WO2018051198A1 - Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse et méthane, en présence de catalyseurs d'oxydes métalliques mixtes de cuivre-manganèse-aluminium - Google Patents

Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse et méthane, en présence de catalyseurs d'oxydes métalliques mixtes de cuivre-manganèse-aluminium Download PDF

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WO2018051198A1
WO2018051198A1 PCT/IB2017/054158 IB2017054158W WO2018051198A1 WO 2018051198 A1 WO2018051198 A1 WO 2018051198A1 IB 2017054158 W IB2017054158 W IB 2017054158W WO 2018051198 A1 WO2018051198 A1 WO 2018051198A1
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mol
mpa
syngas
methane
containing composition
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PCT/IB2017/054158
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English (en)
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Aghaddin Mamedov
Clark Rea
Shahid Shaikh
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Sabic Global Technologies B.V.
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Publication of WO2018051198A1 publication Critical patent/WO2018051198A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention generally concerns a process for hydrogenation of carbon dioxide (C0 2 ) to produce a synthesis gas (syngas) containing composition that includes hydrogen (H 2 ) and carbon monoxide (CO).
  • the process includes contacting a CuMnAl mixed metal oxide catalyst under conditions suitable to produce the syngas composition.
  • Syngas (which includes carbon monoxide and hydrogen gases) is oftentimes used to produce chemicals such as methanol, tert-butyl methyl ether, ammonia, fertilizers, 2-ethyl hexanol, formaldehyde, acetic acid, and 1,4-butane diol.
  • Syngas can be produced by common methods such as methane steam reforming technology as shown in reaction equation (1), partial oxidation of methane as shown in reaction (2), or dry reforming of methane as shown in reaction (3):
  • Equation (4) illustrates the catalyst deactivation event due to carbonization.
  • the discovery is premised on the use of a CuMnAl mixed metal oxide catalyst (i.e., Cu-Mn/Al 2 0 3 or copper oxide-manganese oxide/alumina supported catalyst) at temperatures of at least 550 °C and a pressure greater than atmospheric pressure.
  • a CuMnAl mixed metal oxide catalyst i.e., Cu-Mn/Al 2 0 3 or copper oxide-manganese oxide/alumina supported catalyst
  • Such a process has a C0 2 conversion of at least 30% and can produce syngas compositions suitable for use as an intermediate or as feed material in a subsequent synthesis (e.g., methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins) to form a chemical product or a plurality of chemical products.
  • a subsequent synthesis e.g., methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins
  • the produced syngas is particularly tailored for use in producing oxo-products (e.g., C 2 + alcohols, alkyl ethers, dimethyl ether, or the like).
  • the process can include contacting a CuMnAl mixed metal oxide catalyst with a reactant feed that includes H 2 and C0 2 having a H 2 :C0 2 volume ratio of at least 0.5 (e.g., 0.5 to 1.5) at a temperature of at least 550 °C (e.g., 550 °C to 650 °C, preferably 570 °C to 650 °C, more preferably 580 °C to 645 °C or 630 °C to 650 °C) and a pressure of at least 0.5 MPa (e.g., 0.5 MPa to 6 MPa, 0.5 MPa to 3 MPa, or 0.5 MPa to 2 MPa, or 0.5 MPa to 1.5 MPa) to produce a product stream that includes the syngas containing composition containing H 2 , CO at a molar ratio of 2: 1 or less (e.g., 1.8: 1 or less, preferably 0.5 : 1 to 1.5 : 1, more preferably 0.7: 1 to 1.3
  • the C0 2 is removed from the produced syngas composition (e.g., by amine adsorption).
  • the syngas containing composition can include 5 mol.% to 15 mol.% CO, 55 mol.% to 65 mol.% C0 2 , 15 mol.%) to 25 mol.%> CH 4 , and 5 mol.%> to 15 mol.%> H 2 .
  • the syngas containing composition can include 5 mol.% to 15 mol.% CO, 45 mol.% to 55 mol.% C0 2 , 25 mol.% to 35 mol.% CH 4 , and 10 mol.% to 15 mol.% H 2 .
  • the CuMnAl mixed metal oxide catalyst can include 1% to 10 wt.% Cu, 1 wt.% to 30 wt.% of Mn, and 60% to 98% of A1 2 0 3 .
  • the catalyst includes 3 to 7 wt.% Cu, preferably about 5 wt.% Cu, 5 to 15 wt. % Mn, preferably about 10 wt.% of Mn, and at least 75 wt.% of A1 2 0 3 , preferably about 83 to 87 wt. % A1 2 0 3 .
  • the catalyst includes about 5% Cu, about 10%) Mn and about 85% A1 2 0 3 .
  • the active copper is inhibited from leaching from the catalyst as the co-precipitation produces small particles of copper and manganese embedded in the high interface are of the alumina particles with a common interface area.
  • impregnation techniques produce large particles of pure copper and manganese, and crystallized large particles of alumina with little common interface area.
  • the catalyst can have a surface area of 200 m 2 /g to 300 m 2 /g, 225 m 2 /g to 270 m 2 /g, 250 m 2 /g to 260 m 2 /g, or 254 m 2 /g and/or a density of 0.85 to 0.95 g/cm 3 .
  • a H 2 gas flow rate of can be 30 to 70 mL/min and a C0 2 gas flow rate can be 30 to 70 mL/min.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component.
  • substantially and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
  • the process of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc., disclosed throughout the specification.
  • a basic and novel characteristic of the processes of the present invention are their abilities to hydrogenate carbon dioxide to produce syngas and methane.
  • Embodiment one is a process for hydrogenating carbon dioxide (C0 2 ) to produce an oxo- synthesis syngas and methane (CH 4 ) containing composition.
  • the process includes the steps of contacting a CuMnAl mixed metal oxide catalyst with a reactant feed comprising hydrogen (H 2 ) and C0 2 at a H 2 :C0 2 volume ratio of at least 0.5: 1, wherein the reaction occurs at a temperature of at least 550 °C and a pressure of at least 0.5 MPa to produce a product stream containing H 2 and CO at a H 2 :CO molar ratio of 2 or less and methane (CH 4 ) in an amount of at least 5 molar %.
  • Embodiment 2 is the process of Embodiment 1, wherein temperature is from 550 °C to 650 °C, and preferably 570 °C to 650 °C, or more preferably 600 °C to 645 °C.
  • Embodiment 3 is the process of any one of Embodiments 1 to 2, wherein the pressure is from 0.5 MPa to 6 MPa, 0.5 MPa to 3 MPa, or 0.5 MPa to 2 MPa.
  • Embodiment 4 is the process of any one of Embodiments 1 to 3, wherein the reactant feed contains a H 2 :C0 2 volume ratio of 0.5 to 2, the reaction occurs at a temperature of 570 °C to 600 °C, and a pressure of 0.5 MPa to 3 MPa, and the syngas containing composition contains a H 2 :CO molar ratio of 0.7: 1 to 1.3 : 1, and contains methane (CH 4 ) in an amount of 15 molar % to 25 molar %.
  • Embodiment 5 is the process of any one of Embodiments 1 to 4, wherein the reaction occurs at a temperature of 550 °C to 650 °C and a pressure of 0.5 MPa to 2 MPa, wherein the syngas containing composition contains a H 2 :CO molar ratio of 0.5 to 2, and contains methane (CH 4 ) in an amount of 5 molar % to 35 molar %.
  • Embodiment 6 is the process of any one of Embodiments 1 to 5, wherein the reaction occurs at a temperature of 635 °C to 645 °C and a pressure of 0.5 MPa to 1.5 MPa, and the syngas containing composition contains a H 2 :CO molar ratio of 0.9: 1 to 1.3 : 1, and contains methane (CH 4 ) in an amount of 25 molar % to 35 molar %.
  • Embodiment 7 is the process of any one of Embodiments 1 to 6, wherein the syngas containing composition is used to produce oxo- products.
  • Embodiment 8 is the process of any one of Embodiments 1 to 7, wherein the syngas containing composition contains 30 mol. % C0 2 or more.
  • Embodiment 9 is the process of any one of Embodiments 1 to 8, wherein the CuMnAl mixed metal oxide catalyst contains 1 wt.% to 10 wt.% Cu, 1 wt.% to 30 wt.% of Mn, and 60 wt.% to 98 wt.% of A1 2 0 3 .
  • Embodiment 10 is the process of any one of Embodiments 1 to 9, wherein the CuMnAl mixed metal oxide catalyst contains 3 to 7 wt.% Cu, preferably about 5 wt.% Cu, 5 to 15 wt.
  • Embodiment 11 is the process of any one of Embodiments 1 to 10, wherein the catalyst has a surface area of 200 m 2 /g to 300 m 2 /g, 225 m 2 /g to 270 m 2 /g, or 250 m 2 /g to 260 m 2 /g.
  • Embodiment 12 is the process of any one of Embodiments 1 to 11, further including a H 2 gas flow rate of 30 to 70 mL/min and the C0 2 gas flow rate of 30 to 70 mL/min.
  • Embodiment 13 is the process of Embodiment 12, wherein the H 2 gas flow rate is about 50 mL/min and the C0 2 gas flow rate is about 50 mL/min.
  • Embodiment 14 is the process of any one of Embodiments 1 to 13, wherein the syngas containing composition has a H 2 :CO molar ratio of 0.8: 1 to 1.3 : 1.
  • Embodiment 15 is the process of any one of Embodiments 1 to 13, wherein the syngas containing composition contains 5 mol.% to 15 mol.% CO, 55 mol.% to 65 mol.% C0 2 , 15 mol.% to 25 mol.% CH 4 and 5 mol.% to 15 mol.% H 2 .
  • Embodiment 16 is the process of any one of Embodiments 1 to 14, wherein the syngas containing composition contains 5 mol.% to 15 mol.% CO, 45 mol.% to 55 mol.% C0 2 , 25 mol.% to 35 mol.% CH 4 and 10 mol.% to 15 mol.% H 2 .
  • Embodiment 17 the process of any one of Embodiments 1 to 16, wherein the C0 2 conversion is at least 30%.
  • Embodiment 18 is the process of any one of Embodiments 1 to 17, further including the step of removing the C0 2 from the product stream.
  • Embodiment 19 is the process of any one of Embodiments 1 to 18, further including the step of using the produced syngas mixture as an intermediate or as feed material in a subsequent synthesis to form oxo-products.
  • Embodiment 20 is the process of Embodiment 18, wherein the oxo-products include C2+ alcohols, alkyl ethers, or dimethyl ether.
  • FIG. 1 is an illustration of a process of the present invention to produce syngas and methane using a combined H 2 and C0 2 containing reactant feed gas and the CuMnAl mixed metal oxide catalyst of the present invention.
  • FIG. 2 is an illustration of a process of the present invention to produce syngas and methane using a H 2 reactant feed gas source, a C0 2 reactant feed gas source, and the CuMnAl mixed metal oxide catalyst of the present invention.
  • the discovery is premised on the use of a CuMnAl mixed metal oxide catalyst in the hydrogenation of carbon dioxide reaction at elevated pressure and temperature. This results in a product stream that includes syngas and methane (e.g., at least 5 mol. %) suitable for the production of oxo-products.
  • Conditions sufficient to produce syngas from the hydrogenation of C0 2 reaction include temperature, time, flow rate of feed gases, and pressure.
  • the temperature range for the hydrogenation reaction can range from at least 550 °C to 650 °C, from about 570 °C to 650 °C, or 580 °C to 645 °C and all ranges and values there between (e.g., 550 °C, 555 °C, 560 °C, 565 °C, 570 °C, 575 °C, 580 °C, 585 °C, 590 °C, 595 °C, 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, and 650 °C).
  • the temperature can be 630 °C to 650 °C.
  • the average pressure for the hydrogenation reaction can range from above atmospheric pressure or from 0.5 MPa to about 6 MPa, preferably, about 0.5 MPa to about 3 MPa and all pressures there between ⁇ e.g., 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, and 6 MPa). In one particular instance, the pressure can be 0.5 MPa to 1.5 MPa. The upper limit on pressure can be determined by the reactor used. The conditions for the hydrogenation of C0 2 to syngas can be varied based on the type of the reactor used.
  • the combined flow rate for the for the reactants ⁇ e.g., H 2 and C0 2 ) in the hydrogenation reaction can range from at least 90 mL/min, 100 mL/min to 140 mL/min, from about 100 mL/min to about 105 mL/ min or all ranges and values there between ⁇ e.g., at least 90 mL/min, 91 mL/min, 92 mL/min, 93 mL/min, 94 mL/min, 95 mL/min, 96 mL/min, 97 mL/min 98 mL/min, 99 mL/min, 100 mL/min, 101 mL/min, 102 mL/min, 103 mL/min, 104 mL/min, 105 mL/min, 106 mL/min, 107 mL/min 108 mL/min, 109 mL/min, 110 mL/min,
  • the H 2 flow rate can range from 30 mL/min to 70 mL/min, 35 to 65 mL/min, 40 to 60 mL/min, or all ranges and values there between ⁇ e.g., 30 mL/min, 31 mL/min, 32 mL/min, 33 mL/min, 34 mL/min, 35 mL/min, 36 mL/min, 37 mL/min, 38 mL/min, 39 mL/min, 40 mL/min, 41 mL/min, 42 mL/min, 43 mL/min, 44 mL/min, 45 mL/min, 46 mL/min, 47 mL/min, 48 mL/min, 49 mL/min, 50 mL/min, 51 mL/min, 52 mL/min, 53 mL/min, 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min, 50
  • the C0 2 gas flow rate can range from 30 mL/min to 70 mL/min, 35 to 65 mL/min, 40 to 60 mL/min, or all ranges and values there between (e.g., 30 mL/min, 31 mL/min, 32 mL/min, 33 mL/min, 34 mL/min, 35 mL/min, 36 mL/min, 37 mL/min, 38 mL/min, 39 mL/min, 40 mL/min, 41 mL/min, 42 mL/min, 43 mL/min, 44 mL/min, 45 mL/min, 46 mL/min, 47 mL/min, 48 mL/min, 49 mL/min, 50 mL/min, 51 mL/min, 52 mL/min, 53 mL/min, 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min,
  • the H 2 gas flow rate is 40 to 60 mL/min and the C0 2 gas flow rate is 40 to 60 mL/min at 0.5 MPa to 3 MPa. In a preferred instance, the H 2 gas flow rate is about 50 mL/min and the C0 2 gas flow rate is about 50 mL/min at 0.5 MPa to 2 MPa.
  • the reaction can be carried out over the CuMnAl mixed metal oxide catalyst of the current invention having particular syngas selectivity and conversion results. Therefore, in one aspect, the reaction can be performed with a C0 2 conversion of at least 30 mol%, at least 50 mol%, at least 70 mol%, at least 80 mol%, or at least 99 mol%.
  • the method can further include collecting or storing the produced syngas along with using the produced syngas as a feed source, solvent or a commercial product, and/or separating the carbon dioxide from the syngas composition.
  • the catalyst Prior to use, the catalyst can be subjected to reducing conditions to convert the copper oxide and the other metals in the catalyst to a lower valance state (e.g., Cu +2 to Cu +1 and Cu° species, Mn +2 to Mn°, etc.).
  • reducing conditions includes flowing a gaseous stream that includes a hydrogen gas or hydrogen gas containing mixture (e.g., a H 2 and argon gas stream) at a temperature of 250 °C to 280 °C for a period of time (e.g., 1, 2, or 3 hours) over the catalyst.
  • the system 100 can be used to convert a reactant gas stream of carbon dioxide (C0 2 ) and hydrogen (H 2 ) into syngas using the CuMnAl mixed metal oxide catalyst (e.g., CuO-MnO/Al 2 0 3 ) of the present invention.
  • the system 100 can include a combined reactant gas source 102, a reactor 104, and a collection device 106.
  • the combined reactant gas source 102 can be configured to be in fluid communication with the reactor 104 via an inlet 108 on the reactor.
  • the combined reactant gas source 102 can be configured such that it regulates the amount of reactant feed (e.g., C0 2 and H 2 ) entering the reactor 104.
  • FIG. 2 depicts a system 200 for the process of the present invention having two feed inlets.
  • a hydrogen gas reactant feed source 202 and a carbon dioxide reactant gas feed source 204 are in fluid communication with reactor 104 via hydrogen gas inlet 206 and carbon dioxide gas inlet 208, respectively.
  • the reactor 104 can include a reaction zone 1 10 having the CuMnAl mixed metal oxide catalyst 1 12 of the present invention.
  • the reactor can include various automated and/or manual controllers, valves, heat exchangers, gauges, etc., for the operation of the reactor.
  • the reactor can have insulation and/or heat exchangers to heat or cool the reactor as desired.
  • the amounts of the reactant feed and the mixed metal oxide catalyst 1 12 used can be modified as desired to achieve a given amount of product produced by the systems 100 or 200.
  • a continuous flow reactor can be used.
  • Non-limiting examples of continuous flow reactors include fixed-bed reactors, fluidized reactors, bubbling bed reactors, slurry reactors, rotating kiln reactors, moving bed reactors or any combinations thereof when two or more reactors are used.
  • the reactant gas is preheated prior to being fed to the reactor.
  • reaction zone 1 10 is a multi-zone reactor with different stages of heating in each zone.
  • the reactor 104 can include an outlet 1 14 configured to be in fluid communication with the reaction zone 110 and configured to remove a first product stream comprising syngas from the reaction zone.
  • Reaction zone 1 10 can further include the reactant feed and the first product stream.
  • the products produced can include hydrogen gas, carbon monoxide, and methane.
  • the product stream can also include unreacted carbon dioxide, and water.
  • the catalyst can be included in the product stream.
  • the collection device 106 can be in fluid communication with the reactor 104 via the product outlet 1 14. Reactant gas inlets 108, 206, and 208, and the outlet 1 14 can be opened and closed as desired.
  • the collection device 106 can be configured to store, further process, or transfer desired reaction products (e.g., syngas) for other uses.
  • collection device 106 can be a separation unit or a series of separation units that are capable of separating the gaseous components from each other (e.g., separate carbon dioxide, methane, or water from the stream). Water can be removed from the product stream with any suitable method known in the art (e.g., condensation, liquid/gas separation, etc.). The separated methane can be used as fuel in other applications or subjected to conditions (e.g., reforming reactions) to produce additional syngas.
  • gaseous components e.g., separate carbon dioxide, methane, or water from the stream.
  • Water can be removed from the product stream with any suitable method known in the art (e.g., condensation, liquid/gas separation, etc.).
  • the separated methane can be used as fuel in other applications or subjected to conditions (e.g., reforming reactions) to produce additional syngas.
  • Any unreacted reactant gas e.g., C0 2
  • C0 2 reactant gas
  • the resulting syngas can be sold, stored, or used in other processing units as a feed source.
  • the systems 100 or 200 can also include a heating/cooling source (not shown).
  • the heating/cooling source can be configured to heat or cool the reaction zone 1 10 to a temperature sufficient (e.g., at least 550 °C or 550 °C to 650 °C, preferably 570 °C to 645 °C, or 580 °C to 645 °C, or 635 °C to 645 °C) to convert C0 2 in the reactant feed to syngas via hydrogenation.
  • a heating/cooling source can be a temperature controlled furnace or an external, electrical heating block, heating coils, or a heat exchanger.
  • the CuMnAl mixed metal oxide catalyst of the present invention can include 1% to 10 wt.% Cu, 1 wt.% to 30 wt.% of Mn and 60% to 98% of A1 2 0 3 .
  • the catalyst includes 3 to 7 wt.% Cu, preferably about 5 wt.% Cu, 5 to 15 wt. % Mn, preferably about 10 wt.% of Mn, and at least 75 wt.% of A1 2 0 3 , preferably about 83 to 87 wt. % A1 2 0 3 .
  • the manganese (Mn) and copper (Cu) can each be in form of an oxide (e.g., Mn0 2 , Mn 2 0 3 , Mn 3 0 4 , or any mixture thereof) and (CuO, Cu 2 0, Cu0 2 , Cu 2 0 3 , or any mixture thereof).
  • the manganese oxide is MnO and the copper oxide is CuO.
  • copper metal is present (e.g., Cu°).
  • the content of elemental Mn can range from about 1 wt.% to about 50 wt.% based on total weight of the supported catalyst composition. In certain embodiments, the Mn content ranges from 5 wt.
  • the amount of elemental manganese and the amount of elemental copper present in the catalysts of the present invention can range from 4: 1 to 1 :4, 3 : 1 to about 1 :3, 1 :2 to 2: 1, 1 : 1.5 to 1.5 : 1.
  • the mole ratio is about 1 : 1.
  • the elemental copper content of the catalyst can range from 1 wt.% to 10 wt.% based on the total weight of the catalyst.
  • the copper content ranges from 2.5 wt. % to about 9 wt. %. from 3 wt. % to about 8 wt. %, from 4 wt. % to about 7 wt.
  • % or any range or value there between (e.g., 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.% 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5, wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.% or 10 wt.%).
  • Aluminum in the catalyst can exist as an oxide (e.g., A1 2 0 3 ) and act as a support material for the manganese and copper oxides.
  • the amount of aluminum oxide present in the catalyst can vary depending on the amount of copper and manganese.
  • the alumina (A1 2 0 3 ) content of the catalyst can range from 60 wt.% to 98 wt. % based on the total weight of the catalyst. In other embodiments, the alumina content ranges from 60 wt.% to about 90 wt.%. from 70 wt.% to about 85 wt.
  • the remaining amount of oxygen present in the catalyst can vary depending on the amount and oxidation state of the copper, manganese, and makes up the balance of the catalyst weight.
  • the catalyst can have a surface area of 200 m 2 /g to 300 m 2 /g, 225 m 2 /g to 270 m 2 /g, 250 m 2 /g to 260 m 2 /g, or 254 m 2 /g.
  • the catalyst can have a density of 0.85 to 0.95 g/cm 3 , 0.86 to 0.94 g/cm 3 , 0.87 to 0.90 g/dm 3 , or 0.89 g/cm 3 , 0.86 to 0.94 g/cm 3 , 0.87 to 0.90 g/cm 3 , or 0.89 g/cm 3 .
  • Non-limiting sources for the manganese, copper, and aluminum used in the preparation of the catalysts include nitrates, halides, organic acid, inorganic acid, hydroxides, carbonates, oxyhalides, sulfates and other groups which may exchange with oxygen under high temperatures so that the metal compounds become metal oxides. These materials can be obtained from commercial vendors, for example, Sigma- Aldrich ® (U. S. A).
  • the catalyst can be made using a co- precipitation method.
  • a first metal salt e.g., a copper metal salt
  • a second metal salt e.g., manganese metal salt
  • a third metal salt e.g., an aluminum metal salt
  • a solvent e.g., a water solution
  • the first metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of copper.
  • Examples of the second metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of manganese.
  • Examples of the third metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of aluminum.
  • Cu(N0 3 ) 3 , Mn(N0 3 ) 2 , and A1(N0 3 ) 3 can be solubilized in deionized water. In some embodiments, three solutions are prepared and mixed together.
  • the ratio of Cu:Mn: Al salt can be 1 :2: 16 to 1:1 :5, or 1:2:15, 1:2, 14, 1:2:13, 1:2, 12, 1:2, 11, 1:2:10, 1:2:9, 1:2: 8, 1:2:7, 1:2:6, 1:2:5, 1:1:15, 1:1:14, 1:1:13, 1:1:12, 1:1:11, 1:1:10, 1:1:8, 1:1:7, 1:1:6., or 1:1:5.
  • Aqueous base e.g., ammonium hydroxide or sodium hydroxide
  • the pH of the solution can be 7 to 10, 7.5 to 9.5, or 9 after addition of the base.
  • the Cu/Mn/Al metal hydroxide precursor can be heated from 55 °C to 75 °C, 60 °C to 70 °C and all values there between (e.g., 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 64 °C, 65 °C, 66 °C, 67 °C , 68 °C , 69 °C, 70 °C, 71 °C, 72 °C, 73 °C, 74 °C, or 75 °C) with agitation to further the formation of the Cu/Mn/Al metal hydroxide precursor.
  • the Cu/Mn/Al precursor precipitate can be separated from the solution using known separation techniques (e.g., centrifugation, filtration, etc.).
  • the separated Cu/Mn/Al precursor precipitate can be washed with water (e.g., deionized water) to remove any excess base. Washing and filtering the Cu/Mn/Al precursor precipitate can be repeated as necessary to remove all, or substantially all, of the base from the Cu/Mn/Al precursor precipitate.
  • Residual water can be removed from the Cu/Mn/Al precursor by heating the solution (e.g., drying the solution) at a temperature from 90 °C to 135 °C, or 95 °C to 130 °C, or any value there between (e.g., 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, 110 °C, 111 °C, 112 °C, 113 °C, 114 °C, 115 °C, 116 °C, 117 °C, 118 °C, 119 °C, 120 °C, 121 °C
  • drying is performed at 125 °C for 12 hours.
  • the dried CuMnAl material can be then be heated to 230 °C to 260 °C, 240 °C to 255 °C, or 230 °C, 231 °C, 232 °C, 233 °C, 234 °C, 235 °C, 236 °C, 237 °C, 238 °C, 239 °C, 240 °C, 241 °C, 242 °C, 243 °C, 244 °C, 245 °C, 246 °C, 247 °C, 248 °C,
  • the heat treated CuMnAl material can then be calcined by heating the dried material to an average temperature between 350 °C and 800 °C, 400 °C to 750 °C, with 600 °C being preferred, for 3 to 12 hours or 4 to 8 hours in the presence of a flow of an oxygen source (e.g., air at 250 cc/per minute) to form the CuMnAl mixed metal oxide catalyst.
  • an oxygen source e.g., air at 250 cc/per minute
  • the catalyst particles can be reduced in size (e.g., crushed) to a particle size of 20-50 mesh.
  • Carbon dioxide gas and hydrogen gas can be obtained from various sources.
  • the carbon dioxide can be obtained from a waste or recycle gas stream (e.g., from a plant on the same site such as from ammonia synthesis) or after recovering the carbon dioxide from a gas stream.
  • a benefit of recycling such carbon dioxide as a starting material in the process of the invention is that it can reduce the amount of carbon dioxide emitted to the atmosphere (e.g., from a chemical production site).
  • the hydrogen gas may be from various sources, including streams coming from other chemical processes, like water splitting (e.g., photocatalysis, electrolysis, or the like), additional syngas production, ethane cracking, methanol synthesis, or conversion of methane to aromatics.
  • the volume ratio of H 2 to C0 2 (H 2 :C0 2 ) reactant gas ratio for the hydrogenation reaction can range from 0.5 : 1 to 2: 1 or from 1 : 1 to 1.5 : 1.
  • the reactant gas stream includes 30 to 70 vol.% H 2 and 30 to 70 vol.% C0 2 .
  • the reactant gas stream includes 40 to 60 vol.% H 2 and 40 to 60 vol.% C0 2 .
  • the reactant gas stream includes about 50 vol.% H 2 and about 50 vol.% C0 2 .
  • the reactant gas stream includes about 60 vol.% H 2 and 40 vol.% C0 2 .
  • the streams are not combined.
  • the hydrogen and carbon dioxide can be delivered at the same H 2 :C0 2 molar ratio.
  • the remainder of the reactant gas stream can include another gas or gases provided the gas or gases are inert, such as argon (Ar) or nitrogen (N 2 ), and do not negatively affect the reaction. All possible percentages of C0 2 plus H 2 plus inert gas in the current embodiments can have the described H 2 :C0 2 ratios herein.
  • the reactant mixture is highly pure and substantially devoid of water or steam.
  • the carbon dioxide can be dried prior to use (e.g., pass through a drying media) to contain minimal amounts of water or no water at all.
  • the reactant feed contains only C0 2 and H 2 or a minimal amount of alkanes (e.g., less the 5 mol.% methane and/or CO).
  • the process of the present invention can produce a product stream that includes a mixture of methane, H 2 , and CO having a molar H 2 :CO ratio suitable for the synthesis of various chemical products.
  • Non-limiting examples of synthesis include methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins.
  • Non-limiting examples of products that can be produced include aliphatic oxygenates, methanol, olefin synthesis, aromatics production, carbonylation of methanol, carbonylation of olefins, or reduction of iron oxide in steel production.
  • the molar H 2 :CO ratio can be 2.0: 1 or less, 1.8: 1 or less, 0.70: 1 to 1.3 : 1, 0.8: 1 to 1.2: 1, or about 1 : 1, which is suitable for oxo-products (e.g., C 2 + alcohols, dimethyl ether, etc.).
  • the amount of alkane (e.g., methane) produced in the process of the present reaction can be at least 5 mol.%, at least 10 mol.%, 15 mol.%, 20 mol.%, 25 mol.% 30 mol.%), or 35 mol.%> or any range or value there between (e.g., 10 mol.%>, 1 1 mol.%>, 12 mol.%, 13 mol.%, 14 mol.%, 15 mol.%, 16 mol.%, 17 mol.%, 18 mol.%, 19 mol.%, 20 mol.%, 21 mol.%, 22 mol.%, 23 mol.%, 24 mol.%, 25 mol.%, 26 mol.%, 27 mol.%, 28 mol.%, 29 mol.%, 10 mol.%, 30 mol.%, 31 mol.%, 32 mol.%, 33 mol.%, 34 mol.%, or 35 mol.%),
  • the product stream can include unreacted C0 2 .
  • the product stream can include 40 mol.%, 45 mol.%), 50 mol.%, 55 mol.%, or 60 mol.% of C0 2 based on the total moles of components in the product stream.
  • the syngas containing composition can include 5 mol.% to 15 mol.% CO, 55 mol.% to 65 mol.% C0 2 , 15 mol.% to 25 mol.% CH 4 , and 5 mol.%) to 15 mol.%) H 2 .
  • the syngas containing composition can include 5 mol.% to 15 mol.% CO, 45 mol.% to 55 mol.% C0 2 , 25 mol.% to 35 mol.% CH 4 , and 10 mol.% to 15 mol.% H 2 .
  • the CuMnAl metal oxide precursor material was isolated by filtration and washed with water (2 L) to remove excess base. The washed CuMnAl metal oxide precursor material was dried at 125 °C for 12 hours, and then heated to 250 °C for 6 hours. The heat-treated CuMnAl metal oxide precursor material was calcined at 650 °C in an air flow of 5000 cc/min for 6 hours to form the CuMnAl mixed metal oxide catalyst of the present invention.
  • the catalyst included 5 wt.% Cu, 10 wt.% Mn with the balance being A1 2 0 3 , and had a surface area of 254 m 2 /g and a density of 0.89 g/cm 3 . Surface area was determined by Autosorb Instrument (Quntachrmoe Instruments (U.S.A.), using Nitrogen Adsorbate at 77.35 K temperature. Powder density was determined by packing the powder in a graduated cylinder and then measuring its volume and weight.
  • equation (8) presents the sum of all carbon, products divided by the total number of carbons.
  • Example 2 The general procedure of Example 2 was followed with the following conditions: a pressure of 2.8 MPa, a temperature of 620 °C, a H 2 flow rate of 50 cc/min, and a C0 2 flow rate of 50 cc/min.
  • Time on stream (TOS) Time on stream
  • molar percentage of components in the product stream and % carbon dioxide conversion results are listed in Table 1.
  • Example 2 The general procedure of Example 2 was followed using the following conditions: a pressure of 2.8 MPa, a temperature of 580 °C, a H 2 flow rate of 40 cc/min, and a C0 2 flow rate of 60 cc/min. Results are listed in Table 2.
  • Example 2 The general procedure of Example 2 was followed using the following conditions: a pressure of 2.8 MPa, a temperature of 600 °C, a H 2 flow rate of 60 cc/min, and a C0 2 flow rate of 40 cc/min. Results are listed in Table 3. Table 3
  • Example 2 The general procedure of Example 2 was followed using the following conditions: a pressure of 1 MPa, a temperature of 640 °C, a H 2 flow rate of 50 cc/min, and a C0 2 flow rate of 50 cc/min. Results are listed in Table 4.
  • the process conditions for Examples 3-6 produced syngas with a methane content (e.g., about 13.5 to 29.5 mol.%). Further, the syngas produced at the conditions of Examples 3-5 with the catalyst of the present invention is suitable for use as an intermediate or as feed material in a subsequent synthesis (e.g., olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins) to form a chemical product or a plurality of chemical products (e.g., oxo-products such as C 2 + alcohols or ethers).
  • a subsequent synthesis e.g., olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins
  • a chemical product or a plurality of chemical products e.g., oxo-products such as C 2 + alcohols or ethers

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Abstract

L'invention concerne des procédés et des catalyseurs permettant l'hydrogénation d'une réaction de dioxyde de carbone. L'invention concerne en particulier un procédé d'hydrogénation de dioxyde de carbone (CO2) destiné à produire une composition contenant du gaz de synthèse qui comprend de l'hydrogène (H2), du monoxyde de carbone (CO) et du méthane. Ce procédé peut consister à mettre en contact un catalyseur d'oxydes métalliques mixtes CuMnAl avec H2 et CO2, à une température d'au moins 550 °C et à une pression supérieure à la pression atmosphérique afin de produire la composition contenant du gaz de synthèse.
PCT/IB2017/054158 2016-07-25 2017-07-10 Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse et méthane, en présence de catalyseurs d'oxydes métalliques mixtes de cuivre-manganèse-aluminium WO2018051198A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3213145A (en) * 1960-03-28 1965-10-19 Standard Oil Co Catalytic hydrogenation of esters of aromatic monocarboxylic acids to aryl-substituted methanols
US5243095A (en) * 1992-04-24 1993-09-07 Engelhard Corporation Hydrogenation catalyst, process for preparing and process for using said catalyst
US5496530A (en) * 1992-12-10 1996-03-05 Haldor Topsoe A/S Process for the preparation of carbon monoxide rich gas
CN1127240A (zh) * 1995-09-13 1996-07-24 中国科学院大连化学物理研究所 二氧化碳加氢反应制低碳烯烃新过程及催化剂
US20130150466A1 (en) * 2011-12-08 2013-06-13 Saudi Basic Industries Corporation, Riyadh (Sa) Mixed oxide based catalyst for the conversion of carbon dioxide to syngas and method of preparation and use
CN103551153A (zh) * 2013-10-29 2014-02-05 西南化工研究设计院有限公司 一种用于二氧化碳甲烷化的铜基催化剂及其制备方法
WO2016007607A1 (fr) * 2014-07-11 2016-01-14 Dow Global Technologies Llc Conversion de monoxyde de carbone, de dioxyde de carbone ou d'une combinaison de ces derniers sur catalyseur hybride

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3213145A (en) * 1960-03-28 1965-10-19 Standard Oil Co Catalytic hydrogenation of esters of aromatic monocarboxylic acids to aryl-substituted methanols
US5243095A (en) * 1992-04-24 1993-09-07 Engelhard Corporation Hydrogenation catalyst, process for preparing and process for using said catalyst
US5496530A (en) * 1992-12-10 1996-03-05 Haldor Topsoe A/S Process for the preparation of carbon monoxide rich gas
CN1127240A (zh) * 1995-09-13 1996-07-24 中国科学院大连化学物理研究所 二氧化碳加氢反应制低碳烯烃新过程及催化剂
US20130150466A1 (en) * 2011-12-08 2013-06-13 Saudi Basic Industries Corporation, Riyadh (Sa) Mixed oxide based catalyst for the conversion of carbon dioxide to syngas and method of preparation and use
CN103551153A (zh) * 2013-10-29 2014-02-05 西南化工研究设计院有限公司 一种用于二氧化碳甲烷化的铜基催化剂及其制备方法
WO2016007607A1 (fr) * 2014-07-11 2016-01-14 Dow Global Technologies Llc Conversion de monoxyde de carbone, de dioxyde de carbone ou d'une combinaison de ces derniers sur catalyseur hybride

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