WO2016007825A1 - Methods, systems, and materials for capturing carbon dioxide and converting it to a chemical product - Google Patents

Methods, systems, and materials for capturing carbon dioxide and converting it to a chemical product Download PDF

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Publication number
WO2016007825A1
WO2016007825A1 PCT/US2015/039889 US2015039889W WO2016007825A1 WO 2016007825 A1 WO2016007825 A1 WO 2016007825A1 US 2015039889 W US2015039889 W US 2015039889W WO 2016007825 A1 WO2016007825 A1 WO 2016007825A1
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Prior art keywords
carbon dioxide
dual function
function material
portions
gas
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PCT/US2015/039889
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French (fr)
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Robert J. Farrauto
Melis S. DUYAR
Ah-Hyung Alissa Park
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The Trustees Of Columbia University In The City Of New York
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Publication of WO2016007825A1 publication Critical patent/WO2016007825A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8693—After-treatment of removed components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/202—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1026—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • C0 2 carbon dioxide
  • CCS C0 2 capture and sequestration
  • Embodiments of the disclosed subject matter include methods and systems that utilize a dual function material to capture C0 2 from an emission source and at the same temperature, e.g., about 250 to about 350 degrees Celsius, and in the same reactor, convert it to a chemical product, e.g., synthetic natural gas, requiring no additional heat input.
  • the dual functional material includes ruthenium as a methanation catalyst and nano-dispersed calcium oxide as a C0 2 adsorbent, both of which are supported on a substantially porous carrier fabricated from aluminum oxide or a similar material.
  • a spillover process drives C0 2 from the sorbent to the Ru sites where methanation occur using stored hydrogen gas that is supplied from excess renewable power. This approach utilizes flue gas sensible heat and eliminates the current energy intensive and corrosive capture and storage processes without having to transport captured C0 2 or add external heat.
  • FIG. 1 is a schematic diagram of methods and systems according to some embodiments of the disclosed subject matter
  • FIG. 2 is a schematic diagram of a dual function material according to some embodiments of the disclosed subject matter.
  • FIG. 3 is a chart of a method according to some embodiments of the disclosed subject matter.
  • aspects of the disclosed subject matter include methods, systems, and materials for capturing carbon dioxide and converting it to a chemical product, e.g., synthetic natural gas.
  • dual function materials which include both carbon dioxide adsorbents and methanation catalysts, are used to capture C0 2 from an emission source and at the same temperature in the same reactor convert it to synthetic natural gas.
  • system 100 for capturing carbon dioxide 102 and converting it to a synthetic natural gas 104.
  • system 100 includes a reactor 106 that includes a dual function
  • Reactor 106 includes a plurality of inlets and outlets.
  • a stream of gas 108 e.g., from a power plant 109, including carbon dioxide 102 is in fluid communication with reactor 106 via an inlet 110.
  • a supply of hydrogen gas 111 e.g., typically produced from a renewable source 112 is in fluid communication reactor 106 via an inlet 113.
  • An effluent stream of gas 114 which is substantially free of C0 2 , exits reactor 106 via an outlet 116 and synthetic natural gas 104 produced in the reactor, e.g., methane (CH 4 ), is released from the reactor via an outlet 118.
  • CH 4 released via outlet 118 is compressed, dried, and either recycled and used as fuel in plant 109 or sold to the natural gas grid (not shown).
  • dual function material 107 which is positioned within reactor 106, includes a carrier portion 120, adsorbent portions 122, and catalyst portions 124. Adsorbent portions 122 and catalyst portions 124 are positioned on surfaces 126 of carrier portion 120.
  • Adsorbent portions 122 adsorb carbon dioxide 102 present in stream of gas 108 until the adsorbent portions are substantially saturated with the carbon dioxide.
  • Adsorbent portions 122 are fabricated from materials that desorb carbon dioxide 102 when exposed to hydrogen, e.g., from supply of hydrogen gas 111, at a temperature of about at least 250 degrees Celsius.
  • adsorbent portions 122 include one or more alkaline materials including alkaline earth metal oxides of Ca, Mg, Sr, Ba, and/or combinations thereof.
  • the one or more alkaline metal oxides include CaO, e.g., dual function material 107 includes about 2 to about 10 percent CaO by weight.
  • the CaO is dispersed so as to form nano-sized islands (not shown) on surfaces 126 of carrier portion 120.
  • Methanation catalyst portions 124 which are positioned on carrier portion 120 adjacent adsorbent portions 122, facilitate the formation of synthetic natural gas 104, e.g., CH 4 , from carbon dioxide 102 desorbed from the adsorbent portions and hydrogen from supply of hydrogen gas 111.
  • catalyst portions 124 include one of ruthenium, nickel, platinum, rhodium, copper, cobalt, group VIII transition metals or their oxides, and/or combinations thereof.
  • catalyst portions 124 include ruthenium, e.g., dual function material 107 includes about 1 to about 10 percent Ru by weight. In some embodiments, the Ru is dispersed so as to form nano-sized islands (not shown) on surfaces 126 of carrier portion 120.
  • Carbon dioxide 102 is typically adsorbed and desorbed by adsorbent portions 122 and the carbon dioxide is reacted with hydrogen to form synthetic natural gas 104 such as methane according to Equation (1):
  • substantially similar temperature which is about a temperature of stream of gas 108, i.e., about at least 250 degrees Celsius, before it contacts dual function material 107.
  • system 100 and method 200 typically do not require any additional heat.
  • dual function material 107 is fabricated in a particular order, e.g., adsorbent portions 122 including CaO are dispersed on carrier portion 120 before catalyst portions 124 including Ru are dispersed on the carrier portion.
  • adsorbent portions 122 including CaO are dispersed on carrier portion 120 before catalyst portions 124 including Ru are dispersed on the carrier portion.
  • the term "dispersed” include various known techniques including impregnating adsorbent portions 122 and catalyst portions 124 in carrier portion 120.
  • carrier portion 120 includes one of aluminum oxide (A1 2 0 3 ), ceria (Ce0 2 ), zirconia (Zr0 2 ), silica (Si0 2 ), zeolites (S1O 2 -AI 2 O 3 ), and/or combinations thereof.
  • Carrier portion 120 is typically fabricated so as to be substantially porous.
  • system 100 includes a control module 130 including a plurality of valves ("V") for controlling flows of stream of gas 108, supply of hydrogen gas 111, synthetic natural gas 104 formed, and substantially carbon dioxide-free stream of gas 114 in and out of the plurality of inlets and outlets of reactor 106.
  • control module 130 includes temperature, gas composition detectors, and pressure sensors and control mechanisms (not shown) for monitoring and adjusting temperatures, pressures, and gas compositions within reactor 106.
  • control module 130 is wirelessly connected with various components of system 100.
  • control module 130 is joined with one or more components of systems 100 via hard wire or any other known connection technology.
  • most of any C0 2 remaining in stream of gas 114 is released as a result of the heat generated during methanation and can be converted to methane in a small downstream catalytic reactor (not shown) to upgrade the mixture to pure CH 4 .
  • the downstream reactor typically operates at a lower temperature and achieves more favorable equilibrium conversions.
  • some embodiments include a method 200 for capturing carbon dioxide and converting it to a synthetic natural gas.
  • a dual function material e.g., one having characteristics that are the same as or similar to dual function material 107, which was described previously and shown in FIGS. 1 and 2, is provided.
  • a stream of gas including carbon dioxide is brought into contact with the dual function material until the adsorbent portions of the dual function material are substantially saturated with the carbon dioxide.
  • a stream of hydrogen gas is brought into contact with the dual function material that is substantially saturated with the carbon dioxide.
  • the temperature adjacent the stream of hydrogen gas and the dual function material is about at least 250 degrees Celsius or substantially the same as the temperature of the stream of gas before it is brought into contact with the dual function material.
  • the carbon dioxide is desorbed from the dual function material.
  • the carbon dioxide desorbed from the dual function material is reacted with the hydrogen gas provided at 206 (in the presence of methanation catalysts contained in the dual function material) to form a synthetic natural gas such as methane.
  • oxidation reactions within reactor 106 are selectively controlled to produce various particular products. Similar to how C0 2 is split into Ru— CO and Ru— O, selective oxidation reactions using C0 2 instead of 0 2 are performed. For example, the following products are made via selective oxidation using C0 2 instead of 0 2 : (1) splitting C0 2 into Ag— CO and Ag— O allows the production of ethylene oxide from ethylene; (2) splitting C0 2 on Ag forming Ag— O or O— FeMo allows the production of formaldehyde from methanol; (3) reacting butane on O— vanadium and O— phosphorous oxides both formed from C0 2 allows the production of maleic anhydride; (4) forming O— -Co and O— Mn allows the production of phenol from cumene; and (5) forming O— Rh allows for the production of nitric oxide (NO) from ammonia (NH 3 ).
  • NO nitric oxide
  • adsorbed C0 2 on dual function material 107 is converted via H 2 to oxygenates such as methanol, ethanol, etc., or higher hydrocarbons such as ethane, ethylene, etc., or by substitution of the methanation catalyst with a different catalyst and by varying operating conditions.
  • Dual function materials offer a unique renewable energy storage solution by producing synthetic natural gas directly from industrial flue gas, i.e., dilute C0 2 , while eliminating the energy requirement, corrosion, and transportation issues associated with CCS.
  • the dual function material contains a sorbent as well as a catalyst component, allowing it to both capture C0 2 and convert it to a fuel without an energy intensive thermal swing process.
  • the dual function material process utilizes hydrogen gas produced via electrolysis using renewable electricity, e.g., wind, hydro, geothermal, and/or solar, to make synthetic natural gas via the methanation reaction shown above in Equation (1).
  • Synthetic natural gas as an energy carrier has advantages over hydrogen gas because it can easily be handled and transported via the existing natural gas pipeline infrastructure. Furthermore, by eliminating a thermal swing process, the conversion of C0 2 to synthetic natural gas using dual function materials constrains the energy input to only renewable sources, i.e., in the form of hydrogen gas, thus allowing the C0 2 capture and utilization processes to approach carbon neutrality. Hence, dual function materials can be used to devise a carbon recycling scheme within combustion or fermentation based industries while integrating more renewable energy into the grid.
  • embodiments of the disclosed subject matter provide a simple isothermal CO 2 capture and methanation process that operates in a single reactor at the same temperature. Moreover, by producing synthetic natural gas, embodiments according to the disclosed subject matter approach carbon neutral power generation.

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Abstract

Methods, systems, and materials for capturing carbon dioxide and converting it to a chemical product, e.g., synthetic natural gas, are disclosed. In some embodiments, the methods include the following: providing a dual function material, the dual function material including a carrier portion, adsorbent portions, and methanation catalyst portions; contacting a stream of gas including carbon dioxide with the dual function material until the adsorbent portions are substantially saturated with the carbon dioxide; contacting a stream of hydrogen gas with the dual function material that is substantially saturated with the carbon dioxide; desorbing the carbon dioxide from the dual function material; and reacting the carbon dioxide with the hydrogen gas to form methane; wherein the carbon dioxide is adsorbed and desorbed by the adsorbent portions and the carbon dioxide is reacted with the hydrogen gas to form methane at a substantially similar temperature.

Description

METHODS, SYSTEMS, AND MATERIALS FOR CAPTURING CARBON DIOXIDE AND CONVERTING IT TO A CHEMICAL PRODUCT
CROSS REFERENCE TO RELATED APPLICATION(S)
[0001] This application claims the benefit of U.S. Provisional Application Nos.
62/023,517, filed July 11, 2014, and 62/190,532, filed July 9, 2015, each of which is incorporated by reference as if disclosed herein in its entirety.
BACKGROUND
[0002] The accumulation of carbon dioxide ("C02") emissions in the atmosphere due to industrialization is being held responsible for climate change with increasing certainty by the scientific community. In order to prevent its further accumulation in the atmosphere, C02 must be captured for storage or converted to useful products. Current materials and processes are very energy intensive.
[0003] Given the growing world population, which naturally translates to a growing energy demand, successful energy strategies of the future will have to focus on securing energy while making significant decreases in greenhouse gas emissions. The
intermittency of renewable energy, the logistics and energy penalties of C02 capture and sequestration ("CCS") pose major problems that prevent these technologies from being economically viable on a large scale. Large scale integration of wind and solar energy into the electrical grid requires a storage technology which can supply electricity on demand from these fluctuating sources.
[0004] Current CCS processes suffer from the fact that C02 absorption by corrosive liquids such as monoethanolamine solutions ("MEA") as well as adsorption by solids such as alkaline metal oxides rely on a high temperature thermal swing for their regeneration, i.e., significant amounts of heat and energy are required to release C02 from the MEA aqueous solution. These operations constitute the large portion of the cost of C02 capture. An additional challenge lies in the logistics and energy penalties of managing the concentrated C02 that must be transported to either an underground injection facility or a processing plant for conversion to useful products. SUMMARY
[0005] Embodiments of the disclosed subject matter include methods and systems that utilize a dual function material to capture C02 from an emission source and at the same temperature, e.g., about 250 to about 350 degrees Celsius, and in the same reactor, convert it to a chemical product, e.g., synthetic natural gas, requiring no additional heat input. In some embodiments, the dual functional material includes ruthenium as a methanation catalyst and nano-dispersed calcium oxide as a C02 adsorbent, both of which are supported on a substantially porous carrier fabricated from aluminum oxide or a similar material. A spillover process drives C02 from the sorbent to the Ru sites where methanation occur using stored hydrogen gas that is supplied from excess renewable power. This approach utilizes flue gas sensible heat and eliminates the current energy intensive and corrosive capture and storage processes without having to transport captured C02 or add external heat.
BRIEF DESCRIPTION OF THE DRAWINGS [0006] The drawings show embodiments of the disclosed subject matter for the purpose of illustrating the invention. However, it should be understood that the present application is not limited to the precise arrangements and instrumentalities shown in the drawings, wherein:
[0007] FIG. 1 is a schematic diagram of methods and systems according to some embodiments of the disclosed subject matter;
[0008] FIG. 2 is a schematic diagram of a dual function material according to some embodiments of the disclosed subject matter; and
[0009] FIG. 3 is a chart of a method according to some embodiments of the disclosed subject matter. DETAILED DESCRIPTION
[0010] Referring now to FIGS. 1-3, aspects of the disclosed subject matter include methods, systems, and materials for capturing carbon dioxide and converting it to a chemical product, e.g., synthetic natural gas. In some embodiments, dual function materials, which include both carbon dioxide adsorbents and methanation catalysts, are used to capture C02 from an emission source and at the same temperature in the same reactor convert it to synthetic natural gas.
[0011] Referring now to FIG. 1, some embodiments include a system 100 for capturing carbon dioxide 102 and converting it to a synthetic natural gas 104. In some embodiments, system 100 includes a reactor 106 that includes a dual function
material 107.
[0012] Reactor 106 includes a plurality of inlets and outlets. A stream of gas 108, e.g., from a power plant 109, including carbon dioxide 102 is in fluid communication with reactor 106 via an inlet 110. A supply of hydrogen gas 111, e.g., typically produced from a renewable source 112, is in fluid communication reactor 106 via an inlet 113. An effluent stream of gas 114, which is substantially free of C02, exits reactor 106 via an outlet 116 and synthetic natural gas 104 produced in the reactor, e.g., methane (CH4), is released from the reactor via an outlet 118. CH4 released via outlet 118 is compressed, dried, and either recycled and used as fuel in plant 109 or sold to the natural gas grid (not shown).
[0013] Referring now to FIG. 2, dual function material 107, which is positioned within reactor 106, includes a carrier portion 120, adsorbent portions 122, and catalyst portions 124. Adsorbent portions 122 and catalyst portions 124 are positioned on surfaces 126 of carrier portion 120.
[0014] Adsorbent portions 122 adsorb carbon dioxide 102 present in stream of gas 108 until the adsorbent portions are substantially saturated with the carbon dioxide. Adsorbent portions 122 are fabricated from materials that desorb carbon dioxide 102 when exposed to hydrogen, e.g., from supply of hydrogen gas 111, at a temperature of about at least 250 degrees Celsius.
[0015] In some embodiments, adsorbent portions 122 include one or more alkaline materials including alkaline earth metal oxides of Ca, Mg, Sr, Ba, and/or combinations thereof. In some embodiments, the one or more alkaline metal oxides include CaO, e.g., dual function material 107 includes about 2 to about 10 percent CaO by weight. In some embodiments, the CaO is dispersed so as to form nano-sized islands (not shown) on surfaces 126 of carrier portion 120.
[0016] Methanation catalyst portions 124, which are positioned on carrier portion 120 adjacent adsorbent portions 122, facilitate the formation of synthetic natural gas 104, e.g., CH4, from carbon dioxide 102 desorbed from the adsorbent portions and hydrogen from supply of hydrogen gas 111. In some embodiments, catalyst portions 124 include one of ruthenium, nickel, platinum, rhodium, copper, cobalt, group VIII transition metals or their oxides, and/or combinations thereof. In some embodiments, catalyst portions 124 include ruthenium, e.g., dual function material 107 includes about 1 to about 10 percent Ru by weight. In some embodiments, the Ru is dispersed so as to form nano-sized islands (not shown) on surfaces 126 of carrier portion 120.
[0017] Carbon dioxide 102 is typically adsorbed and desorbed by adsorbent portions 122 and the carbon dioxide is reacted with hydrogen to form synthetic natural gas 104 such as methane according to Equation (1):
C02 + 4H2→ CH4 + 2H20 ΔΗ = -164 kJ/mol. (1)
[0018] The adsorption, desorption, and methanation of C02 all occur at a
substantially similar temperature, which is about a temperature of stream of gas 108, i.e., about at least 250 degrees Celsius, before it contacts dual function material 107. In this way, other than the heat included in stream of gas 108, system 100 and method 200 typically do not require any additional heat.
[0019] In some embodiments, dual function material 107 is fabricated in a particular order, e.g., adsorbent portions 122 including CaO are dispersed on carrier portion 120 before catalyst portions 124 including Ru are dispersed on the carrier portion. As one skilled in the art will appreciate, the term "dispersed" include various known techniques including impregnating adsorbent portions 122 and catalyst portions 124 in carrier portion 120.
[0020] Still referring to FIG. 2, in some embodiments, carrier portion 120 includes one of aluminum oxide (A1203), ceria (Ce02), zirconia (Zr02), silica (Si02), zeolites (S1O2-AI2O3), and/or combinations thereof. Carrier portion 120 is typically fabricated so as to be substantially porous.
[0021] Referring again to FIG. 1, system 100 includes a control module 130 including a plurality of valves ("V") for controlling flows of stream of gas 108, supply of hydrogen gas 111, synthetic natural gas 104 formed, and substantially carbon dioxide-free stream of gas 114 in and out of the plurality of inlets and outlets of reactor 106. In some embodiments, control module 130 includes temperature, gas composition detectors, and pressure sensors and control mechanisms (not shown) for monitoring and adjusting temperatures, pressures, and gas compositions within reactor 106. As shown in FIG. 1, in some embodiments control module 130 is wirelessly connected with various components of system 100. Of course, although not shown, in some embodiments, control module 130 is joined with one or more components of systems 100 via hard wire or any other known connection technology.
[0022] Still referring to system 100, in some embodiments, most of any C02 remaining in stream of gas 114 is released as a result of the heat generated during methanation and can be converted to methane in a small downstream catalytic reactor (not shown) to upgrade the mixture to pure CH4. The downstream reactor typically operates at a lower temperature and achieves more favorable equilibrium conversions.
[0023] Referring now to FIG. 3, some embodiments include a method 200 for capturing carbon dioxide and converting it to a synthetic natural gas. At 202, a dual function material, e.g., one having characteristics that are the same as or similar to dual function material 107, which was described previously and shown in FIGS. 1 and 2, is provided. At 204, a stream of gas including carbon dioxide is brought into contact with the dual function material until the adsorbent portions of the dual function material are substantially saturated with the carbon dioxide. At 206, a stream of hydrogen gas is brought into contact with the dual function material that is substantially saturated with the carbon dioxide. During 206, the temperature adjacent the stream of hydrogen gas and the dual function material is about at least 250 degrees Celsius or substantially the same as the temperature of the stream of gas before it is brought into contact with the dual function material. At 208, the carbon dioxide is desorbed from the dual function material. At 210, the carbon dioxide desorbed from the dual function material is reacted with the hydrogen gas provided at 206 (in the presence of methanation catalysts contained in the dual function material) to form a synthetic natural gas such as methane.
[0024] In some embodiments, oxidation reactions within reactor 106 are selectively controlled to produce various particular products. Similar to how C02 is split into Ru— CO and Ru— O, selective oxidation reactions using C02 instead of 02 are performed. For example, the following products are made via selective oxidation using C02 instead of 02: (1) splitting C02 into Ag— CO and Ag— O allows the production of ethylene oxide from ethylene; (2) splitting C02 on Ag forming Ag— O or O— FeMo allows the production of formaldehyde from methanol; (3) reacting butane on O— vanadium and O— phosphorous oxides both formed from C02 allows the production of maleic anhydride; (4) forming O— -Co and O— Mn allows the production of phenol from cumene; and (5) forming O— Rh allows for the production of nitric oxide (NO) from ammonia (NH3).
[0025] While the embodiments above describe the production of methane, as one skilled in the art will appreciate, methods, systems, and materials described herein are also used to produce other chemical products. For example, in some embodiments, adsorbed C02 on dual function material 107 is converted via H2 to oxygenates such as methanol, ethanol, etc., or higher hydrocarbons such as ethane, ethylene, etc., or by substitution of the methanation catalyst with a different catalyst and by varying operating conditions.
[0026] Embodiments of the disclosed subject matter offer benefits over known technologies. Dual function materials offer a unique renewable energy storage solution by producing synthetic natural gas directly from industrial flue gas, i.e., dilute C02, while eliminating the energy requirement, corrosion, and transportation issues associated with CCS. The dual function material contains a sorbent as well as a catalyst component, allowing it to both capture C02 and convert it to a fuel without an energy intensive thermal swing process. The dual function material process utilizes hydrogen gas produced via electrolysis using renewable electricity, e.g., wind, hydro, geothermal, and/or solar, to make synthetic natural gas via the methanation reaction shown above in Equation (1).
[0027] Synthetic natural gas as an energy carrier has advantages over hydrogen gas because it can easily be handled and transported via the existing natural gas pipeline infrastructure. Furthermore, by eliminating a thermal swing process, the conversion of C02 to synthetic natural gas using dual function materials constrains the energy input to only renewable sources, i.e., in the form of hydrogen gas, thus allowing the C02 capture and utilization processes to approach carbon neutrality. Hence, dual function materials can be used to devise a carbon recycling scheme within combustion or fermentation based industries while integrating more renewable energy into the grid.
[0028] Although the chemical conversion of C02 as a means to offset the costs of CO2 capture has previously been considered, embodiments of the disclosed subject matter provide a simple isothermal CO2 capture and methanation process that operates in a single reactor at the same temperature. Moreover, by producing synthetic natural gas, embodiments according to the disclosed subject matter approach carbon neutral power generation.
[0029] Although the disclosed subject matter has been described and illustrated with respect to embodiments thereof, it should be understood by those skilled in the art that features of the disclosed embodiments can be combined, rearranged, etc., to produce additional embodiments within the scope of the invention, and that various other changes, omissions, and additions may be made therein and thereto, without parting from the spirit and scope of the present invention.

Claims

CLAIMS What is claimed is:
1. A method for capturing carbon dioxide and converting it to a chemical product, said method comprising:
providing a dual function material, said dual function material including a carrier portion, adsorbent portions that adsorb carbon dioxide present in a stream of gas, said adsorbent portions being positioned on surfaces of said carrier portion, and catalyst portions for facilitating the formation of a chemical product from carbon dioxide desorbed from said adsorbent portions and hydrogen from said supply of hydrogen gas, said catalyst portions being positioned on said carrier portion adjacent said adsorbent portions;
contacting a stream of gas including carbon dioxide with said dual function material until said adsorbent portions are substantially saturated with said carbon dioxide;
contacting a stream of hydrogen gas with said dual function material that is substantially saturated with said carbon dioxide;
desorbing said carbon dioxide from said dual function material; and
reacting said carbon dioxide with said hydrogen gas to form said chemical product; wherein said carbon dioxide is adsorbed and desorbed by said adsorbent portions and said carbon dioxide is reacted with said hydrogen gas to form said chemical product at a substantially similar temperature.
2. The method according to claim 1, wherein said chemical product is one of methane, methanol, ethanol, ethane, ethylene, and combinations thereof.
3. The method according to claim 1, wherein said substantially similar temperature is about a temperature of said stream of gas before it contacts said dual function material.
4. The method according to claim 3, wherein said substantially similar temperature is about at least 250 degrees Celsius.
5. The method according to claim 1, wherein said adsorbent portions include CaO.
6. The method according to claim 2, wherein said dual function material includes about 2 to about 10 percent CaO by weight.
7. The method according to claim 1, wherein said catalyst portions include one of
ruthenium, nickel, platinum, rhodium, copper, cobalt, group VIII transition metals or their oxides, and combinations thereof.
8. The method according to claim 7, wherein said dual function material includes about 1 to about 10 percent Ru by weight.
9. A system for capturing carbon dioxide and converting it to a synthetic natural gas, said system comprising:
a reactor including a plurality of inlets and outlets;
a stream of gas including carbon dioxide in fluid communication with said plurality of inlets of said reactor;
a supply of hydrogen gas in fluid communication with said plurality of inlets of said reactor; and
a dual function material positioned within said reactor, said dual function material including a carrier portion, adsorbent portions that adsorb carbon dioxide present in said stream of gas until said adsorbent portions are substantially saturated with said carbon dioxide, said adsorbent portions being positioned on surfaces of said carrier portion, wherein said adsorbent portions are fabricated from materials that desorb said carbon dioxide when exposed to renewable hydrogen from said supply of hydrogen gas at a temperature of about at least 250 degrees Celsius, and methanation catalyst portions for facilitating the formation of methane from carbon dioxide desorbed from said adsorbent portions and hydrogen from said supply of hydrogen gas, said catalyst portions being positioned on said carrier portion adjacent said adsorbent portions; wherein said methane formed and a substantially carbon dioxide-free stream of gas are in fluid communication with said plurality of outlets of said reactor.
10. The system according to claim 9, further comprising:
a control module including a plurality of valves for controlling flows of said stream of gas, said supply of hydrogen gas, said methane formed, and said substantially carbon dioxide-free stream of gas in and out of said plurality of inlets and outlets of said reactor, and temperature, gas composition detectors and pressure sensors and control mechanisms for monitoring and adjusting said reactor's internal temperature, gas composition, and pressure.
11. A dual function material for capturing carbon dioxide and converting it to a synthetic natural gas, said dual function material comprising:
a carrier portion;
adsorbent portions that adsorb carbon dioxide present in a feed stream until said adsorbent portions are substantially saturated with said carbon dioxide, said adsorbent portions being positioned on surfaces of said carrier portion, wherein said adsorbent portions are fabricated from materials that desorb said carbon dioxide when exposed to hydrogen at a temperature of about at least 250 degrees Celsius; and
methanation catalyst portions for facilitating the formation of methane from carbon dioxide desorbed from said adsorbent portions and hydrogen, said catalyst portions being positioned on said carrier portion adjacent said adsorbent portions.
12. The dual function material according to claim 11, wherein said adsorbent portions include one or more alkaline materials including alkaline earth metal oxides of Ca, Mg, Sr, Ba, and combinations thereof.
13. The dual function material according to claim 12, wherein said one or more alkaline metal oxides include CaO.
14. The dual function material according to claim 13, wherein said dual function material includes about 2 to about 10 percent CaO by weight.
15. The dual function material according to claim 13, wherein said CaO is dispersed so as to form nano-sized islands on said surfaces of said carrier portion.
16. The dual function material according to claim 11, wherein said catalyst portions
include one of ruthenium, nickel, platinum, rhodium, copper, cobalt, group VIII transition metals or their oxides, and combinations thereof.
17. The dual function material according to claim 16, wherein said dual function material includes about 1 to about 10 percent Ru by weight.
18. The dual function material according to claim 11, wherein said adsorbent portions include CaO, said catalyst portions include Ru, and said Ru is dispersed on said carrier portion after said CaO is dispersed on said carrier portion.
19. The dual function material according to claim 11, wherein said carrier portion includes one of aluminum oxide (AI2O3), ceria (Ce02), zirconia (Zr02), silica (Si02), zeolites
(S1O2-AI2O3), and combinations thereof.
20. The dual function material according to claim 11, wherein said adsorbent portions and said catalyst portions are impregnated in said carrier portion.
PCT/US2015/039889 2014-07-11 2015-07-10 Methods, systems, and materials for capturing carbon dioxide and converting it to a chemical product WO2016007825A1 (en)

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