13.1-13.4, which are according to the present invention, lead to a process with high selectivity to C3 oxygenate products, and particularly 2-pronanol. In Comparative Examples 13.5-13.7, which are not according to the present invention, the selectivity to 2-propanol is essentially null. The results illustrate the technical effect of high selectivity to 2-propanol for a process in accordance with the present invention.
Brief description of figures
Figure 1 : shows schematic drawings for different configurations of catalyst packed-beds in a tubular reactor, wherein in a) a single packed bed loading scheme I is shown, in b) a two packed beds loading scheme II, and in c) a three packed beds loading scheme III, wherein the arrows indicate the direction of the gas flow through the reactor.
Cited literature
Gehrmann & Tenhumberg, “Production and Use of Sustainable C2-C4 Alcohols - An Industrial Perspective” Chemie Ingenieur Technik, Volume 92, 2020, pages 1444-1458
- US 6930213 B1
- US 7041857 B1
- US 2013/0035517 A1
- CN 112403510 A
- WO 2022/144480 A1
- EP 2590922 B1
- CN 104892361 A
- EP 2173694 B1

Claims

Ciaims
1 . A process for producing 2-propanol, the process comprising
(i) providing a reactor comprising one or more carbonylation catalysts C1 , one or more ketonization catalysts C2, and one or more catalysts C3, wherein the one or more catalysts C3 independently from one another comprise one or more metals M3 and a support material S3, wherein the one or more metals M3 are supported on the support material S3, and wherein the one or more metals M3 are selected from the group consisting of Cu, Ag, Au, Pd, Pt, and mixtures of two or more thereof;
(ii) preparing a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof;
(iii) feeding the gas stream prepared according to (ii) into the reactor provided according to (i) and contacting the gas stream with the one or more carbonylation catalysts C1 , the one or more ketonization catalysts C2, and the one or more catalysts C3, obtaining a product gas stream comprising 2-propanol.
2. The process of claim 1 , wherein each of the one or more carbonylation catalysts C1 , independently from one another, comprises one or more metals M1 , and a support material S1 , wherein the one or more metals M1 are supported on the support material S1 .
3. The process of claim 2, wherein the one or more metals M1 are selected from the group consisting of Ag, Ga, Pd, Cu, In, Sn, Ir, Pt, Rh, Co, Re, Zn, and mixtures of two or more thereof.
4. The process of claim 2 or 3, wherein the support material S1 comprises one or more of a zeolitic material and a metal oxide.
5. The process of any one of claims 1 to 4, wherein each of the one or more carbonylation catalysts C1 , independently from one another, comprises a zeolitic material.
6. The process of any one of claims 1 to 5, wherein each of the one or more ketonization catalysts C2 independently from one another comprises one or more metals M2, and a support material S2, wherein the one or more metals M2 are supported on the support material S2.
7. The process of claim 6, wherein the one or more metals M2 are selected from the group consisting of Pd, Pt, Ag, Fe, Ru, Os, Co, Rh, Ir, Ni, Cu, Au, and mixtures of two or more thereof.
8. The process of claim 6 or 7, wherein each of the one or more ketonization catalysts C2 independently from one another comprises a zeolitic material.
9. The process of any one of claims 6 to 8, wherein the support material S2 comprises a metal oxide.
10. The process of any one of claims 1 to 9, wherein each of the one or more catalysts C3 further comprise one or more co-catalyst metals in addition to the one or more metals M3, wherein the one or more co-catalyst metals are selected from the group consisting of In, Sn, Ge, Mo, Mn, Ti, Ru, Rh, Re, Os, Ir, and mixtures thereof, wherein the one or more co- catalyst metals are supported on the support material S3 in addition to the one or more metals M3.
11 . The process of any one of claims 1 to 10, wherein contacting according to (iii) comprises heating the one or more carbonylation catalysts 01 , the one or more ketonization catalysts C2, and the one or more catalysts C3 to a temperature in the range of from 100 to 400 °C.
12. The process of any one of claims 1 to 11 , wherein the process further comprises a heat treatment after (ii) and prior to (iii).
13. The process of any one of claims 1 to 12, wherein the process further comprises a catalyst activation after (ii) or after the heat treatment according to claim 12, and prior to (iii), wherein the catalyst activation comprises
(b.1) feeding a gas stream comprising H2 and one or more inert gases selected from the group consisting of Ar, N2, and mixtures of two or more thereof into the reactor provided according to (i);
(b.2) heating the one or more carbonylation catalysts 01 , the one or more ketonization catalysts 02, and the one or more catalysts C3 comprised in the reactor provided according to (i) to a temperature in the range of from 175 to 325 °C;
(b.3) contacting the one or more carbonylation catalysts 01 , the one or more ketonization catalysts C2, and the one or more catalysts C3 comprised in the reactor provided according to (i) with the gas stream fed into the reactor according to (b.1).
14. The process of any one of claims 1 to 13, further comprising prior to (i)
(A) preparing a gas stream comprising H2, CO, and optionally CO2;
(B) contacting the gas stream prepared according to (A) with a catalyst, for obtaining a gas stream comprising CO, H2, and an oxygenate selected from the group consisting of methanol, dimethyl ether, and mixtures thereof.
15. The process of any one of claims 1 to 14, further comprising after (iii)
(iv) recovering 2-propanol from the product gas stream obtained according to (iii).
PCT/EP2024/057042 2023-03-17 2024-03-15 Process for producing 2-propanol Ceased WO2024194205A1 (en)

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