WO2018015828A1 - Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseurs supportés à base d'oxyde de chrome - Google Patents

Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseurs supportés à base d'oxyde de chrome Download PDF

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Publication number
WO2018015828A1
WO2018015828A1 PCT/IB2017/053926 IB2017053926W WO2018015828A1 WO 2018015828 A1 WO2018015828 A1 WO 2018015828A1 IB 2017053926 W IB2017053926 W IB 2017053926W WO 2018015828 A1 WO2018015828 A1 WO 2018015828A1
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flow rate
gas flow
mpa
catalyst
syngas
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PCT/IB2017/053926
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English (en)
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Aghaddin Mamedov
Clark Rea
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Sabic Global Technologies B.V.
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Publication of WO2018015828A1 publication Critical patent/WO2018015828A1/fr

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    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal 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
    • 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 used chromium oxide supported 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 (3) 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).
  • U.S. Patent No. 8,288,446 to Mamedov et al. describes a process to make a syngas mixture that includes hydrogen, carbon monoxide and carbon dioxide with a spent chromia/alumina catalyst at temperatures of 300 to °C to 900 °C, at a pressure of from 0.1 to 5 MPa, at combined feed gas flow rate of 52 ml/min with temperature of 600 °C and atmospheric pressure being preferred.
  • U.S. Patent Application Publication No. 2015/0080482 to Mamedov et al. describes a process for the hydrogenation of carbon dioxide using a chromia/alumina supported catalyst at atmospheric pressure and a temperature of 450 °C to 1000 °C with high amounts of CO in the feed gas.
  • the discovery is premised on the use of a used supported chromium oxide catalyst at temperatures of at least 600 °C, a pressure greater than atmospheric pressure at high feed gas flow rates.
  • 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 syngas composition is applicable for methanol production, oxo- product production, and/or olefin production.
  • 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 used chromium oxide supported 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 625 °C, or 620 °C, a pressure greater than atmospheric pressure (e.g., 0.5 MPa to 6 MPa, or 1 MPa to 3 MPa), and a combined gas flow rate of H 2 and C0 2 of at least 54 mL/min to produce a product stream that includes the syngas containing composition containing H 2 and CO.
  • a reaction temperature of at least 600 °C or 610 °C to 650 °C, or 615 °C to 625 °C, or 620 °C
  • a pressure greater than atmospheric pressure e.g.
  • the process can include contacting a used chromium oxide supported catalyst with H 2 and C0 2 at a reaction temperature of at least 600 °C, or 610 °C to 650 °C, or 615 °C to 625 °C, or 620 °C, a pressure of at least 0.5 MPa, and a combined gas flow rate of H 2 and C0 2 of at least 54 mL/min, where the H 2 gas flow rate is at least 3.5 times greater than the C0 2 gas flow rate in the combined gas flow rate to produce a product stream that includes the syngas containing composition containing H 2 and CO.
  • the process can include contacting a used chromium oxide supported catalyst with H 2 and C0 2 at a temperature of at least 600 °C or 610 °C to 650 °C, or 615 °C to 625 °C, or 620 °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 containing H 2 and CO.
  • the used chromium oxide catalyst can include from 5 wt.% to 30 wt.
  • the catalyst can include from 0.2 to 30 wt. % of lithium (Li), potassium (K), cesium (Cs) or strontium (Sr) based on the total weight of the catalyst.
  • the supported catalyst is a used chromium oxide/alumina catalyst that has been previously used in a dehydrogenation reaction (e.g., an z ' so-butane dehydrogenation reaction).
  • the volume ratio of the reactants H 2 and C0 2 can be least 3 : 1.
  • the reaction conditions can include a H 2 gas flow rate of 75 mL/min to 100 mL/min, preferably 80 mL/min to 90 mL/min, a C0 2 gas flow rate of 15 mL/min to 25 mL/min, preferably 20 mL/min to 25 mL/min, a temperature of 600 °C to 650 °C, preferably 610 °C to 630 °C, and a pressure of 2.5 MPa to 3.5 MPa, preferably 2.5 MPa to 3 MPa.
  • the reaction conditions can include a H 2 gas flow rate of 30 mL/min to 50 mL/min, preferably 40 mL/min to 45 mL/min, a C0 2 gas flow rate of 5 mL/min to 15 mL/min, preferably 10 mL/min to 15 mL/min, a temperature of 600 °C to 650 °C, preferably 610 °C to 630 °C, and a pressure of 0.5 MPa to 1.5 MPa, preferably 0.8. MPa to 1.2 MPa.
  • the produced syngas has a H 2 :CO molar ratio from 1 : 1 to 5 : 1, or 2: 1 to 4: 1, or 3 : 1 to 4.5 : 1.
  • the syngas composition can also include less than 5 mol.% of alkanes, preferably, methane.
  • 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.
  • Embodiment 1 relates to 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 used chromium oxide supported catalyst with H 2 and C0 2 at a temperature of at least 600 °C, a pressure greater than atmospheric pressure, and a combined gas flow rate of H 2 and C0 2 of at least 54 mL/min to produce the syngas containing composition comprising H 2 and CO.
  • Embodiment 2 is the process of Embodiment 1, wherein the temperature is 610 °C to 650 °C, and is preferably 615 °C to 620 °C.
  • Embodiment 3 is the process of any one of Embodiments 1 or 2, wherein the pressure is at least 0.5 MPa, and where the H 2 gas flow rate is at least 3.5 times greater than the C0 2 gas flow rate.
  • Embodiment 4. is the process of any one of Embodiments 1 to 3, wherein the pressure is 1 MPa to 3 MPa, and wherein the combined gas flow rate of H 2 and C0 2 includes 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.
  • Embodiment 5 is the process of any one of Embodiments 1 to 4, wherein the pressure is 2 MPa to 3 MPa and the H 2 gas flow rate is 80 to 90 mL/min and the C0 2 gas flow rate is 20 to 25 mL/min.
  • Embodiment 6 is the process of any one of Embodiments 1 to 5, wherein the pressure is 0.5 MPa to 1.5 MPa, and wherein the combined gas flow rate of H 2 and C0 2 comprises a H 2 gas flow rate of 40 to 50 mL/min, and a C0 2 gas flow rate of 10 to 20 mL/min.
  • Embodiment 7 is the process of any one of Embodiments 1 to 6, wherein the volume ratio of the H 2 to C0 2 during contacting is 2.5: 1 to 5: 1.
  • Embodiment 8 is the process of any one of Embodiments 1 to 7, wherein the catalyst contains from 5 to 30 wt. % of chromium.
  • Embodiment 9 is the process of any one of Embodiments 1 to 8, wherein the catalyst contains from 0.2 to 30 wt. % of at least one member selected from the group consisting of Li, K, Cs and Sr.
  • Embodiment 10 is the process of any one of Embodiments 1 to 9, wherein the supported catalyst is a used chromium oxide/alumina catalyst that has been previously used as a catalyst for a dehydrogenation reaction.
  • Embodiment 11 is the process of any one of Embodiments 1 to 10, wherein syngas composition has a H 2 :CO molar ratio from 1 : 1 to 5: 1.
  • Embodiment 12 is the process of any one of Embodiments 1 to 11, wherein the H 2 :CO molar ratio is 2: 1 to 5: 1, or 4: 1.
  • Embodiment 13 is the process of any one of Embodiments 1 to 12, wherein the syngas composition comprises less than 5 mol.% of an alkane.
  • Embodiment 14 is the process of Embodiment 13, wherein the alkane is methane.
  • Embodiment 15 is the process of any one of Embodiments 1 to 14, wherein the C0 2 conversion is at least 50%.
  • Embodiment 16 is the process of any one of Embodiments 1 to 15, 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 17 is the process of Embodiment 16, 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.
  • Embodiment 18 is the process of Embodiment 17, wherein the chemical product is methanol.
  • 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 used chromium oxide supported 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 used chromium oxide supported catalyst of the present invention.
  • the discovery is premised on the use of a used chromium oxide supported 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) at elevated temperatures and pressures. Furthermore, these results can be achieved at processing conditions having a temperature of at least 600 °C and greater than atmospheric pressure.
  • the syngas composition produced can be used in methanol production, oxo-processes and/or olefin production.
  • 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 655 °C, 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, or 655 °C).
  • the average pressure for the hydrogenation reaction can range from above atmospheric pressure, at least 0.5 MPa, 0.5 MPa to about 6 MPa, preferably, 1 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).
  • 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., combination of the H 2 and C0 2 flow rate) in hydrogenation reaction can range from at least 54 mL/min, 54 to 120 mL/min, 100 mL/min to 120 mL/min, 100 mL/min to 105 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,
  • 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
  • the C0 2 gas flow rate is 20 to 30 mL/min, preferably about 21 mL/min at a pressure of 2.5 MPa to 3.5 MPa, or preferably 2.5 MPa to 3.0 MPa.
  • the reaction can be carried out over the used chromium oxide supported 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. Prior to use, the catalyst can be subjected to reducing conditions to convert the chromium oxide and the other metals in the catalyst to a lower valance state or the metallic form.
  • a non-limiting example of 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 stream) at a temperature of 500 °C to 700 °C for a period of time (e.g., 1 to 8 hours) under atmospheric pressure over the catalyst.
  • a system 100 is illustrated, which can be used to convert a reactant gas stream of carbon dioxide (C0 2 ) and hydrogen (H 2 ) into syngas using the used chromium oxide supported 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 110 having the used chromium oxide supported catalyst 112 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 used chromium oxide catalyst 112 used can be modified as desired to achieve a given amount of product produced by the systems 100 or 200. In a preferred aspect, 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 reactor can made of materials that are corrosion and oxidation resistant.
  • the reactor can be lined with, or made from, Inconel, or be a quartz reactor.
  • the reactant gas is preheated prior to being fed to the reactor.
  • reaction zone 110 is a multi-zone reactor with different stages of heating in each zone.
  • the reactor 104 can include an outlet 114 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 110 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 114. 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) 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 catalyst can include chromium (Cr) as the catalytic active metal.
  • the chromium can be in the form of one or more oxides (e.g., Cr 2 0 3 , Cr0 2 , and CrO) on a metal oxide support (e.g., alumina, A1 2 0 3 ).
  • the catalyst can also include a promotor (e.g., alkali metal, alkaline earth metals, or both), a binder material, or usual impurities, as known to the skilled person.
  • the chromium (Cr) content of the catalyst can be 1 to 50 wt.%, 5 to 30 wt.%, 10 to 20 wt.%), or 13 to 17 wt. %, or any range or value there between (e.g., 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 1 1 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%,
  • the catalyst can also include at least one alkali metal or alkaline earth metal as a promoter.
  • alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs).
  • alkaline earth metals include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).
  • the alkali metal or alkaline earth metal content can be 0.1 to 40 wt.%, 0.2 to 30 wt.%, 2 to 10 wt.
  • % or 2 to 5 wt.%) or any range or value there between (e.g., 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 1 1 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22
  • the promoter can be Li, K, Cs, Sr, or any combination thereof. Without wishing to be bound by theory, it is believed that the inclusion of an alkali metal or alkaline earth metal can suppress coke formation and/or methanation reactions, thereby improving the catalyst stability /life-time and reducing the amount of unwanted by-products.
  • the catalyst used in the process according to the invention can have alumina as carrier or support material. Without wishing to be bound to any theory, it is believed that chemical interactions between chromium and alumina lead to structural properties (e.g., spinel type structures) that enhance catalytic performance in the targeted reaction. In some instances, the catalyst has a surface area of at least 50 m 2 /g.
  • the catalyst composition according to the invention may further contain an inert binder or support material other than alumina (e.g., silica or titanium oxides).
  • the catalyst that is used in the process of the invention may be prepared by any conventional catalyst synthesis method as known in the art.
  • the catalyst can be prepared by making aqueous solutions of the desired metal components, for example from their nitrate or other soluble salt, mixing the solutions with alumina, forming a solid catalyst precursor by precipitation (or impregnation) followed by removing water and drying, and then calcining the precursor composition by a thermal treatment in the presence of oxygen.
  • the catalyst may be applied in the process of the invention in various geometric forms, for example as spherical pellets.
  • Non-limiting examples of chromium oxide/alumina supported catalysts that can be used in dehydrogenation reactions include the CATOFIN® catalysts (Clariant, U. S.A.). After being used in a dehydrogenation reaction, the used catalyst typically has low residual activity for such reaction. The low catalytic activity is most likely due to deactivation caused by coke formation. Coke deposition on the spent catalyst is generally thought to result in a change in physical properties of the catalyst particles, like a lower surface area and increased pore size; and the resulting decreased activity of the dehydrogenation catalyst cannot be increased again by a regeneration process. Regeneration with oxygen can remove coke, but will not restore the original structure.
  • the spent catalyst can include ceramic particles.
  • the spent catalyst can be a mixture of ceramic particles and spent chromium oxide supported catalyst.
  • the spent catalyst includes 50 to 70 wt.% spent chromium oxide supported catalyst, including all values there between (e.g.
  • the spent catalyst includes about 60 wt. % spent catalyst and about 40 wt. % ceramic particles.
  • 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 a reverse water gas shift reaction) 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 can 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 :C0 2 reactant gas for the hydrogenation reaction can range from 2.5 : 1 to 5 : 1, from 3 : 1 to 4: 1.
  • the reactant gas stream includes 40 to 90 vol.% H 2 , 10 to 35 vol.% C0 2 , or 65 to 85 vol.% H 2 , and 20 to 30 vol.% C0 2 , preferably, 84 vol.% H 2 and 21 vol.% C0 2 .
  • the streams are not combined.
  • the reactant hydrogen and carbon dioxide can be delivered at the same H 2 :C0 2 ratios and volume percentages as used for the combined reactant gas feed.
  • 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 ), methane, 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) or contain a minimal amount 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 as an intermediate or as feed material in a subsequent synthesis to form a chemical product or a plurality of chemical products to produce one or more 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.).
  • the molar H 2 :CO ratio can be about 1.9: 1 to 5 : 1, 2: 1 to 4: 1, or 3 : 1 to 4.5 : 1, which is suitable for the production of methanol from syngas.
  • a purge gas from the methanol synthesis reaction containing hydrogen and carbon dioxide, is recycled back to the carbon dioxide hydrogenation step.
  • the process can produce a mixture suitable for the production of methanol having at least 2 mol.% of C0 2 up to 16 mol.% 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 14.5 mol.% CO, about 13.5 mol.% C0 2 , about 3.8 mol.% CH 4 , and about 68.2 mol.% H 2 .
  • the product stream can include about 14.8 mol.%> CO, about 14 mol.%) C0 2 , about 4 mol.%> CH 4 , and about 67.2 mol.%> H 2 .
  • the product stream can include about 13.9 mol.%> CO, about 14.9 mol.%> C0 2 , about 4.7 mol.%> CH 4 , and about 66.7 mol.%> H 2 .
  • the product stream can include about 13.9 mol.% CO, about 14.8 mol.% C0 2 , about 4.4 mol.% CH 4 , and about 66.9 mol.% H 2 .
  • a used commercial chromia/alumina dehydrogenation catalyst marketed by Clariant (USA) as Catofin® for dehydrogenation of propane or iso-butane, was applied as catalyst composition in this experiment.
  • This catalyst contains about 13 to 17 wt.% of Cr.
  • equation (8) presents the sum of all carbon, products divided by the total number of carbons.
  • Example 1 The general procedure of Example 1 was followed with the following conditions: a pressure of 2.8 MPa, a temperature of 620 °C, a H 2 flow rate of 84 cubic centimeter (cc)/min, and a C0 2 flow rate of 21 cc/min.
  • Time on stream (TOS) molar percentage of components in the product stream and percent (%) carbon dioxide conversion and results are listed in Table 1.
  • Example 2 The general procedure of Example 1 was followed using the following conditions: a pressure of 1 MPa, a temperature of 620 °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 2.
  • Example 1 The general procedure of Example 1 was followed using the following conditions: a pressure of 2.8 MPa, a temperature of 620 °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. Table 3
  • Example 4 From the comparison of Example 4 with Examples 2 and 3, it was determined that the combination of high pressure and low flow rates is not as efficient for producing syngas, as a majority of the carbon dioxide converts to methane (Example 4).
  • Examples 2 and 3 provide processing conditions allowing for syngas production having a methane content of 3.8 to 4.7 %, which is similar to the content of methane present in product streams obtain from methane reforming syngas reactions.
  • Syngas produced at the conditions of Examples 2 and 3 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 de la réaction du dioxyde de carbone. Un procédé d'hydrogénation de dioxyde de carbone (CO2) pour produire une composition contenant du gaz de synthèse comprenant de l'hydrogène (H2) et du monoxyde de carbone (CO) peut comprendre la mise en contact d'un catalyseur supporté à base d'oxyde de chrome avec H2 et CO2 à une température d'au moins 600 °C et à une pression supérieure à la pression atmosphérique.
PCT/IB2017/053926 2016-07-18 2017-06-29 Procédé d'hydrogénation à haute pression de dioxyde de carbone en gaz de synthèse en présence de catalyseurs supportés à base d'oxyde de chrome WO2018015828A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100105962A1 (en) * 2007-06-25 2010-04-29 Saudi Basic Industries Corporation Catalytic hydrogenation of carbon dioxide into syngas mixture
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
WO2014003817A1 (fr) * 2012-06-29 2014-01-03 Saudi Basic Industries Corporation Procédé de formation d'un mélange de gaz de synthèse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100105962A1 (en) * 2007-06-25 2010-04-29 Saudi Basic Industries Corporation Catalytic hydrogenation of carbon dioxide into syngas mixture
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
WO2014003817A1 (fr) * 2012-06-29 2014-01-03 Saudi Basic Industries Corporation Procédé de formation d'un mélange de gaz de synthèse

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