WO2018015827A1 - Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseurs à oxyde métallique mixte cuivre-manganèse-aluminium - Google Patents

Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseurs à oxyde métallique mixte cuivre-manganèse-aluminium Download PDF

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WO2018015827A1
WO2018015827A1 PCT/IB2017/053918 IB2017053918W WO2018015827A1 WO 2018015827 A1 WO2018015827 A1 WO 2018015827A1 IB 2017053918 W IB2017053918 W IB 2017053918W WO 2018015827 A1 WO2018015827 A1 WO 2018015827A1
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mol
syngas
mpa
metal oxide
carbon dioxide
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PCT/IB2017/053918
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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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    • 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
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • 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
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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-butanediol.
  • 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 600 °C and a pressure greater than atmospheric pressure.
  • Such a process has a C0 2 conversion of at least 50% 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 methanol.
  • a process for hydrogenation of carbon dioxide (C0 2 ) to produce a syngas containing composition that includes hydrogen (H 2 ) and carbon monoxide (CO) is described.
  • the process can include contacting a CuMnAl mixed metal oxide catalyst with a reactant feed that includes H 2 and C0 2 at a temperature of at least 600 °C (e.g., 600 °C to 650 °C, preferably 610 °C to 630 °C, more preferably 615 °C to 625 °C, or most preferably about 620 °C) and a pressure greater than atmospheric pressure (e.g., 0.5 MPa to 6 MPa, preferably 2 MPa to 4 MPa, or more preferably 2.5 MPa to 3.5 MPa, or most preferably 2.5 MPa to 3 MPa) to produce a product stream that includes the syngas containing composition containing H 2 and CO.
  • 600 °C e.g., 600 °C to 650 °C, preferably 610 °C to
  • 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/mL.
  • the volume ratio of the reactant H 2 to reactant C0 2 can be least 3 : 1 or about 4: 1, and/or a H 2 gas flow rate of can be 75 to 110 mL/min and a C0 2 gas flow rate can be 20 to 30 mL/min.
  • the produced syngas composition can have a methane content of less than 5 mol%.
  • the produced syngas can have a H 2 to CO molar ratio of at least 1 : 1, preferably 1 : 1 to 4: 1.
  • 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.
  • 10 moles of component in 100 moles of the material is 10 mol.% of component.
  • substantially and its variations are defined as being largely but not necessarily wholly what is specified as understood by one of ordinary skill in the art, and in one non-limiting embodiment substantially refers to 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 process of the present invention are their abilities to hydrogenate carbon dioxide to produce syngas.
  • Embodiment 1 is a process for hydrogenating carbon dioxide (C0 2 ) to produce a syngas containing composition including hydrogen (H 2 ) and carbon monoxide (CO).
  • the process includes the step of contacting a CuMnAl mixed metal oxide catalyst with H 2 and C0 2 at a temperature of at least 600 °C and a pressure greater than atmospheric pressure to produce the syngas containing composition containing H 2 and CO.
  • Embodiment 2 is the process of Embodiment 1, wherein the temperature is from 610 °C to 650 °C, preferably 610 °C to 630 °C, or more preferably 615 °C to 625 °C.
  • Embodiment 3 is the process of any one of Embodiments 1 or 2, wherein the pressure is from 0.5 MPa to 6 MPa, preferably 2 MPa to 4 MPa, or more preferably 2.5 MPa to 3.5 MPa.
  • Embodiment 4 is the process of any one of Embodiments 1 to 3, wherein the reaction conditions include a temperature of 615 °C to 625 °C and a pressure of 2.5 MPa to 3.5 MPa, wherein the syngas containing composition includes a H 2 :CO molar ratio of 1 : 1 to 4: 1 and includes less than 5 mol.% of methane.
  • Embodiment 5 is the process of any one of Embodiments 1 to 4, wherein the syngas containing composition is used to produce methanol.
  • Embodiment 6 is the process of any one of Embodiments 1 to 5, wherein the syngas containing composition includes less than 5 mol.% of methane, preferably 2 to 4 mol % of methane.
  • Embodiment 7 is the process of any one of Embodiments 1 to 6, wherein the syngas containing composition includes 15 mol. % C0 2 or less.
  • Embodiment 8 is the process of any one of Embodiments 1 to 7, wherein the CuMnAl mixed metal oxide catalyst includes 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 9 is the process of any one of Embodiments 1 to 8, wherein the CuMnAl mixed metal oxide catalyst contains 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 .
  • Embodiment 10 is the process of any one of Embodiments 1 to 9, 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 11 is the process of any one of Embodiments 1 to 10, wherein the surface area is about 254 m 2 /g.
  • Embodiment 12 is the process of any one of Embodiments 1 to 11, wherein the volume ratio of H 2 to C0 2 during contact with the CuMnAl mixed metal oxide catalyst is at least 3 : 1 or 4: 1.
  • Embodiment 13 is the process of any one of Embodiments 1 to 12, further including a H 2 gas flow rate of 75 to 110 mL/min and the C0 2 gas flow rate of 20 to 30 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 at least 1 : 1, preferably 1 : 1 to 4: 1.
  • Embodiment 15 is the process of any one of Embodiments 1 to 14, further including the step of using the produced syngas mixture as an intermediate or as feed material in a subsequent synthesis to form a chemical product or a plurality of chemical products.
  • Embodiment 16 is the process of Embodiment 15, wherein the subsequent synthesis is selected from the group consisting of methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins.
  • FIG. 1 is an illustration of a process of the present invention to produce syngas 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 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, which results in relatively high carbon dioxide conversions with minimal (e.g., less than 5 mol. %) or no production of alkane byproducts (e.g., methane).
  • these results can be achieved at processing conditions having a temperature of at least 600 °C and greater than atmospheric pressure to produce syngas compositions suitable for the production of methanol.
  • 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 600 °C to 655 °C, from about 615 °C to 625 °C, or about 620 °C and all ranges and values there between (e.g., 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, 655 °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 2 MPa to about 4 MPa and all pressures there between (e.g., 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, and 6 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 hydrogenation reaction can range from at least 75 mL/min, 100 mL/min to 120 mL/min, from about 100 mL/min to about 105 mL/ min or all ranges and values there between (e.g., at least 75 mL/min, 76 mL/min, 77 mL/min, 78 mL/min, 79 mL/min, 80 mL/min, 81 mL/min, 82 mL/min, 83 mL/min, 84 mL/min, 85 mL/min, 86 mL/min, 87 mL/min, 88 mL/min, 89 mL/min, 90 mL/min, 91 mL/min, 92 mL/min, 93 mL/min, 94 mL/min, 95 mL/min,
  • the H 2 flow rate can range from 75 mL/min to 1 10 mL/min, 80 to 100 mL/min, 85 to 105 mL/min, or all ranges and values there between (e.g., 75 mL/min, 76 mL/min, 77 mL/min, 78 mL/min, 79 mL/min, 80 mL/min, 81 mL/min, 82 mL/min, 83 mL/min, 84 mL/min, 85 mL/min, 86 mL/min, 87 mL/min, 88 mL/min, 89 mL/min, 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
  • the C0 2 gas flow rate can be 20 mL/min to 30 mL/min or 20 mL/min, 21 mL/min, 22 mL/min, 23 mL/min, 24 mL/min, 25 mL/min, 26 mL/min, 27 mL/min, 28 mL/min, 29 mL/min, or 30 mL/min.
  • the H 2 gas flow rate is 75 to 1 10 mL/min and the C0 2 gas flow rate is 20 to 30 mL/min at 2 MPa to 4 MPa.
  • the reaction can be carried out over the CuMnAl mixed metal redox 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 50 mol%, at least 60 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.
  • the catalyst Prior to use, 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 to Cu and Cu species, Mn to Mn°, etc.).
  • a non-limiting example of 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.
  • a hydrogen gas or hydrogen gas containing mixture e.g., a H 2 and argon gas stream
  • a system 100 which 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 metal 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 and carbon monoxide.
  • the product stream can also include unreacted carbon dioxide, water, and less than 5 mol.% of alkanes (e.g., methane).
  • 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 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.).
  • Any unreacted reactant gas can be recycled and included in the reactant feed to maximize the overall conversion of C0 2 to syngas, which increases the efficiency and commercial value of the C0 2 to syngas conversion process of the present invention.
  • 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 600 °C or 600 °C to 650 °C, preferably 610 °C to 630 °C, or more preferably 615 °C to 625 °C, or most preferably about 620 °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. In some embodiments, the catalyst can have a density of 0.85 to 0.95 g/mL, 0.86 to 0.94 g/mL, 0.87 to 0.90 g/mL, or 0.89 g/mL.
  • 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 : 1.5 :8.
  • 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, 1 10 °C, 1 1 1 °C, 1 12 °C, 1 13 °C, 1 14 °C, 1 15 °C, 1 16 °C, 1 17 °C, 1 18 °C, 1 19 °C, 120 °C, 121
  • 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, 249 °C, 250 °C, 251 °C, 252 °C, 253 °C, 254 °C, 255 °C, 256 °C, 257 °C, 258 °C, 259 °C, or 250 °C for a desired amount of time (e.g., 2 tol
  • 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 650 °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 500 cc/per minute) to form the CuMnAl mixed metal oxide catalyst.
  • an oxygen source e.g., air at 500 cc/per minute
  • the catalyst particles can be reduced in size (e.g., crushed) to a particle size of 30-50 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 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 2.5 : 1 to 5 : 1 or from 3 : 1 to 4: 1, preferably 4: 1.
  • the reactant gas stream includes 50 to 90 vol.% H 2 and 15 to 35 vol.% C0 2 .
  • the reactant gas stream includes 65 to 85 vol.% H 2 and 20 to 30 vol.% C0 2 .
  • the reactant gas stream includes about 84 vol.% H 2 and about 21 vol.% C0 2 .
  • the reactant gas stream includes about 78.7 vol.% H 2 and 26.2 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 process of the present invention can produce a product stream that includes a mixture of 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 0.90 to 1.1 or 1, which is suitable for oxo-products (e.g., C 2 + alcohols, dimethyl ether, etc.). In yet another example, the molar H 2 :CO ratio can be 1.9 to 2.1 or 2, which is suitable for the production of methanol from syngas. In embodiments, when C0 2 is present in the product stream, the process can produce a mixture suitable for the production of methanol having at least 2 mol.% up to 16 mol.% of C0 2 in the syngas composition.
  • the amount of alkane (e.g., methane) produced in the process of the present reaction can be less than 5 mol.%, less than 4 mol.%, 3 mol.%, 2 mol.%, 1 mol.% or 0 mol.% based on the total moles of components in the product stream.
  • the product stream can include unreacted C0 2 .
  • the product stream can include less than 20 mol.%, 19 mol.%, 18 mol.%, 17 mol.%, 16 mol.%, 15 mol.%, 14 mol.%, 13 mol.%, 12 mol.%, 1 1 mol.%, 10 mol.%, 9 mol.%, 8 mol.%, 7 mol.%, 5 mol.%, 4 mol.%, 3 mol.%, 2 mol.%), 1 mol.%) or 0 mol.% of C0 2 based on the total moles of components in the product stream.
  • the product stream which includes the produced syngas can include about 17.8 mol.% CO, about 13 mol.% C0 2 , about 3.0 mol.% CH 4 , and about 66.2 mol.%) H 2 .
  • the product stream can include about 17.0 mol.% CO, about 14.1 mol.%) C0 2 , about 3.2 mol.% CH 4 , and about 65.7 mol.% H 2 .
  • the syngas composition can include about 17.6 mol.% CO, about 12.8 mol.% C0 2 , about 2.5 mol.% CH 4 , and about 67.1 mol.% H 2 .
  • the syngas composition can include about 17.0 mol.% CO, about 13.1 mol.% C0 2 , about 3.0 mol.% CH 4 , and about 66.9 mol.% H 2 .
  • Copper nitrate (5.63 g, Cu(N0 3 ) 3 *2.5H 2 0), manganese nitrate (14.6 g, ⁇ ( ⁇ 0 3 ) 3 ⁇ 4 ⁇ 2 0), and aluminum nitrate (90.15 g, ⁇ 1( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0) were dissolved in water (500 mL).
  • Ammonium hydroxide (NH 4 OH) was added gradually to the solution to co- precipitate the CuMnAl metal oxide precursor material. The pH of the solution was maintained at 9 and heated to a temperature of 70 °C and held for 2 hours, and then cooled to room temperature.
  • 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 4 hours. The heat-treated CuMnAl metal oxide precursor material was calcined at 650 °C in an air flow of 5000 cc/min for 4 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/mL.
  • BET Brunauer-Emmett-Teller
  • 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 78.7 cc/min and a C0 2 flow rate of 26.2 cc/min.
  • Time on stream (TOS) Time on stream
  • molar percentage of components in the product stream and % carbon dioxide conversion and 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 620 °C, a H 2 flow rate of 84 cc/min and a C0 2 flow rate of 21 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 2.65 MPa, a temperature of 660 °C, a H 2 flow rate of 100 cc/min and a C0 2 flow rate of 25 cc/min. Results are listed in Table 3.
  • 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 78.7 cc/min and a C0 2 flow rate of 26.2 cc/min. Results are listed in Table 4. Table 4
  • Example 5 From the comparison of Example 5 with Examples 3, 4 and 6, it was determined that increasing the temperature above 650 °C under high pressure converted less of the carbon dioxide to carbon monoxide and produced more of the methane by-product. From comparison of Example 6 with Examples 3 and 4, it was determined that the temperature of 600 °C did not produce syngas in an efficient manner as the CO concentration in the product mixture was low. A CO concentration of less than 8 mol.% with a C0 2 concentration of 17 mol.% did not meet the syngas composition requirement for methanol synthesis (e.g., a C0 2 concentration of less than 16 mol.%).
  • the process conditions for Examples 3 and 4 produced syngas with a methane content (e.g., 2.5 to 3.0 mol.%) similar to the methane content of syngas produced from methane reforming.
  • Syngas produced at the conditions of Examples 3 and 4 with the catalyst of the present invention is 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

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Abstract

L'invention concerne des procédés et des catalyseurs pour l'hydrogénation de la réaction du dioxyde de carbone. Un procédé d'hydrogénation de dioxyde de carbone (CO2) pour produire une composition contenant de gaz de synthèse composé d'hydrogène (H2) et de monoxyde de carbone (CO) peut comprendre la mise en contact d'un catalyseur d'oxyde métallique mixte CuMnAl avec H 2 et CO 2 à une température d'au moins 600 °C et à une pression supérieure à la pression atmosphérique.
PCT/IB2017/053918 2016-07-18 2017-06-29 Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseurs à oxyde métallique mixte cuivre-manganèse-aluminium WO2018015827A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2024003843A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Catalyseurs au manganèse pour conversion eau-gaz inverse et procédés de fischer-tropsch intégrés

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Publication number Priority date Publication date Assignee Title
US20110105630A1 (en) * 2009-11-04 2011-05-05 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Catalytic Support for use in Carbon Dioxide Hydrogenation Reactions
US8815767B2 (en) * 2008-11-05 2014-08-26 Sued-Chemie Catalysts Italia S.R.L. Mixed oxides catalysts
WO2015066117A1 (fr) * 2013-10-29 2015-05-07 Saudi Basic Industries Corporation Procédé d'hydrogénation de dioxyde de carbone d'un gaz synthétique et intégration du procédé dans des procédés de conversion de gaz synthétique
WO2015153610A1 (fr) * 2014-04-03 2015-10-08 Saudi Basic Industries Corporation Procédé permettant de convertir du gaz de synthèse de reformage de vapeur de méthane avec du co2

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Publication number Priority date Publication date Assignee Title
US8815767B2 (en) * 2008-11-05 2014-08-26 Sued-Chemie Catalysts Italia S.R.L. Mixed oxides catalysts
US20110105630A1 (en) * 2009-11-04 2011-05-05 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Catalytic Support for use in Carbon Dioxide Hydrogenation Reactions
WO2015066117A1 (fr) * 2013-10-29 2015-05-07 Saudi Basic Industries Corporation Procédé d'hydrogénation de dioxyde de carbone d'un gaz synthétique et intégration du procédé dans des procédés de conversion de gaz synthétique
WO2015153610A1 (fr) * 2014-04-03 2015-10-08 Saudi Basic Industries Corporation Procédé permettant de convertir du gaz de synthèse de reformage de vapeur de méthane avec du co2

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024003843A1 (fr) * 2022-06-30 2024-01-04 Bp P.L.C. Catalyseurs au manganèse pour conversion eau-gaz inverse et procédés de fischer-tropsch intégrés

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