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WO2024194205A1 - Procédé de production de 2-propanol - Google Patents

Procédé de production de 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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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

La présente invention concerne un procédé de production de 2-propanol, le procédé comprenant (i) la mise à disposition d'un réacteur comprenant un ou plusieurs catalyseurs de carbonylation C1, un ou plusieurs catalyseurs de cétonisation C2, et un ou plusieurs catalyseurs C3, chacun du ou des catalyseurs C3 indépendamment les uns des autres comprenant un ou plusieurs métaux M3 et un matériau de support S3, le ou les métaux M3 étant supportés sur le matériau de support S3, et le ou les métaux M3 étant choisis dans le groupe constitué par Cu, Ag, Au, Pd, Pt, et des mélanges d'au moins deux de ceux-ci ; (ii) la préparation d'un flux gazeux comprenant CO, H2, et un composé oxygéné choisi dans le groupe constitué par le méthanol, l'éther diméthylique et des mélanges de ceux-ci ; (iii) l'introduction du flux gazeux dans le réacteur et la mise en contact du flux gazeux avec le ou les catalyseurs de carbonylation C1, le ou les catalyseurs de cétonisation C2, et le ou les catalyseurs C3, l'obtention d'un flux de gaz produit.
PCT/EP2024/057042 2023-03-17 2024-03-15 Procédé de production de 2-propanol Pending WO2024194205A1 (fr)

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