WO2018129426A1

WO2018129426A1 - Conversion of greenhouse gases by dry reforming

Info

Publication number: WO2018129426A1
Application number: PCT/US2018/012722
Authority: WO
Inventors: Paul E. King; Ben Zion Livneh
Original assignee: Ecokap Technologies Llc
Priority date: 2017-01-07
Filing date: 2018-01-07
Publication date: 2018-07-12

Abstract

A method for conversion of greenhouse gases comprises: introducing a flow of a dehumidified gaseous source of carbon dioxide into a reaction vessel; introducing a flow of a dehumidified gaseous source of methane into the reaction vessel; and irradiating catalytic material in the reaction vessel with microwave energy. The irradiated catalytic material is heated and catalyzes an endothermic reaction of carbon dioxide and 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; electric arcing, electric discharge, and plasma generation are suppressed. A mixture that includes carbon monoxide and hydrogen can undergo catalyzed reactions producing multiple- carbon reaction products in a lower-temperature portion of the reaction vessel.

Description

CONVERSION OF GREENHOUSE GASES BY DRY REFORMING

PRIORITY CLAIM

[0001] This application claims priority of U.S. provisional App. No. 62/443,703 filed 07 JAN 2017 in the names of Paul E. King and Ben Zion Livneh, said provisional application being hereby incorporated by reference as if fully set forth herein.

FIELD OF THE INVENTION

[0002] The field of the present invention relates to greenhouse gas conversion. In particular, conversion of greenhouse gases by dry reforming is disclosed herein.

BACKGROUND

[0003] The subject matter of the present application may be related to subject matter disclosed in:

- U.S. Pub. No. 2003/0162846 entitled "Process and apparatus for the production of synthesis gas" published 08/28/2003 in the names of

Wang et al;

- U.S. Pub. No. 2004/00031731 entitled "Process for the microwave

treatment of oil sands and shale oils" published 02/19/2004 in the names of Honeycutt et al;

- U.S. Pub. No. 2004/0209303 entitled "Methods and compositions for directed microwave chemistry" published 10/21 /2004 in the name of Martin;

- U.S. Pub. No. 2007/0004809 entitled "Production of synthesis gas blends for conversion to methanol or Fischer-Tropsch liquids" published

01 /04/2007 in the names of Lattner et al;

- U.S. Pub. No. 2009/0205254 entitled "Method And System For Converting

A Methane Gas To A Liquid Fuel" published 08/20/2009 in the names of Zhu et al;

- U.S. Pub. No. 2010/0005720 entitled "Gasifier" published 01 /14/2010 in the names of Stadler et al; - U.S. Pub. No. 2010/0219107 entitled "Radio frequency heating of petroleum ore by particle susceptors" published 01 /14/2010 in the name of Parsche;

- U.S. Pub. No. 2012/0055851 entitled "Method and apparatus for producing liquid hydrocarbon fuels from coal" published 03/08/2012 in the name of

Kyle;

- U.S. Pub. No. 2012/0024843 entitled "Thermal treatment of carbonaceous materials" published 02/02/2012 in the names of Lissiaski et al;

- U.S. Pub. No. 2013/0197288 entitled "Process for the conversion of synthesis gas to olefins" published 08/01 /2013 in the names of Schafer et al;

- U.S. Pub. No. 2013/0213795 entitled "Heavy Fossil Hydrocarbon

Conversion And Upgrading Using Radio-Frequency or Microwave Energy" published 08/22/2013 in the names of Strohm et al;

- U.S. Pub. No. 2013/0303637 entitled "Method and apparatus for producing liquid hydrocarbon fuels from coal" published 1 1 /14/2013 in the name of Kyle;

- U.S. Pub. No. 2014/0051775 entitled "Method and apparatus for producing liquid hydrocarbon fuels" published 02/20/2014 in the name of Kyle;

- U.S. Pub. No. 2014/0066526 entitled "Method and apparatus for producing liquid hydrocarbon fuels" published 03/06/2014 in the name of Kyle;

- U.S. Pub. No. 2014/0163120 entitled "Method and apparatus for producing liquid hydrocarbon fuels" published 06/12/2014 in the name of Kyle;

- U.S. Pub. No. 2014/0346030 entitled "Methods and apparatus for

liquefaction of organic solids" published 1 1 /27/2014 in the name of Livneh;

- U.S. Pub. No. 2015/0246337 entitled "Plasma dry reforming apparatus" published 09/03/2015 in the names of Hong et al;

- U.S. Pub. No. 2016/0222300 entitled "Process and apparatus for

converting greenhouse gases into synthetic fuels" published 08/04/2016 in the name of Livneh;

- U.S. Pub. No. 2016/0333281 entitled "Method and apparatus for producing liquid hydrocarbon fuels" published 1 1 /17/2016 in the name of Kyle;

- U.S. Pat. No. 3,505,204 entitled "Direct conversion of carbonaceous material to hydrocarbons" issued 04/07/1970 to Hoffman; - U.S. Pat. No. 4,256,654 entitled "Conversion of hydrogen and carbon monoxide into C1-C4 range hydrocarbons" issued 03/17/1981 to

Schlinger et al;

- U.S. Pat. No. 4,392,940 entitled "Coal-oil slurry preparation" issued

07/12/1983 to Tao;

- U.S. Pat. No. 4,435,374 entitled "Method of producing carbon monoxide and hydrogen by gasification of solid carbonaceous material involving microwave irradiation" issued 03/06/1984 to Helm;

- U.S. Pat. No. 5,205,912 entitled "Conversion of methane using pulsed microwave radiation" issued 04/27/1993 to Murphy;

- U.S. Pat. No. 5,266,175 entitled "Conversion of methane, carbon dioxide and water using microwave radiation" issued 1 1 /30/1993 to Murphy;

- U.S. Pat. No. 5,972,175 entitled "Catalytic microwave conversion of gaseous hydrocarbons" issued 10/26/1999 to Tanner et al;

- U.S. Pat. No. 7,887,694 entitled "Methods of sequestering CO2" issued

02/15/201 1 to Constantz et al;

- U.S. Pat. No. 8,779,013 entitled "Process and apparatus for converting greenhouse gases into synthetic fuels" issued 07/15/2014 to Livneh;

- U.S. Pat. No. 9,238,214 entitled "Process and apparatus for converting greenhouse gases into synthetic fuels" issued 01 /19/2016 to Livneh;

- U.S. Pat. No. 9,353,323 entitled "Method and apparatus for producing liquid hydrocarbon fuels" issued 05/31 /2016 to Kyle;

- WO 2008/009644 published 01 /24/2008 in the names of O'Connor et al;

- Fidalgo et al; "Microwave-assisted dry reforming of methane"; Intl. J.

Hydrogen Energy Vol 22 p 4337 (2008);

- Fidalgo et al; "Syngas Production by CO2 Reforming of CH₄ under

Microwave Heating - Challenges and Opportunities"; Syngas: Production, Application and Environmental Impact, Indarto and Palguandi Eds. p 121 (2103);

- Hunt et al; "Microwave-Specific Enhancement of the Carbon-Carbon

Dioxide (Boudouard) Reaction"; J. Phys. Chem. C Vol 1 1 1 No 5 p 26871 (2013); and - Lavoie; "Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation"; Frontiers in Chem. Vol 2 Article 81 (2014).

Each one of those patents, publications, and applications is incorporated by reference as if fully set forth herein.

SUMMARY

[0004] 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. The carbon monoxide and the hydrogen can undergo catalyzed reactions producing one or more multiple-carbon reaction products in a lower-temperature portion of the reaction vessel.

[0005] Objects and advantages pertaining to dry reforming of greenhouse gases may become apparent upon referring to the example embodiments illustrated in the drawings and disclosed in the following written description or appended claims.

[0006] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The drawing illustrates schematically microwave-assisted catalyzed conversion of carbon dioxide and methane to carbon monoxide and hydrogen in a higher-temperature portion of a single reaction vessel, and catalyzed conversion carbon monoxide and hydrogen into one or more multiple-carbon reaction products in a lower-temperature portion of the same reaction vessel.

[0008] The embodiments depicted are shown only schematically: all features may not be shown in full detail or in proper proportion, certain features or structures may be exaggerated relative to others for clarity, and the drawings should not be regarded as being to scale. The embodiments shown are only examples: they should not be construed as limiting the scope of the present disclosure or appended claims.

DETAILED DESCRIPTION OF EMBODIMENTS

[0009] A method, for simultaneously consuming carbon dioxide and generating one or more multiple-carbon reaction products in a single reaction vessel 100, is illustrated schematically in the drawing. A flow of a dehumidified gaseous source 130 of carbon dioxide enters the reaction vessel 100 through an input port into a higher-temperature portion 101 of the reaction vessel 100. A flow of a dehumidified gaseous source 140 of methane enters the reaction vessel 100 through an input port into the higher-temperature portion 101 of the reaction vessel 100. Although separate ports are shown, the source gas flows 130/140 could instead be combined upstream and introduced into the high-temperature portion 101 of the reaction vessel 100 through a single port.

[0010] The higher-temperature reaction vessel portion 101 contains a catalytic material 1 1 1 . Any suitable catalytic material 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. Examples of 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)). In one example, the catalytic material 1 1 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 1 1 1 in the higher- temperature reaction vessel portion 101 is irradiated with microwave energy, thereby driving an endothermic reaction (catalyzed by the material 1 1 1 ) of the carbon dioxide and the methane to produce hydrogen and carbon monoxide {e.g., according to the dry gas reforming reaction CO2 + CH₄→ 2CO + 2H2; other reactions or pathways might occur as well).

[0011] In the example shown, the reaction vessel 100 contains within its volume a quartz-lined passage 1 10 that contains the catalytic material 1 1 1 . The quartz is substantially transparent to microwaves, and so acts as windows for transmitting the microwaves to propagate into the catalytic material 1 1 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 1 1 1 and the gases 130/140 flowing through it. Examples of suitable materials can include, but are not limited to, quartz, silica, zirconia, cordierite, boron nitride, alumina, and so forth. In the example shown the microwaves enter the reaction vessel 100 through waveguides 120. The arrangement shown in Fig. 1 is only one example of a suitable arrangement for the reaction vessel 100, microwave- transmitting windows or containment, microwave waveguides, and so forth; myriad other suitable arrangements can be implemented within the scope of the present disclosure or appended claims. In some examples, there is no space between the passage 1 10 and the reaction vessel 100. In some other examples, there is no distinct passage 1 10, and the quartz or other microwave-transmitting material is present only where microwave waveguides 120 enter the reaction vessel 100. In some examples, instead of or in addition to the waveguides 120, 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 1 1 1 .

[0012] For a given geometry of the reaction vessel 100 and the catalytic material 1 1 1 , differing numbers or arrangements of the waveguides 120 can be employed, as well as differing relative amplitudes and phases, to obtain an optimized, or at least adequate, distribution of microwave energy within the catalytic material 1 1 1 in the higher-temperature reaction vessel portion 101 . The higher-temperature portion 101 of the reaction vessel 100, the catalytic material 1 1 1 , or the irradiating of the catalytic material 1 1 1 are arranged so as to suppress or prevent electric arcing, electric discharge, and plasma generation within the reaction vessel 100 (in contrast to the methods disclosed in, e.g., U.S. Pat. No. 5,266,175 or U.S. Pub. No. 2015/0246337). Such arcing, discharge, or plasma generation is undesirable due to resultant damage to the catalytic material 1 1 1 or the reaction vessel 100, 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 120 or the higher-temperature portion 101 of the reaction vessel 100 can result in prevention or sufficient suppression. In some examples the one or more frequencies or phases of the microwave radiation can be selected to result in prevention or sufficient suppression. In some examples, use of multiple 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).

[0013] In the example shown, the microwave waveguides 120 are arranged on opposing sides of the reaction vessel 100 and offset from one another along a direction of flow through the reaction vessel 100. In that example arrangement, one suitable distribution of microwave energy within the higher-temperature reaction vessel portion 101 is obtained when the phases of microwave radiation entering the reaction vessel 100 through the waveguides 120 differ from each other by about a quarter of a period of the microwave radiation {i.e., a phase difference of about π/2). Other numbers and positions of waveguides 120, 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 1 1 1 . In some examples, 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) radio 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.

[0014] In the example shown, a lower-temperature portion 102 of the reaction vessel 100 is cooled so as to establish a suitable temperature gradient within the reaction vessel 100. The irradiated, higher-temperature portion 101 of the reaction vessel 100 exhibits a higher temperature than the cooled, lower-temperature portion 102 of the reaction vessel 100. At least a portion of heat required to maintain the temperature gradient is supplied by the microwave energy irradiating the first catalytic material 1 1 1 in the higher-temperature portion 101 of the reaction vessel 100; additional heating can be applied if need or desired. In the example shown, a cooling jacket 150 surrounds the lower-temperature reaction vessel portion 102, allowing cooling water to flow and reduce the temperature relative to the higher-temperature portion 101 ; cooling water can flow through any suitable arrangement of one or more jackets, pipes, coils, and so forth. Cooling of the lower-temperature portion 102 of the reaction vessel 100 can be achieved in any suitable way, including but not limited to wet or dry cooling, evaporative cooling, refrigeration, thermoelectric cooling, or cryogenic cooling.

[0015] The hydrogen and the carbon monoxide produced in the higher- temperature reaction vessel portion 101 flow from the higher-temperature portion 101 into the lower-temperature reaction vessel portion 102 containing a second catalytic material 1 12. As with the catalytic material 1 1 1 , the second catalytic material 1 12 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. In one example, the catalytic material 1 12 is a packed bed that includes magnetite pellets intermixed with inert alumina pellets (or other one or more suitable inert materials). In fact, in the example shown there need not be any distinct boundary between the catalytic materials 1 1 1 and 1 12; those materials might only differ in that the material 1 1 1 is heated by microwave irradiation while the material 1 12 is cooled by the cooling jacket 150. In other examples there can be a distinct boundary between the two catalytic materials {e.g., by physical separation by a screen or other gas-permeable barrier, or by differing catalytic material compositions).

[0016] The second catalytic material 1 12 in the lower-temperature reaction vessel portion 102 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 lower-temperature reaction vessel portion 102 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 100 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. At least a portion of the one or more multiple-carbon reaction products 160 can be separated from the remainder 170 of the product mixture. The one or more multiple-carbon reaction products 160 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.

[0017] Reaction conditions {e.g., temperatures and pressure) in both higher- and lower-temperature portions 101 /102 of the reaction vessel as well as compositions and flow rates of the input reactant gas flows 130/140 can be altered or optimized to obtain various desired distributions of product compounds. For example, pressures between about 1 atm and about 70 atm can be employed; 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. In some examples in which longer-chain multiple- carbon reaction products are desired, at least a portion of the multiple-carbon reaction products {e.g., one or more shorter-chain multiple-carbon reaction products) can be separated from the mixture leaving the reaction vessel 100 and reintroduced into the reaction vessel 100 {e.g., into the lower-temperature portion 102) to undergo further reactions to produce the desired longer-chain multiple- carbon reaction products. In some of those examples, the separated multiple- carbon reaction products can be dehumidified before reintroduction into the reaction vessel 100. The chain lengths encompassed by the terms "longer-chain" and "shorter-chain" will vary according to each particular application of the disclosed methods and the particular distribution of reaction products desired from the application of those methods.

[0018] The conversion of carbon dioxide entering the reaction vessel 100 in the input gas stream 130 begins as the temperature in the higher-temperature reaction vessel portion 101 reaches about 400°C (from heating of the catalytic material 1 1 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 1 1 1 only as much as necessary to maintain a temperature between about 600°C and about 700°C in the higher-temperature portion 101 of the reaction vessel 100; 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 1 1 1 or the reaction vessel 100. 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 1 1 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 100.

[0019] The lower-temperature portion 102 of the reaction vessel 100 is maintained at a lower temperature using the cooling jacket 150. Lower temperature conditions favor production of longer-chain products of Fischer-Tropsch processes. The cooling jacket 150 is used to keep the lower-temperature reaction vessel portion 102, and the catalytic material 1 12 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. [0020] The carbon dioxide source gas 130 and the methane source gas 140 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 130/140. Natural gas can be employed as the methane source gas 140, 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 140. Depending on the origin of the carbon dioxide source gas 130, dehumidification of the source gas 130 before introducing it into the reaction vessel 100 might be required, if the source gas 130 is not sufficiently dehumidified to begin with. Preferably, water content of the gaseous carbon dioxide source 130 and the gaseous methane source 140 is less than about 1 % by volume, and the water content of the combination of all gases entering the reaction vessel 100 is less than about 3% by volume, less about 2%, or less than about 1 % by volume. Within those ranges, water content can, if needed or desired, be controlled (by dehumidification) as a process parameter for controlling or optimizing the

conversion of carbon dioxide. Note that the term "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.

[0021] In some examples, the carbon dioxide source gas 130 is pure, or nearly pure, carbon dioxide; in many other examples, the carbon dioxide source gas 130 is not pure carbon dioxide, but will include other gases, typically inert gases. A common component of the carbon dioxide source gas 130 is nitrogen, which in some examples can be present in the carbon dioxide source gas 130 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 1 1 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 1 1 1 /1 12, and carries more heat away from the irradiated catalytic material 1 1 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.

[0022] The processes disclosed herein can be advantageously employed to convert carbon dioxide and methane, which are both potent greenhouse gases, into higher-value, multiple-carbon organic compounds, such as hydrocarbons, alcohols, aldehydes, ketones, and so forth. The processes disclosed herein can be operated so that less carbon dioxide leaves the reaction vessel 100 in the mixtures 160/170 than is introduced into the reaction vessel 100 in the source gas 130, so that a net decrease in atmospheric carbon dioxide occurs. To further reduce atmospheric carbon dioxide, at least a portion of carbon dioxide present in the mixture 170 can be recovered and reintroduced into the source gas stream 130 into the reaction vessel 100. If needed, that recovered carbon dioxide can be dehumidified (by any suitable method disclosed above) before its reintroduction into the source gas stream 130 into the reaction vessel 100.

[0023] Various plentiful sources of carbon dioxide can be employed to obtain the carbon dioxide source gas stream 130, 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. Some examples in which the carbon dioxide source gas stream 130 comprises 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). Before introducing the flue gas into the reaction vessel 100 as the carbon dioxide source gas 130, it is dehumidified by any suitable process. [0024] It has been observed that the reaction rate of carbon dioxide and methane in the higher-temperature reaction vessel portion 101 (as measured by carbon dioxide conversion) decreases over time as the reactant source gases 130/140 continue to flow into the input ports of the reaction vessel 100. It has been proposed that the decreased reaction rate might be due to so-called "coking" of the catalytic material 1 1 1 {i.e., deposition of elemental carbon on the catalytic material 1 1 1 ). Whatever the mechanism for the decreased reaction rate, it has also been observed that interrupting the flow of the methane source gas 140 into the reaction vessel 100 causes the carbon dioxide conversion rate to increase. A proposed mechanism for the increase is reaction of carbon dioxide in the source gas 130 with elemental carbon deposited on the catalytic material {e.g., according to the Boudouard reaction C + CO2→ 2CO). Whatever the mechanism, the methane source gas 140 can be reintroduced into the reaction chamber 100 and carbon dioxide conversion will resume at about its original rate. When the rate slows again, 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 1 1 1 ; restoration of the reaction rate by any known or unknown mechanism shall fall within the scope of the present disclosure or appended claims). Instead, or in addition, a flow of steam can be introduced into the higher-temperature portion 101 of the reaction vessel 100 (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 C + H2O→ CO + H2). Whatever the mechanism, the flow of steam can be terminated and carbon dioxide conversion will continue at about its original rate. When the rate slows again, the introduction and termination of the flow of steam can be repeated as needed to restore the reaction rate (presumably by restoration of activity of the catalytic material 1 1 1 ; restoration of the reaction rate by any known or unknown mechanism shall fall within the scope of the present disclosure or appended claims). [0025] In addition to the preceding, the following examples fall within the scope of the present disclosure or appended claims:

[0026] Example 1 . A method for simultaneously consuming carbon dioxide and generating one or more multiple-carbon reaction products in a single reaction vessel, the method comprising: (A) introducing a flow of a dehumidified gaseous source of carbon dioxide into a higher-temperature portion of a reaction vessel; (B) introducing a flow of a dehumidified gaseous source of methane into the higher-temperature portion of the reaction vessel; (C) irradiating first catalytic material in the higher-temperature portion of the reaction vessel with microwave energy so as to heat the first catalytic material and drive an endothermic reaction of the carbon dioxide and the methane, catalyzed by the first catalytic material, that produces hydrogen and carbon monoxide; (D) cooling a lower-temperature portion of the reaction vessel, thereby establishing a temperature gradient within the reaction vessel wherein the irradiated, higher-temperature portion of the reaction vessel exhibits a higher temperature than the cooled, lower-temperature portion of the reaction vessel; (E) allowing the hydrogen and the carbon monoxide produced to flow from the higher-temperature portion of the reaction vessel into the lower- temperature portion of the reaction vessel, wherein second catalytic material in the lower-temperature portion of the reaction vessel catalyzes exothermic reactions involving the carbon monoxide and the hydrogen to produce the one or more multiple-carbon reaction products; (F) allowing a mixture that includes the one or more multiple-carbon reaction products to flow out of the reaction vessel from the lower-temperature portion thereof; and (G) separating at least a portion of the one or more multiple-carbon reaction products from the mixture that leaves the reaction vessel, wherein: (H) at least a portion of heat required to maintain the temperature gradient is supplied by the microwave energy irradiating the first catalytic material in the higher-temperature portion of the reaction vessel; and (I) the higher- temperature portion of the reaction vessel, the catalytic material, or the irradiating of the catalytic material is arranged so as to suppress electric arcing, electric discharge, and plasma generation within the reaction vessel.

[0027] Example 2. The method of Example 1 wherein the higher-temperature portion of the reaction vessel, the catalytic material, or the irradiating of the catalytic material is arranged so as to prevent electric arcing, electric discharge, and plasma generation within the reaction vessel. [0028] 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.

[0029] Example 4. The method of any one of Examples 1 through 3 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.

[0030] Example 5. The method of any one of Examples 1 through 4 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.

[0031] Example 6. The method of any one of Examples 1 through 5 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.

[0032] Example 7. The method of any one of Examples 1 through 6 wherein less carbon dioxide leaves the reaction vessel in the mixture than is introduced into the reaction vessel.

[0033] Example 8. The method of any one of Examples 1 through 7 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 higher-temperature portion of the reaction vessel.

[0034] Example 9. The method of Example 8 further comprising dehumidifying the recovered carbon dioxide before reintroduction into the higher-temperature portion of the reaction vessel.

[0035] Example 10. The method of any one of Examples 1 through 9 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. [0036] Example 1 1 . The method of any one of Examples 1 through 10 further comprising maintaining the lower-temperature portion of the reaction vessel at a temperature below about 350°C.

[0037] Example 12. The method of any one of Examples 1 through 1 1 wherein the temperature gradient is established without relying on heat produced by oxidation of the methane or other hydrocarbon or carbonaceous fuel.

[0038] Example 13. The method of any one of Examples 1 through 12 wherein the gaseous source of carbon dioxide comprises combustion exhaust.

[0039] Example 14. The method of Example 13 further comprising dehumidifying the combustion exhaust before introducing the combustion exhaust into the higher- temperature portion of the reaction vessel.

[0040] 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. [0041] Example 16. The method of any one of Examples 1 through 15 wherein the gaseous source of methane comprises natural gas.

[0042] Example 17. The method of any one of Examples 1 through 16 wherein the higher-temperature portion of the reaction vessel includes one or more windows comprising one or more materials that transmit the microwave energy, and the microwave energy irradiating the first catalytic material in the higher- temperature portion of the reaction vessel passes through the one or more windows.

[0043] Example 18. The method of any one of Examples 1 through 17 wherein the higher-temperature portion of the reaction vessel includes one or more of quartz, silica, zirconia, cordierite, boron nitride, alumina, or other suitable

microwave-transmitting material.

[0044] Example 19. The method of any one of Examples 1 through 18 wherein the microwave energy is introduced into the higher-temperature portion of 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. [0045] Example 20. The method of any one of Examples 1 through 19 wherein the first or second 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.

[0046] Example 21 . The method of any one of Examples 1 through 20 wherein the first or second catalytic material includes magnetite.

[0047] Example 22. The method of any one of Examples 1 through 21 wherein the lower-temperature portion of the reaction vessel is cooled by a cooling water jacket, piping, or coils.

[0048] Example 23. The method of any one of Examples 1 through 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.

[0049] Example 24. The method of any one of Examples 1 through 23 further comprising separating from the mixture that leaves the reaction vessel at least a portion of the multiple-carbon reaction products present in that mixture, and reintroducing the separated multiple-carbon reaction products into the reaction vessel.

[0050] Example 25. The method of Example 24 further comprising dehumidifying the separated multiple-carbon reaction products before reintroduction into the reaction vessel.

[0051] Example 26. The method of any one of Examples 1 through 25 further comprising: (J) 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 (K) 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.

[0052] Example 27. The method of any one of Examples 1 through 26 further comprising: (J) upon observing a decrease in a rate of carbon dioxide conversion in the reaction vessel, introducing a flow of steam into the higher-temperature portion of the reaction vessel; and (K) 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 higher-temperature portion of the reaction vessel.

[0053] Example 28. The method of any one of Examples 1 through 27 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.

[0054] It is intended that equivalents of the disclosed example embodiments and methods shall fall within the scope of the present disclosure or appended claims. It is intended that the disclosed example embodiments and methods, and

equivalents thereof, may be modified while remaining within the scope of the present disclosure or appended claims.

[0055] In the foregoing Detailed Description, various features may be grouped together in several example embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that any claimed embodiment requires more features than are expressly recited in the corresponding claim. Rather, as the appended claims reflect, inventive subject matter may lie in less than all features of a single disclosed example embodiment. Thus, the appended claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separate disclosed embodiment. However, the present disclosure shall also be construed as implicitly disclosing any embodiment having any suitable set of one or more disclosed or claimed features {i.e., a set of features that are neither incompatible nor mutually exclusive) that appear in the present disclosure or the appended claims, including those sets that may not be explicitly disclosed herein. In addition, for purposes of disclosure, each of the appended dependent claims shall be construed as if written in multiple dependent form and dependent upon all preceding claims with which it is not inconsistent. It should be further noted that the scope of the appended claims does not necessarily encompass the whole of the subject matter disclosed herein.

[0056] For purposes of the present disclosure and appended claims, the conjunction "or" is to be construed inclusively {e.g., "a dog or a cat" would be interpreted as "a dog, or a cat, or both"; e.g., "a dog, a cat, or a mouse" would be interpreted as "a dog, or a cat, or a mouse, or any two, or all three"), unless: (i) it is explicitly stated otherwise, e.g., by use of "either... or," "only one of," or similar language; or (ii) two or more of the listed alternatives are mutually exclusive within the particular context, in which case "or" would encompass only those

combinations involving non-mutually-exclusive alternatives. For purposes of the present disclosure and appended claims, the words "comprising," "including," "having," and variants thereof, wherever they appear, shall be construed as open ended terminology, with the same meaning as if the phrase "at least" were appended after each instance thereof, unless explicitly stated otherwise. For purposes of the present disclosure or appended claims, when terms are employed such as "about equal to," "substantially equal to," "greater than about," "less than about," and so forth, in relation to a numerical quantity, standard conventions pertaining to measurement precision and significant digits shall apply, unless a differing interpretation is explicitly set forth. For null quantities described by phrases such as "substantially prevented," "substantially absent," "substantially eliminated," "about equal to zero," "negligible," and so forth, 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. [0057] For purposes of the present disclosure and appended claims, 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. In the appended claims, if the provisions of 35 USC § 1 12(f) are desired to be invoked in an apparatus claim, then the word "means" will appear in that apparatus claim. If those provisions are desired to be invoked in a method claim, the words "a step for" will appear in that method claim. Conversely, if the words "means" or "a step for" do not appear in a claim, then the provisions of 35 USC § 1 12(f) are not intended to be invoked for that claim.

[0058] If any one or more disclosures are incorporated herein by reference and such incorporated disclosures conflict in part or whole with, or differ in scope from, the present disclosure, then to the extent of conflict, broader disclosure, or broader definition of terms, the present disclosure controls. If such incorporated disclosures conflict in part or whole with one another, then to the extent of conflict, the later- dated disclosure controls.

[0059] The Abstract is provided as required as an aid to those searching for specific subject matter within the patent literature. However, the Abstract is not intended to imply that any elements, features, or limitations recited therein are necessarily encompassed by any particular claim. The scope of subject matter encompassed by each claim shall be determined by the recitation of only that claim.

Claims

CLAIMS What is claimed is:

1 . A method for simultaneously consuming carbon dioxide and generating one or more multiple-carbon reaction products in a single reaction vessel, the method comprising:

(A) introducing a flow of a dehumidified gaseous source of carbon dioxide into a higher-temperature portion of a reaction vessel;

(B) introducing a flow of a dehumidified gaseous source of methane into the higher-temperature portion of the reaction vessel;

(C) irradiating first catalytic material in the higher-temperature portion of the reaction vessel with microwave energy so as to heat the first catalytic material and drive an endothermic reaction of the carbon dioxide and the methane, catalyzed by the first catalytic material, that produces hydrogen and carbon monoxide;

(D) cooling a lower-temperature portion of the reaction vessel, thereby establishing a temperature gradient within the reaction vessel wherein the irradiated, higher-temperature portion of the reaction vessel exhibits a higher temperature than the cooled, lower-temperature portion of the reaction vessel;

(E) allowing the hydrogen and the carbon monoxide produced to flow from the higher-temperature portion of the reaction vessel into the lower- temperature portion of the reaction vessel, wherein second catalytic material in the lower-temperature portion of the reaction vessel catalyzes exothermic reactions involving the carbon monoxide and the hydrogen to produce the one or more multiple-carbon reaction products;

(F) allowing a mixture that includes the one or more multiple-carbon reaction products to flow out of the reaction vessel from the lower- temperature portion thereof; and

(G) separating at least a portion of the one or more multiple-carbon reaction products from the mixture that leaves the reaction vessel

wherein: (H) at least a portion of heat required to maintain the temperature gradient is supplied by the microwave energy irradiating the first catalytic material in the higher-temperature portion of the reaction vessel; and

(I) the higher-temperature portion of the reaction vessel, the catalytic material, or the irradiating of the catalytic material are arranged so as to suppress electric arcing, electric discharge, and plasma generation within the reaction vessel.

2. The method of Claim 1 wherein the higher-temperature portion of the reaction vessel, the catalytic material, or the irradiating of the catalytic material are arranged so as to prevent electric arcing, electric discharge, and plasma generation within the reaction vessel.

3. The method of Claim 1 further comprising dehumidifying the gaseous source of carbon dioxide or the gaseous source of methane before introduction into the reaction vessel.

4. The method of Claim 1 wherein water content of the gaseous source of carbon dioxide and the gaseous source of methane is less than about 1 % by volume.

5. The method of Claim 1 wherein water content of a combination of all gases entering the reaction vessel is less than about 3% by volume.

6. The method of Claim 1 wherein the gaseous source of carbon dioxide includes a non-zero amount of nitrogen up to about 80% nitrogen by volume.

7. The method of Claim 1 wherein less carbon dioxide leaves the reaction vessel in the mixture than is introduced into the reaction vessel.

8. The method of Claim 1 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 higher- temperature portion of the reaction vessel.

9. The method of Claim 8 further comprising dehumidifying the recovered carbon dioxide before reintroduction into the higher-temperature portion of the reaction vessel.

10. The method of Claim 1 further comprising maintaining the higher-

5 temperature portion of the reaction vessel at a temperature above about 475°C and maintaining the lower-temperature portion of the reaction vessel at a temperature below about 350°C.

1 1 . The method of Claim 1 wherein the temperature gradient is established without relying on heat produced by oxidation of the methane or other hydrocarbon o or carbonaceous fuel.

12. The method of Claim 1 wherein the gaseous source of carbon dioxide comprises combustion exhaust.

13. The method of Claim 12 further comprising dehumidifying the combustion exhaust before introducing the combustion exhaust into the higher-5 temperature portion of the reaction vessel.

14. The method of Claim 12 wherein the combustion exhaust comprises flue gas from an electrical or steam generation facility.

15. The method of Claim 1 wherein the gaseous source of methane comprises natural gas. 0

16. The method of Claim 1 wherein the higher-temperature portion of the reaction vessel includes one or more windows comprising one or more materials that transmit the microwave energy, and the microwave energy irradiating the first catalytic material in the higher-temperature portion of the reaction vessel passes through the one or more windows. 5

17. The method of Claim 1 wherein the higher-temperature portion of the reaction vessel includes one or more of quartz, silica, zirconia, cordierite, boron nitride, or alumina.

18. The method of Claim 1 wherein the microwave energy is introduced into the higher-temperature portion of 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.

19. The method of Claim 1 wherein the first or second catalytic material includes magnetite.

20. The method of Claim 1 wherein the lower-temperature portion of the reaction vessel is cooled by a cooling water jacket, piping, or coils.

21 . The method of Claim 1 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.

The method of Claim 1 further comprising

(J) 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

(K) 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.

The method of Claim 1 further comprising

(J) introducing a flow of steam into the higher-temperature portion of the reaction vessel only upon observing a decrease in a rate of carbon dioxide conversion in the reaction vessel; and (K) 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 higher-temperature portion of the reaction vessel.