WO2018015824A1 - Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseur à base d'oxydes métalliques mixtes de cuivre-manganèse-zirconium - Google Patents

Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseur à base d'oxydes métalliques mixtes de cuivre-manganèse-zirconium Download PDF

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WO2018015824A1
WO2018015824A1 PCT/IB2017/053716 IB2017053716W WO2018015824A1 WO 2018015824 A1 WO2018015824 A1 WO 2018015824A1 IB 2017053716 W IB2017053716 W IB 2017053716W WO 2018015824 A1 WO2018015824 A1 WO 2018015824A1
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mol
syngas
metal oxide
flow rate
containing composition
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PCT/IB2017/053716
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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
    • 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
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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

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 CuZnZr 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.
  • This process which is also known as a reverse water gas shift reaction, is mildly endothermic and generally takes place at temperatures of at least about 450 °C, with C0 2 conversion of 50% at temperatures between 560 °C to 580 °C. Furthermore, some methane can be formed as a by-product due to the methanation reaction as shown in equations (6) and (7).
  • the discovery is premised on the use of a CuZnZr mixed metal oxide catalyst ⁇ i.e., CuO-ZnO-Zr0 2 ) 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 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 syngas composition is applicable for methanol synthesis.
  • 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 CuZnZr mixed metal oxide catalyst with a reactant feed that includes H 2 and C0 2 at a reaction temperature of at least 600 °C or 610 °C to 650 °C, or 615 °C to 630 °C and a pressure greater than atmospheric pressure (e.g., 0.5 MPa to 6 MPa, or 1 MPa to 3 MPa) to produce a product stream comprising the syngas containing composition that includes H 2 and CO.
  • the process can include contacting a CuZnZr mixed metal oxide catalyst with a reactant feed that includes H 2 and C0 2 at a reaction temperature of at least 600 °C or 610 °C to 650 °C, or 615 °C to 630 °C, a pressure of at least 1 MPa, and a combined gas flow rate of H 2 and CO of at least 54 mL/min to produce a product stream that includes the syngas containing composition that includes H 2 and CO.
  • the combined flow rate is at least 60 mL/min to 120 mL/min, preferably, 100 mL/min to 110 mL/min.
  • the gas hourly space velocity of the combined flow rate is about 300 to 1000 h "1 .
  • the process can include contacting a CuZnZr mixed metal oxide catalyst with a reactant feed that includes H 2 and C0 2 at a temperature of at least 600 °C or 610 °C to 650 °C, or 615 °C to 630 °C, a pressure of 1 MPa to 3 MPa, a H 2 gas flow rate of 70 to 100 mL/min, and a C0 2 gas flow rate of 15 to 30 mL/min, to produce a product stream that includes the syngas containing composition that includes H 2 and CO.
  • the H 2 gas flow rate can be 80 to 90 mL/min and the C0 2 gas flow rate can be 20 to 30 mL/min.
  • the CuZnZr mixed metal oxide catalyst can include 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO and 15 wt. % to 25 wt. % of Zr0 2 .
  • the catalyst includes about 55.19 wt. % CuO, 24.9 wt. % ZnO, and 19.9 wt. % Zr0 2 .
  • the mixed oxides can be in the form of crystal phases forming separate phases of Zr0 2 , ZnO and CuO/Cu. All phases can be separate phases of oxides in the solid material forming solid solution of mixed oxides in the crystal lattice of the solid solution.
  • the catalyst can have a surface area of 103 m 2 /g.
  • the molar ratio of the reactant H 2 and C0 2 can be least 3 : 1, preferably 4: 1.
  • the produced syngas has a stoichiometric number of from 0.1 to 3.0 and, preferably, can have a methane content of less than 5 mol.%.
  • the produced syngas can have a H 2 to CO molar ratio of 1 : 1 to 5: 1, or 3 : 1 to 4.6: 1.
  • Embodiment 1 is a process for hydrogenating carbon dioxide (C0 2 ) to produce a syngas containing composition comprising hydrogen (H 2 ) and carbon monoxide (CO).
  • the process includes contacting a CuZnZr 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 comprising H 2 and CO.
  • Embodiment 2 is the process of Embodiment 1, wherein temperature is 610 °C to 650 °C, and preferably, the temperature is 615 °C to 630 °C.
  • Embodiment 3 is the process of Embodiments 1 or 2, wherein the pressure is at least 1 MPa.
  • Embodiment 4 is the process of any one of Embodiments 1 to 3 wherein the pressure is from 1 MPa to 3 MPa.
  • Embodiment 5 is the process of any one of Embodiments 1 to 4, wherein the combined gas flow rate of H 2 and C0 2 is at least 54 mL/min, and preferably 60 mL/min to 120 mL/min or more preferably, 100 mL/min to 110 mL/min.
  • Embodiment 6 the process of any one of Embodiments 1 to 5, wherein the H 2 gas flow rate is 70 to 100 mL/min and the C0 2 gas flow rate is 15 to 30 mL/min.
  • Embodiment 7 is the process of any one of Embodiments 1 to 6, wherein the pressure is at least 1 MPa and the combined gas flow rate of H 2 and C0 2 is at least 54 mL/min.
  • Embodiment 8 is the process of any one of Embodiments 1 to 7, wherein the pressure is 1 MPa to 3 MPa, the H 2 gas flow rate is 70 to 100 mL/min, and the C0 2 gas flow rate is 15 to 30 mL/min.
  • Embodiment 9 is the process of any one of Embodiments 1 to 8, wherein the CuZnZr mixed metal oxide catalyst includes 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt.
  • Embodiment 10 is the process of any one of Embodiments 1 to 9, wherein the methane content in the produced syngas containing composition is 5 mol. % or less, or is from 2 mol. % to 5 mol. %.
  • Embodiment 11 the process of any one of Embodiments 1 to 10, wherein the produced syngas containing composition is used to produce methanol.
  • Embodiment 12 is the process of any one of Embodiments 1 to 10, wherein the produced syngas containing composition is used to produce an olefin; preferably the olefin is a C 2 to C 4 olefin or a mixture thereof.
  • Embodiment 13 is the process of any one of Embodiments 1 to 12, wherein the CuZnZr mixed metal oxide catalyst is contacted with H 2 and C0 2 at a H 2 :C0 2 volume ratio of at least 3 : 1, and preferably 4: 1.
  • Embodiment 14 is the process of any one of Embodiments 1 to 13, wherein the produced syngas containing composition has a H 2 to CO molar ratio of 1 : 1 to 5: 1.
  • Embodiment 15 is the process of any one of Embodiments 1 to 14 wherein the produced syngas containing composition has a H 2 to CO molar ratio of about 4: 1.
  • Embodiment 16 is the process of any one of Embodiments 1 to 15 wherein the combined gas flow rate of H 2 and C0 2 is at least 60 mL/min to 120 mL/min.
  • Embodiment 17 is the process of Embodiments 1 to 16 wherein the combined gas flow rate of H 2 and C0 2 is at least 100 mL/min to 110 mL/min.
  • Embodiment 18 is the process of Embodiment 12, wherein the produced syngas containing composition is used to produce a C 2 to C 4 olefin or a mixture thereof.
  • Embodiment 19 is the process of any one of Embodiments 1 to 18, wherein the methane content in the produced syngas containing composition is 2 mol. % to 5 mol. %.
  • Embodiment 20 is the process of any one of Embodiments 1 to 19 wherein the CuZnZr mixed metal oxide catalyst is contacted with H 2 and C0 2 at a H 2 :C0 2 volume ratio of at least 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.
  • 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 is the ability to hydrogenate carbon dioxide to produce syngas.
  • FIG. 1 is an illustration of a process of the present invention to produce syngas using a combined C0 2 and H 2 containing reactant feed gas and the CuZnZr 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 CuZnZr mixed metal oxide catalyst of the present invention.
  • the discovery is premised on the use of a CuZnZr 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). Furthermore, these results can be achieved at processing conditions having a temperature of at least 600 °C and greater than atmospheric pressure.
  • 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, 600 °C to 650 °C, 615 °C to 630 °C, or about 620 °C and all ranges and values there between including 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, or 650 °C.
  • the average pressure for the hydrogenation reaction can range from above atmospheric pressure, at least 1 MPa, 1 MPa to about 6 MPa, preferably 1 MPa to 3 MPa and all pressures there between (e.g., 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 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 the hydrogenation reaction can range from at least 54 mL/min, 60 mL/min to 120 mL/min, from about 100 mL/min to about 1 10 mL/ min or all ranges and values there between (e.g., at least 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min, 58 mL/min, 59 mL/min, 60 mL/min, 61 mL/min, 62 mL/min, 63 mL/min, 64 mL/min, 65 mL/min, 66 mL/min, 67 mL/min, 68 mL/min, 69 mL/min, 70 mL/min, 71 mL/min, 72 mL/min, 73 mL/min, 74 mL/min, 75 mL/min
  • the H 2 flow rate can range from 70 mL/min to 100 mL/min, 75 to 95 mL/min, 80 to 90 mL/min, or all ranges and values there between (e.g., 70 mL/min, 71 mL/min, 72 mL/min, 73 mL/min, 74 mL/min, 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 C0 2 gas flow rate can be 15 mL/min to 30 mL/min, 20 to 30 mL/min or any range or value there between (e.g., 15 mL/min, 16 mL/min, 17 mL/min, 18 mL/min, 19 mL/min, 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 80 to 90 mL/min, preferably about 85 mL/min and the C0 2 gas flow rate is 20 to 30 mL/min, preferably about 21 mL/min.
  • the reaction can be carried out over the CuZnZr 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 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, 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, Zn +2 to Zn°, etc.).
  • reducing conditions includes flowing a gaseous stream that includes a hydrogen gas or a hydrogen gas containing mixture (e.g., a H 2 and argon gas mixture) at a temperature of 250 °C to 280 °C for a sufficient period of time (e.g., 1, 2, or 3 hours).
  • 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 CuZnZr mixed metal oxide catalyst 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.
  • the combined reactant gas source 102 is one unit feeding into one inlet 108.
  • 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 CuZnZr 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 1 10 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, 204, 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) 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 CuZnZr mixed metal oxide catalyst of the present invention can include 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO and 10 wt. % to 25 wt. % of Zr0 2 or any value or range there between.
  • the catalyst can include 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, 56 wt. %, 57 wt. %, 58 wt. %, 59 wt. %, 60 wt.
  • the catalyst can include 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, 25 wt. %, 26 wt. %, 27 wt. %, 28 wt. %, 29 wt. %, or 30 wt. % ZnO.
  • the catalyst can include 10 wt. %, 1 1 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, 15 wt. %, 16 wt. %, 17 wt. %, 18 wt.
  • the catalyst includes about 55.19% CuO, 24.9% ZnO, and 19.9% Zr0 2 .
  • the weight percentage of the elements can be 40 to 45 wt.% Cu, 15 to 25 wt.% Zn, and 10 to 15 wt.% Zr, or about 44 wt.% Cu, about 20 wt.% Zn and about 13.7 wt.% Zr.
  • the weight ratio of Cu:Zn:Zr can range from 2.5 : 1 :0.5 to 3.0: 1 : 1 or 2.2: 1 :0.68.
  • the catalyst can have a surface area from 100 m 2 /g to 1 10 m 2 /g, or 100 to 105 m 2 /g, or 103 m 2 /g.
  • Such a catalyst can be hard and have mechanical stability (e.g., the catalyst does not break apart during use).
  • Suitable sources for the metals for use in the preparation of the catalysts of this invention include, without limitation, 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.
  • the catalyst can be made using a co- precipitation method.
  • a first metal salt e.g., copper metal salt
  • a second metal salt e.g., zinc metal salt
  • a third metal salt e.g., zirconium metal salt
  • the first metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of copper.
  • the second metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of zinc.
  • Examples of the third metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, halides of zirconium.
  • Cu(N0 3 ) 3 , Zn(N0 3 ) 2 , and Zr(N0 3 ) 3 can be solubilized in deionized water.
  • three solutions are prepared and mixed together.
  • the metal salts can be obtained from commercial vendors, for example, Sigma-Aldrich ® (U.S.A.).
  • Aqueous base e.g., ammonium hydroxide or sodium hydroxide
  • Aqueous base can be added to the solution in an amount effective to precipitate a Cu/Zn/Zr metal hydroxide precursor from the solution.
  • the pH of the solution can be 7 to 9, 7.5 to 8.5, or 8 after addition of the base.
  • the Cu/Zn/Zr metal hydroxide precursor can be heated from 55 °C to 75 °C, 60 °C to 70 °C and all values there between including 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/Zn/Zr metal hydroxide precursor.
  • the Cu/Zn/Zr precursor precipitate can be separated from the solution using known separation techniques (e.g., centrifugation, filtration, etc.).
  • the separated Cu/Zn/Zr precursor precipitate can be washed with water (e.g., deionized water) to remove any excess base. Washing and filtering the Cu/Zn/Zr precursor precipitate can be repeated as necessary to remove all, or substantially all, of the base from the Cu/Zn/Zr precursor precipitate.
  • Residual water can be removed from the Cu/Zn/Zr precursor by heating the solution (e.g., drying the solution) at a temperature from 90 °C to 1 10 °C, or 95 °C to 105 °C, or any value there between including 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, or 1 10 °C for a time period sufficient (e.g., 3 to 24 hours, 8 to 20 hours, or 12 hours) to remove all or a majority of the water to produce a dried powdered material.
  • a time period sufficient (e.g., 3 to 24 hours, 8 to 20
  • drying is performed at 105 °C for 12 hours.
  • the dried CuZnZr material can be then be calcined within 8 hours of drying by heating the dried material to an average temperature between 350 °C and 600 °C, 400 °C to 550 °C, with 400 °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 CuZnZr 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 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 molar H 2 :C0 2 reactant gas ratio for the hydrogenation reaction can range from 2.5 : 1 to 5 : 1, from 3 : 1 to 4: 1.
  • the reactant gas stream includes 50 to 90 vol.% H 2 and 15 to 35 vol.% C0 2 , preferably 65 to 85 vol.% H 2 and 20 to 30 vol.% C0 2 , or more preferably about 84 vol.% H 2 and about 21 vol.% C0 2 or about 78.7 vol.% H 2 and about 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.
  • 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 about 1.9: 1 to 5 : 1, or 3 : 1, 3.5 : 1, 3.6: 1, 4: 1, 4.5 : 1, 4.6: 1 or 5 : 1, 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 20 mol.% of C0 2 .
  • 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 can include about 15.8 mol%> CO, about 14 mol%> C0 2 , about 3.6 mol%> CH 4 , and about 66.2 mol%> H 2 .
  • the product stream can include about 16.3 mol%> CO, about 13 mol%> C0 2 , about 2.4 mol%> CH 4 , and about 68.3 mol%> H 2 .
  • the product stream can include about 13.9 mol% CO, about 17.5 mol% C0 2 , about 4.2 mol% CH 4 , and about 64.4 mol% H 2 .
  • the product stream can include about 14 mol%> CO, about 17.2 mol%> C0 2 , about 4.8 mol% CH 4 , and about 64 mol% H 2 .
  • Copper nitrate (35.7g, Cu(N0 3 ) 3 .3H 2 0), zinc nitrate (20.9 g, Zn(N0 3 ) 2 .6H 2 0), and zirconium nitrate (11.6 g, Zr(N0 3 ) 3 «6H 2 0) were dissolved in water (500 mL). Under stirring, using overhead motor, the solution was heated to 85 °C. Sodium carbonate (Na 2 C0 3 , 30 wt.% solution) was added gradually to the solution to co-precipitate the CuZnZr metal oxide precursor material. The pH of the solution was maintained at 8 and heated to a temperature of 80 to 85 °C for 2 hours.
  • the CuZnZr metal oxide precursor material was isolated by filtration, and washed with warm (60 °C) water (3 X 500 mL) to remove excess base. The washed CuZnZr metal oxide precursor material was dried at 105 °C for 12 hours. The dried CuZnZr metal oxide precursor material was calcined at 400 °C in air flow of 250 cc/min for 8 hours to form the black CuZnZr mixed metal oxide catalyst of the present invention. Prior to use, the CuZnZr mixed metal oxide catalyst was crushed to a particle size of 20-50 mesh. The CuZnZr mixed metal oxide catalyst had a surface area of 103 m 2 /g.
  • 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 84 cc/min and a C0 2 flow rate of 21 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 1 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. 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 650 °C, a H 2 flow rate of 42 cc/min and a C0 2 flow rate of 12 cc/min. Results are listed in Table 3.
  • Example 5 From the comparison of Example 5 with Example 3 and 4, it was determined that decreasing the flow rates of reactant gas by about 50% to 53% at high pressure converted less of the carbon dioxide to carbon monoxide and produced more of the methane by-product.
  • the process conditions for Examples 3 and 4 produced syngas with a methane content (e.g., 3.8 to 4.7 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 également des procédés et des catalyseurs pour l'hydrogénation du dioxyde de carbone (CO2) pour produire une composition contenant un gaz de synthèse. Le procédé peut comprendre la mise en contact d'un catalyseur d'oxyde métallique mixte CuZnZr avec de l'hydrogène H2) et CO2 à une température d'au moins 600 °C et à une pression supérieure à la pression atmosphérique pour produire la composition contenant du gaz de synthèse.
PCT/IB2017/053716 2016-07-18 2017-06-21 Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseur à base d'oxydes métalliques mixtes de cuivre-manganèse-zirconium WO2018015824A1 (fr)

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