WO2018129424A1 - Conversion de gaz à effet de serre en gaz de synthèse par reformage à sec - Google Patents

Conversion de gaz à effet de serre en gaz de synthèse par reformage à sec Download PDF

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WO2018129424A1
WO2018129424A1 PCT/US2018/012720 US2018012720W WO2018129424A1 WO 2018129424 A1 WO2018129424 A1 WO 2018129424A1 US 2018012720 W US2018012720 W US 2018012720W WO 2018129424 A1 WO2018129424 A1 WO 2018129424A1
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reaction vessel
carbon dioxide
catalytic material
methane
flow
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PCT/US2018/012720
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English (en)
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Paul E. KING
Benzion LIVNEH
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King Paul E
Livneh Benzion
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Publication of WO2018129424A1 publication Critical patent/WO2018129424A1/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122Incoherent waves
    • B01J19/126Microwaves
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00027Process aspects
    • B01J2219/0004Processes in series
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0881Two or more materials
    • B01J2219/0883Gas-gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0892Materials to be treated involving catalytically active material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12Processes employing electromagnetic waves
    • B01J2219/1203Incoherent waves
    • B01J2219/1206Microwaves
    • B01J2219/1209Features relating to the reactor or vessel
    • B01J2219/1221Features relating to the reactor or vessel the reactor per se
    • B01J2219/1224Form of the reactor
    • B01J2219/1227Reactors comprising tubes with open ends
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12Processes employing electromagnetic waves
    • B01J2219/1203Incoherent waves
    • B01J2219/1206Microwaves
    • B01J2219/1209Features relating to the reactor or vessel
    • B01J2219/1221Features relating to the reactor or vessel the reactor per se
    • B01J2219/1242Materials of construction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12Processes employing electromagnetic waves
    • B01J2219/1203Incoherent waves
    • B01J2219/1206Microwaves
    • B01J2219/1248Features relating to the microwave cavity
    • B01J2219/1269Microwave guides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/062Hydrocarbon production, e.g. Fischer-Tropsch process
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0855Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0872Methods of cooling
    • C01B2203/0883Methods of cooling by indirect heat exchange
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock

Definitions

  • the field of the present invention relates to greenhouse gas conversion.
  • conversion of greenhouse gases to synthesis gas by dry reforming is disclosed herein.
  • a method for conversion of greenhouse gases comprises: (a) introducing a flow of a dehumidified gaseous source of carbon dioxide into a reaction vessel; (b) introducing a flow of a dehumidified gaseous source of methane into the reaction vessel; and (c) irradiating catalytic material in the reaction vessel with microwave energy.
  • the irradiated catalytic material is heated and catalyzes an endothermic reaction of the carbon dioxide and the methane that produces hydrogen and carbon monoxide. At least a portion of heat required to maintain a temperature within the reaction vessel is supplied by the microwave energy irradiating the catalytic material; electric arcing, electric discharge, and plasma generation are suppressed.
  • a mixture that includes the carbon monoxide and the hydrogen can flow out of the reaction vessel and be introduced into a second reaction vessel to undergo catalyzed reactions producing one or more multiple-carbon reaction products.
  • Fig. 1 illustrates schematically microwave-assisted catalyzed conversion of carbon dioxide and methane to carbon monoxide and hydrogen in a reaction vessel.
  • Fig. 2 illustrates schematically catalyzed conversion carbon monoxide and hydrogen into one or more multiple-carbon reaction products in a second reaction vessel.
  • a method, for consuming carbon dioxide and generating carbon monoxide and hydrogen in a reaction vessel 200 is illustrated schematically in Fig. 1 .
  • a flow of a dehumidified gaseous source 230 of carbon dioxide enters the reaction vessel 200 through an input port, and a flow of a dehumidified gaseous source 240 of methane enters the reaction vessel 200 through an input port.
  • the source gas flows 230/240 could instead be combined upstream and introduced into the reaction vessel 200 through a single port.
  • the reaction vessel 200 contains a catalytic material 21 1 .
  • a catalytic material 21 1 can be employed in any suitable physical form, e.g., a packed bed, coated media of any suitable shape or form, a flowing fluidized particulate catalyst, and so on.
  • suitable catalytic materials include catalysts based on, e.g., iron, cobalt, nickel, rhodium, ruthenium, platinum, palladium, or a combination of one or more of those catalytic materials.
  • a catalytic material "based on" a given element can include one or more of the elemental form ⁇ e.g., metallic nickel), oxides ⁇ e.g., an iron oxide such as magnetite (Fe304)), or other compounds that include the element ⁇ e.g., an iron-containing compound such as pyrrhotite (FeS)).
  • the catalytic material 21 1 is a packed bed that includes magnetite pellets intermixed with inert alumina pellets (or other one or more suitable inert materials). The catalytic material 21 1 in the reaction vessel 200 is irradiated with microwave energy, thereby driving an endothermic reaction
  • the reaction vessel 200 contains within its volume a quartz-lined passage 210 that contains the catalytic material 21 1 .
  • the quartz is substantially transparent to microwaves, and so acts as windows for transmitting the microwaves to propagate into the catalytic material 21 1 .
  • Any suitably strong and chemically compatible material that is substantially transparent to microwave radiation can be employed as window material or to contain the catalytic material 21 1 and the gases 230/240 flowing through it. Examples of suitable materials can include, but are not limited to, quartz, silica, zirconia, cordierite, boron nitride, alumina, and so forth.
  • the microwaves enter the reaction vessel 200 through waveguides 220. The arrangement shown in Fig.
  • microwaves can be delivered into the reaction chamber using one or more cables ⁇ e.g., coaxial cables) each terminating in a corresponding antenna ⁇ e.g., a dipole antenna) arranged so as to irradiate the catalytic material 21 1 .
  • the reaction vessel 200, the catalytic material 21 1 , or the irradiating of the catalytic material 21 1 are arranged so as to suppress or prevent electric arcing, electric discharge, and plasma generation within the reaction vessel 200 (in contrast to the methods disclosed in, e.g., U.S. Pat. No. 5,266,175 or U.S. Pub. No. 2015/0246337).
  • arcing, discharge, or plasma generation is undesirable due to resultant damage to the catalytic material 21 1 or the reaction vessel 200, or due to interference with the desired catalyzed reactions of carbon dioxide and methane.
  • "Suppressing" in this context means that any electric arcing, electric discharge, or plasma generation that might occur is only incidental and intermittent, and does not result in any appreciable occurrence of the undesirable side effects noted above.
  • the suppressing or preventing of arcing, discharge, or plasma generation can be achieved in any suitable way, including one or more of the following. In some examples, simply limiting the microwave power can result in prevention or sufficient suppression (while still high enough to drive the desired catalyzed reactions). In some examples, the spatial arrangement of the
  • waveguides 220 or the reaction vessel 200 can result in prevention or sufficient suppression.
  • the one or more frequencies or phases of the microwave radiation can be selected to result in prevention or sufficient
  • microwave frequencies or one or more time-varying microwave frequencies, can result in prevention or sufficient suppression ⁇ e.g., as disclosed in U.S. non-provisional App. No. 15/292,100 filed 10/12/2016 in the name of Paul E. King, which is incorporated by reference as if fully set forth herein).
  • the microwave waveguides 220 are arranged on opposing sides of the reaction vessel 200 and offset from one another along a direction of flow through the reaction vessel 200.
  • one suitable distribution of microwave energy within the reaction vessel 200 is obtained when the phases of microwave radiation entering the reaction vessel 200 through the waveguides 220 differ from each other by about a quarter of a period of the microwave radiation ⁇ i.e., a phase difference of about ⁇ /2).
  • Other numbers and positions of waveguides 220, and corresponding relative phases of microwave energy emerging from those waveguides can be employed.
  • Microwave energy at any one or more frequencies, each with one or more corresponding relative phases can be employed that results in adequate heating of the catalytic material 21 1 .
  • the microwave energy is at one or more frequencies between about 300 MHz and about 10 GHz, e.g., frequencies within the so-called industrial, scientific, and medical (ISM) frequency bands; in some examples, the microwave energy is at one or more frequencies, e.g., between about 500 MHz and about 3 GHz, between about 2.4 GHz and about 2.5 GHz, between about 5 GHz and about 7 GHz, at about 500 MHz, at about 915 MHz, or at about 896 MHz.
  • ISM industrial, scientific, and medical
  • the conversion of carbon dioxide entering the reaction vessel 200 in the input gas stream 230 begins as the temperature in the reaction vessel 200 reaches about 400°C (from heating of the catalytic material 21 1 by microwave irradiation; additional heating can be applied if need or desired). At that temperature, the conversion of carbon dioxide is around 40%.
  • the carbon dioxide conversion rate increases to nearly 100% as the temperature increases from 400°C to about 600°C or 700°C. It is therefore useful to irradiate the catalytic material 21 1 only as much as necessary to maintain a temperature between about 600°C and about 700°C in the reaction vessel 200; any further heating beyond about 700°C does not improve the carbon dioxide conversion rate, but might cause excessive heating and potential damage to the catalytic material 21 1 or the reaction vessel 200.
  • Temperatures between about 400°C and about 600°C ⁇ e.g., greater than about 475°C) can also be maintained, albeit with correspondingly lower conversion rates of CO2 ⁇ e.g., it may be desirable in some examples to remain below the Curie temperature of a magnetite catalyst (about 585°C); note that at 475°C about 80% conversion of CO2 has been observed using magnetite). Note that the elevated temperature of the catalytic material 21 1 can be maintained without relying on heat produced by oxidation of the methane (or other hydrocarbon or carbonaceous fuel), which would reduce the net conversion of carbon dioxide by the reaction vessel 200.
  • Pressures between about 1 atm and about 70 atm can be employed in the reaction vessel 200; in some examples pressures between about 1 atm and about 30 atm can be employed; in some examples pressures between about 1 atm and about 10 atm can be employed; in some other examples pressures between about 15 atm and about 25 atm, or at about 20 atm, can be employed; in some other examples pressures between about 35 atm and about 45 atm, or at about 40 atm, can be employed; in some other examples pressures between about 55 atm and about 65 atm, or at about 60 atm, can be employed.
  • the carbon dioxide source gas 230 and the methane source gas 240 are dehumidified by any suitable method ⁇ e.g., by condensation on cooling elements using wet or dry cooling, refrigerant cooling, thermoelectric cooling, or cryogenic cooling, or by using a dry or wet desiccant) to reduce or substantially eliminate water from the input gas streams 230/240.
  • Natural gas can be employed as the methane source gas 240, and is often sufficiently dehumidified without requiring a further dehumidification process; other methane source gases might contain more water and require dehumidification before introduction as the methane source gas stream 240.
  • water content of the gaseous carbon dioxide source 230 and the gaseous methane source 240 is less than about 2% by volume or less than about 1 % by volume, and the water content of the combination of all gases entering the reaction vessel 200 is less than about 3% by volume or less than about 1 % by volume.
  • water content can, if needed or desired, be controlled (by dehumidification) as a process parameter for controlling or optimizing the conversion of carbon dioxide.
  • dehumidified can refer to a source gas that has undergone a dehumidification process as part of the disclosed methods, or that has a sufficiently low water content as supplied without a requiring a separate dehumidification step.
  • the degree to which one or both source gases are dehumidified can be selected, e.g., so as to achieve optimized conversion of carbon dioxide, or to achieve an acceptable level of carbon dioxide conversion while limiting the expense or energy consumption of any needed dehumidification process.
  • the carbon dioxide source gas 230 is pure, or nearly pure, carbon dioxide; in many other examples, the carbon dioxide source gas 230 is not pure carbon dioxide, but will include other gases, typically inert gases.
  • a common component of the carbon dioxide source gas 230 is nitrogen, which in some examples can be present in the carbon dioxide source gas 230 at non-zero levels up to about 80% by volume ⁇ e.g., greater than about 60% by volume, greater than about 70% by volume, or equal to about 78% by volume).
  • the carbon dioxide conversion rates observed above were obtained at gas flow rates that resulted in residence times of the gases in the irradiated catalytic material 21 1 on the order of 100 milliseconds or less.
  • the main effects of the presence of nitrogen (or other inert gas) is that it decreases the effective residence times of the carbon dioxide and methane in the catalytic material 21 1 , and carries more heat away from the irradiated catalytic material 21 1 . Both of those effects appear to be relatively minor, however. For example, higher microwave power can offset the heat carried away by the nitrogen flow.
  • the processes disclosed herein can be advantageously employed to convert carbon dioxide and methane, which are both potent greenhouse gases, into a higher-value mixture of carbon monoxide and hydrogen ⁇ i.e., synthesis gas, or syngas). A mixture that includes the carbon monoxide and the hydrogen flows out of the reaction vessel 200.
  • At least a portion of the carbon monoxide and hydrogen produced can be separated from the stream 270 that can include unreacted (or regenerated) carbon dioxide, unreacted (or regenerated) methane, or other reaction byproducts.
  • the processes disclosed herein can be operated so that less carbon dioxide leaves the reaction vessel 200 in the mixtures 260/270 than is introduced into the reaction vessel 200 in the source gas 230, so that a net decrease in atmospheric carbon dioxide occurs.
  • At least a portion of carbon dioxide present in the mixture 270 can be recovered and reintroduced into the source gas stream 230 into the reaction vessel 200. If needed, that recovered carbon dioxide can be dehumidified (by any suitable method disclosed above) before its reintroduction into the source gas stream 230 into the reaction vessel 200.
  • carbon dioxide source gas stream 230 Various plentiful sources of carbon dioxide can be employed to obtain the carbon dioxide source gas stream 230, including but not limited to combustion exhaust, biomass digestion ⁇ e.g., in the course of ethanol production), chemical processing byproducts ⁇ e.g., from hydrogen generation, production of lime or cement, ethylene production, or ammonia production), smelting or other mineral or ore processing, or any other natural or anthropogenic source of carbon dioxide.
  • combustion exhaust include flue gas produced by, e.g., an electrical generation facility ⁇ e.g., gas- or coal-fired) or a steam generation facility.
  • Flue gas typically comprises about 60% or more (by volume) of nitrogen, about 10% or more (by volume) of carbon dioxide, and about 10% or more (by volume) of water vapor, with the remainder being oxygen and various trace gases ⁇ e.g., SO2, SO3, HCI, and so forth).
  • SO2, SO3, HCI various trace gases
  • reaction rate of carbon dioxide and methane in the reaction vessel 200 decreases over time as the reactant source gases 230/240 continue to flow into the input ports of the reaction vessel 200. It has been proposed that the decreased reaction rate might be due to so-called "coking" of the catalytic material 21 1 ⁇ i.e., deposition of elemental carbon on the catalytic material 21 1 ). Whatever the mechanism for the decreased reaction rate, it has also been observed that interrupting the flow of the methane source gas 240 into the reaction vessel 200 causes the carbon dioxide conversion rate to increase. A proposed mechanism for the increase is reaction of carbon dioxide in the source gas 230 with elemental carbon deposited on the catalytic material ⁇ e.g., according to the Boudouard reaction
  • the methane source gas 240 can be reintroduced into the reaction chamber 200 and carbon dioxide conversion will resume at about its original rate.
  • the interruption and resumption of methane flow can be repeated as needed to restore the reaction rate (presumably by restoration of activity of the catalytic material 21 1 ; restoration of the reaction rate by any known or unknown mechanism shall fall within the scope of the present disclosure or appended claims).
  • a flow of steam can be introduced into the reaction vessel 200 (only upon observation of a decrease in the rate of carbon dioxide conversion). The steam appears to restore the carbon dioxide conversion rate to its original rate.
  • a proposed mechanism is reaction of the steam with the carbon deposits ⁇ e.g., according to
  • the carbon monoxide and hydrogen in the output stream 260 can be used for any suitable or desirable purpose, e.g., as feedstock for any number of chemical processes.
  • the output stream is be introduced into a separate, second reaction vessel 300.
  • Other gases can be introduced into the reaction vessel 300 as well, as needed or desired, for modifying, modulating, or controlling reactive processes in the reaction vessel 300.
  • the hydrogen and the carbon monoxide produced in the output stream 260 flows into the reaction vessel 300 containing a second catalytic material 31 1 .
  • the second catalytic material 31 1 can comprise any suitable catalytic material provided in any suitable physical form, e.g., a packed bed, coated media of any suitable shape or form, a flowing fluidized particulate catalyst, and so on.
  • the catalytic material 31 1 is a packed bed that includes magnetite pellets intermixed with inert alumina pellets (or other one or more suitable inert materials).
  • the second catalytic material 31 1 in the reaction vessel 300 catalyzes exothermic reactions involving the carbon monoxide and the hydrogen to produce one or more multiple-carbon reaction products ⁇ i.e., organic compounds containing two or more carbon atoms).
  • the reactions occurring in the reaction vessel 300 can include myriad different reactions occurring in parallel or in sequence; many of the reactions may fall within the general category of Fischer-Tropsch processes, however, any pertinent reactions or mechanisms shall fall within the scope of the present disclosure or appended claims.
  • a product mixture exits the reaction vessel 300 and can include unreacted (or regenerated) carbon dioxide or methane, unreacted (or regenerated) carbon monoxide or hydrogen, one or more multiple- carbon reaction products, or other reaction byproducts.
  • the one or more multiple-carbon reaction products 360 can include one or more of: (i) one or more linear or branched-chain aliphatic hydrocarbons ⁇ i.e., alkanes, alkenes, or alkynes), (ii) one or more linear or branched-chain aliphatic primary alcohols, (iii) one or more linear or branched- chain aliphatic aldehydes or ketones; (iv) one or more linear or branched-chain aliphatic carboxylic acids, (v) one or more linear or branched-chain aliphatic esters, (vi) one or more linear or branched-chain aliphatic acid anhydrides, or (vii) other multiple-carbon organic compounds.
  • Reaction conditions ⁇ e.g., temperatures and pressure
  • composition and flow rate of the input reactant gas flows can be altered or optimized to obtain various desired distributions of product compounds.
  • pressures between about 1 atm and about 30 atm can be employed; in some examples pressures between about 15 atm and about 25 atm, or at about 20 atm, can be employed.
  • the reaction vessel 300 typically is maintained at a lower temperature than the reaction vessel 200. If needed or desired, a cooling jacket or other cooling apparatus can be employed. Lower temperature conditions favor production of longer-chain products of Fischer-Tropsch processes.
  • the cooling apparatus is used to keep the reaction vessel portion 300, and the catalytic material 31 1 in it, below about 350°C. Any suitable type of cooling can be employed, including but not limited to a water-cooled jacket, piping, or coils, wet or dry cooling, other coolant-based refrigeration, thermoelectric cooling, cryogenic cooling, and so forth.
  • Example 1 A method for generating a mixture of carbon monoxide and hydrogen, the method comprising: (a) introducing a flow of a dehumidified gaseous source of carbon dioxide into a reaction vessel; (b) introducing a flow of a dehumidified gaseous source of methane into the reaction vessel; (c) irradiating catalytic material in the reaction vessel with microwave energy so as to heat the catalytic material and drive an endothermic reaction of the carbon dioxide and the methane, catalyzed by the catalytic material, that produces hydrogen and carbon monoxide; and (d) allowing a mixture that includes the carbon monoxide and the hydrogen to flow out of the reaction vessel, wherein: (e) at least a portion of heat required to maintain a temperature within the reaction vessel is supplied by the microwave energy irradiating the catalytic material in the reaction vessel; and (f)
  • Example 3 The method of any one of Examples 1 or 2 further comprising dehumidifying the gaseous source of carbon dioxide or the gaseous source of methane before introduction into the reaction vessel.
  • Example 4 The method of any one of Examples 1 through 3 further comprising separating at least a portion of the carbon monoxide and the hydrogen from the mixture that leaves the reaction vessel.
  • Example 5 The method of any one of Examples 1 through 4 wherein water content of the gaseous source of carbon dioxide and the gaseous source of methane is (i) less than about 2% by volume or (ii) less than about 1 % by volume.
  • Example 6 The method of any one of Examples 1 through 5 wherein water content of a combination of all gases entering the reaction vessel is (i) less than about 3% by volume, (ii) less than about 2% by volume, or (iii) less than about 1 % by volume.
  • Example 7 The method of any one of Examples 1 through 6 wherein the gaseous source of carbon dioxide includes a non-zero amount of nitrogen (i) up to about 80% nitrogen by volume, (ii) greater than about 60% nitrogen by volume, (iii) greater than about 70% nitrogen by volume, or (iv) about equal to 78% nitrogen by volume.
  • Example 8 The method of any one of Examples 1 through 7 wherein less carbon dioxide leaves the reaction vessel in the mixture than is introduced into the reaction vessel.
  • Example 9 The method of any one of Examples 1 through 8 further comprising recovering from the mixture that leaves the reaction vessel at least a portion of carbon dioxide present in that mixture, and reintroducing the recovered carbon dioxide into the reaction vessel.
  • Example 10 The method of Example 9 further comprising dehumidifying the recovered carbon dioxide before reintroduction into the reaction vessel.
  • Example 1 1 The method of any one of Examples 1 through 10 further comprising maintaining the reaction vessel at a temperature (i) between about 400°C and about 600°C, (ii) above about 475°C, or (iii) between about 600°C and about 700°C.
  • Example 12 The method of any one of Examples 1 through 1 1 wherein temperature within the reaction vessel is maintained without relying on heat produced by oxidation of the methane or other hydrocarbon or carbonaceous fuel.
  • Example 13 The method of any one of Examples 1 through 12 wherein the gaseous source of carbon dioxide comprises combustion exhaust.
  • Example 14 The method of Example 13 further comprising dehumidifying the combustion exhaust before introducing the combustion exhaust into the reaction vessel.
  • Example 15 The method of any one of Examples 13 or 14 wherein the combustion exhaust comprises flue gas from an electrical or steam generation facility.
  • Example 16 The method of any one of Examples 1 through 15 wherein the gaseous source of methane comprises natural gas.
  • Example 17 The method of any one of Examples 1 through 16 wherein the reaction vessel includes one or more windows comprising one or more materials that transmit the microwave energy, and the microwave energy irradiating the catalytic material in the reaction vessel passes through the one or more windows.
  • Example 18 The method of any one of Examples 1 through 17 wherein the reaction vessel includes one or more of quartz, silica, zirconia, cordierite, boron nitride, alumina, or other suitable micro-wave-transmitting material.
  • Example 19 The method of any one of Examples 1 through 18 wherein the microwave energy is introduced into the reaction vessel through a pair of microwave waveguides, the microwave waveguides are arranged on opposing sides of the reaction vessel and offset from one another along a direction of flow through the reaction vessel, and phases of microwave radiation entering the reaction vessel from the waveguides differ from each other by about a quarter of a period of the microwave radiation.
  • Example 20 The method of any one of Examples 1 through 19 wherein the catalytic material includes one or more materials based on one or more of iron, cobalt, nickel, rhodium, ruthenium, platinum, palladium, other one or more suitable catalytic materials, or combinations thereof.
  • Example 21 The method of any one of Examples 1 through 20 wherein the catalytic material includes magnetite.
  • Example 22 The method of any one of Examples 1 through 21 further comprising introducing at least a portion of the mixture that leaves the reaction vessel into a second reaction vessel containing a second catalytic material, wherein the second catalytic material in the second reaction vessel catalyzes exothermic reactions involving the carbon monoxide and the hydrogen to produce one or more multiple-carbon reaction products.
  • Example 23 The method of any one of Examples 1 through 21 further comprising introducing at least a portion of the mixture that leaves the reaction vessel into a second reaction vessel containing a second catalytic material, wherein the second catalytic material in the second reaction vessel catalyzes exothermic reactions involving the carbon monoxide and the hydrogen to produce one or more multiple-carbon reaction products.
  • Example 22 wherein the one or more multiple-carbon reaction products includes one or more of: (i) one or more linear or branched-chain aliphatic hydrocarbons, (ii) one or more linear or branched-chain aliphatic primary alcohols, (iii) one or more linear or branched-chain aliphatic aldehydes or ketones; (iv) one or more linear or branched-chain aliphatic carboxylic acids, (v) one or more linear or branched-chain aliphatic esters, or (vi) one or more linear or branched-chain aliphatic acid anhydrides.
  • Example 24 The method of any one of Examples 1 through 23 further comprising: (i) upon observing a decrease in a rate of carbon dioxide conversion in the reaction vessel, interrupting the flow of the gaseous source of methane into the reaction vessel, and (ii) upon observing an increase in the rate of carbon dioxide conversion in the reaction vessel after interrupting the flow of the gaseous source of methane into the reaction vessel, restoring the flow of the gaseous source of methane into the reaction vessel.
  • Example 25 Example 25.
  • the method of any one of Examples 1 through 24 further comprising: (g) introducing a flow of steam into the reaction vessel only upon observing a decrease in a rate of carbon dioxide conversion in the reaction vessel; and (h) upon observing an increase in the rate of carbon dioxide conversion in the reaction vessel after introducing the flow of steam into the reaction vessel, terminating the flow of steam into the reaction vessel.
  • Example 26 The method of any one of Examples 1 through 25 wherein the microwave energy is at one or more frequencies: (i) between about 300 MHz and about 10 GHz; (ii) within the so-called industrial, scientific, and medical (ISM) radio bands; (iii) between about 500 MHz and about 3 GHz; (iv) between about 2.4 GHz and about 2.5 GHz; (v) between about 5 GHz and about 7 GHz; (vi) at about 500 MHz; (vii) at about 915 MHz; or (viii) at about 896 MHz.
  • ISM industrial, scientific, and medical
  • each such phrase shall denote the case wherein the quantity in question has been reduced or diminished to such an extent that, for practical purposes in the context of the intended operation or use of the disclosed or claimed apparatus or method, the overall behavior or performance of the apparatus or method does not differ from that which would have occurred had the null quantity in fact been completely removed, exactly equal to zero, or otherwise exactly nulled.
  • any labelling of elements, steps, limitations, or other portions of an example or claim ⁇ e.g., first, second, etc., (a), (b), (c), etc., or (i), (ii), (iii), etc.) is only for purposes of clarity, and shall not be construed as implying any sort of ordering or precedence of the portions so labelled. If any such ordering or precedence is intended, it will be explicitly recited in the example or claim or, in some instances, it will be implicit or inherent based on the specific content of the example or claim.

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Abstract

L'invention concerne une méthode pour la conversion de gaz à effet de serre, qui consiste : à introduire un flux d'une source gazeuse déshumidifiée de dioxyde de carbone dans une cuve de réaction ; à introduire un flux d'une source gazeuse déshumidifiée de méthane dans la cuve de réaction ; et à exposer à l'énergie de micro-ondes un matériau catalytique dans la cuve de réaction. Le matériau catalytique exposé est chauffé et catalyse une réaction endothermique de dioxyde de carbone et de méthane qui produit de l'hydrogène et du monoxyde de carbone. Au moins une partie de la chaleur requise pour maintenir une température à l'intérieur de la cuve de réaction est fournie par l'énergie micro-onde; un arc électrique, une décharge électrique et une génération de plasma sont supprimés. Si on le souhaite, un mélange qui comprend du monoxyde de carbone et de l'hydrogène peut s'écouler hors de la cuve de réaction et être introduit dans une seconde cuve de réaction pour subir des réactions catalysées produisant de multiples produits de réaction de carbone.
PCT/US2018/012720 2017-01-07 2018-01-07 Conversion de gaz à effet de serre en gaz de synthèse par reformage à sec WO2018129424A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130197288A1 (en) * 2012-01-31 2013-08-01 Linde Ag Process for the conversion of synthesis gas to olefins
US20140163120A1 (en) * 2010-09-08 2014-06-12 Ecokap Technologies Llc Method and apparatus for producing liquid hydrocarbon fuels
US20150246337A1 (en) * 2012-09-07 2015-09-03 Korea Basic Science Institute Plasma dry reforming apparatus
US9238214B2 (en) * 2011-10-17 2016-01-19 Ecokap Technologies Llc Process and apparatus for converting greenhouse gases into synthetic fuels
WO2016207892A1 (fr) * 2015-06-25 2016-12-29 Technology Innovation Momentum Fund (Israel) Limited Partnership, C/O Ramot At Tel-Aviv University Ltd. Catalyseur de reformage à sec du méthane et son procédé de préparation
WO2017027330A1 (fr) * 2015-08-07 2017-02-16 Ecokap Power Llc Conversion de gaz à effet de serre en gaz de synthèse par reformage à sec

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140163120A1 (en) * 2010-09-08 2014-06-12 Ecokap Technologies Llc Method and apparatus for producing liquid hydrocarbon fuels
US9238214B2 (en) * 2011-10-17 2016-01-19 Ecokap Technologies Llc Process and apparatus for converting greenhouse gases into synthetic fuels
US20130197288A1 (en) * 2012-01-31 2013-08-01 Linde Ag Process for the conversion of synthesis gas to olefins
US20150246337A1 (en) * 2012-09-07 2015-09-03 Korea Basic Science Institute Plasma dry reforming apparatus
WO2016207892A1 (fr) * 2015-06-25 2016-12-29 Technology Innovation Momentum Fund (Israel) Limited Partnership, C/O Ramot At Tel-Aviv University Ltd. Catalyseur de reformage à sec du méthane et son procédé de préparation
WO2017027330A1 (fr) * 2015-08-07 2017-02-16 Ecokap Power Llc Conversion de gaz à effet de serre en gaz de synthèse par reformage à sec

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