Catalytic-redox moving bed chemical looping systems and methods

Abstract

Exemplary chemical looping systems comprising a redox reactor, a catalytic reactor, and a regeneration reactor. Exemplary methods of operating a chemical looping system may include circulating metal oxide particles through each reactor in the system and providing a reactor feed to each reactor. The metal oxide particles are reduced in the redox reactor by reacting with a carbonaceous feed. The metal oxide particles facilitate a reaction involving one or more hydrocarbons within the catalytic reactor. The reduced metal oxide particles are regenerated in the regeneration reactor by reacting with air, restoring them to their original oxidation state. After traveling through each of a plurality of reactors, the metal oxide particles are returned to the first reactor, completing a loop.

Description

Attorney Docket No. 029784-0012-W001CATALYTIC-REDOX MOVING BED CHEMICAL LOOPING SYSTEMS AND METHODSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 744,074, filed on January 10, 2025, the entire contents of which are incorporated herein by reference.TECHNICAL FIELD

[0002] The instant disclosure relates to utilizing the catalytic and redox properties of metal oxide particles to generate selected products. More particularly, exemplary systems and methods utilize metal oxide particles in chemical looping systems.INTRODUCTION

[0003] Carbonaceous fuels can be converted into valuable products and chemicals through three main thermochemical routes. Gasification is the conversion of fuel in a limited supply of oxygen to partial oxidation products with a high composition of carbon monoxide (CO) and hydrogen (H2), also called syngas. Syngas is a platform chemical to synthesize high-value products such as methanol, ammonia, etc. A second thermochemical method of converting carbonaceous fuel is reforming it into value-added products or chemicals, whereby the carbonaceous fuel is broken down into smaller, valuable compounds (for example, H2). A third method includes the combustion of carbonaceous fuel to generate thermal heat energy.

[0004] Chemical looping is an established technology for the thermochemical conversion of different carbonaceous fuels (for example, but not limited to biomass, municipal solid waste, plastics, and methane). Some chemical looping technologies include a moving bed reducer and fluidized bed combustor reactor. The reducer section deals with gasification, reforming, or combustion of carbonaceous fuels.SUMMARY

[0005] In some aspects, the techniques described herein relate to a method of operating a chemical looping system including a redox reactor, a catalytic reactor, and a regeneration reactor. The method includes: providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed including a carbonaceous feed to a redox reactor feed inlet; providing a redox reactor gas outlet stream including H2 and CO via a redox reactor gasAttorney Docket No. 029784-0012-W001outlet; discharging the metal oxide particles from a redox reactor solids outlet to a catalytic reactor solids inlet, wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state; providing a catalytic reactor feed including one or more hydrocarbons to a catalytic reactor feed inlet; providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor; providing air to the regeneration reactor, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.

[0006] In some aspects, the techniques described herein relate to a method of operating a chemical looping system including a redox reactor, a catalytic reactor, and a regeneration reactor. The method includes: providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed including a carbonaceous feed to a redox reactor feed inlet; providing a redox reactor gas outlet stream including H2 and CO via a redox reactor gas outlet; discharging the metal oxide particles from a redox reactor solids outlet of the redox reactor to a catalytic reactor solids inlet, wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state; providing a catalytic reactor feed including flue gas to a catalytic reactor feed inlet; providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet, wherein the catalytic reactor gas outlet stream is substantially free of NOX; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor; providing air to the regeneration reactor via a regeneration reactor air inlet, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.

[0007] In some aspects, the techniques described herein relate to a method of removing carbon deposition in a chemical looping system including a catalytic reactor and a regeneration reactor. The method includes: providing metal oxide particles to a catalytic reactor solids inlet positioned near a top of the catalytic reactor; providing a catalytic reactor feed including a solid carbonaceous feed to a catalytic reactor feed inlet, wherein the catalytic reactor feed reacts within the catalyticAttorney Docket No. 029784-0012-W001reactor to deposit a solid onto a surface of the metal oxide particles; providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet positioned near a bottom of the catalytic reactor to a regeneration reactor solids inlet; providing a regeneration reactor feed to a regeneration reactor feed inlet, wherein the regeneration reactor feed reacts with the solid on the surface of the metal oxide particles to remove the solid from the surface; providing a regeneration reactor gas outlet stream via a regeneration reactor gas outlet; and discharging the metal oxide particles from a regeneration reactor solids outlet.

[0008] In some aspects, the techniques described herein relate to a chemical looping system, including: a redox reactor including: a redox reactor solids inlet positioned near a top of the redox reactor and arranged to receive metal oxide particles, wherein the metal oxide particles enter the redox reactor at a first oxidation state; a redox reactor feed inlet arranged to receive a redox reactor feed; a redox reactor gas outlet configured to provide a redox reactor gas outlet stream; and a redox reactor solids outlet positioned near a bottom of the redox reactor and configured to provide metal oxide particles, wherein the metal oxide particles exit the redox reactor at a second oxidation state and the second oxidation state is more reduced than the first oxidation state; a catalytic reactor including: a catalytic reactor solids inlet positioned near a top of the catalytic reactor and arranged to receive metal oxide particles; a catalytic reactor feed inlet arranged to receive a catalytic reactor feed; a catalytic reactor gas outlet configured to provide a catalytic reactor gas outlet stream; and a catalytic reactor solids outlet positioned near a bottom of the catalytic reactor and configured to provide metal oxide particles, wherein the metal oxide particles received at the catalytic reactor solids inlet are at the same oxidation state as the metal oxide particles provided at the catalytic reactor solids outlet; and a regeneration reactor, including: a regeneration reactor air inlet configured to provide air to the regeneration reactor; a regeneration reactor solids inlet positioned near a top of the regeneration reactor and arranged to receive metal oxide particles, wherein the metal oxide particles enter the regeneration reactor at the second oxidation state; and a regeneration reactor solids outlet positioned near a bottom of the regeneration reactor and configured to provide metal oxide particles, wherein the metal oxide particles exit the regeneration reactor at the first oxidation state; wherein the metal oxide particles at the second oxidation state react with air to provide metal oxide particles at the first oxidation state; and wherein the redox reactor is configured to provide the metal oxide particles to the catalytic reactor solids inlet, the catalyticAttorney Docket No. 029784-0012-W001reactor is configured to provide the metal oxide particles to the regeneration reactor solids inlet, and the regeneration reactor is configured to provide the metal oxide particles to the redox reactor solids inlet.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIG. l isa schematic diagram of an example embodiment of a chemical looping system for dehydrogenating or catalytic cracking of hydrocarbons with co-current flow of each reactor feed with the metal oxide particles.

[0010] FIG. 2 is a schematic diagram of another example embodiment of a chemical looping system for dehydrogenating or catalytic cracking of hydrocarbons with counter-current flow of the redox reactor feed relative to the metal oxide particles.

[0011] FIG. 3 is a schematic diagram of another example embodiment of a chemical looping system for dehydrogenating or catalytic cracking of hydrocarbons wherein the redox reactor feed inlet is located on a side of the redox reactor.

[0012] FIG. 4 is a schematic diagram of an example embodiment of a chemical looping system for removing NOx from flue gas with co-current flow of each reactor feed with the metal oxide particles.

[0013] FIG. 5 is a schematic diagram of another example embodiment of a chemical looping system for removing NOx from flue gas wherein a redox reactor feed inlet is located on a side of the redox reactor.

[0014] FIG. 6 is a schematic diagram of another example embodiment of a chemical looping system for removing NOx from flue gas wherein the catalytic reactor provides the metal oxide particles to the redox reactor.

[0015] FIG. 7 is a schematic diagram of another example embodiment of a chemical looping system for removing NOx from flue gas wherein a redox reactor feed inlet is located on a side of the redox reactor and the metal oxide particles are provided to the catalytic reactor at the first oxidation state.

[0016] FIG. 8 is a schematic diagram of an example embodiment of a chemical looping system comprising a first catalytic reactor, a redox reactor, and a second catalytic reactor.

[0017] FIG. 9 is a schematic diagram of another example embodiment of a chemical looping system wherein both the redox reactor feed and catalytic reactor feed comprise a carbonaceousAttorney Docket No. 029784-0012-W001feed.

[0018] FIG. 10 is a schematic diagram of another example embodiment of a chemical looping system wherein both the redox reactor feed and catalytic reactor feed comprise a carbonaceous feed, and the redox reactor feed inlet is located at or near a middle of the redox reactor.

[0019] FIG. 11 is a schematic diagram of another example embodiment of a chemical looping system wherein the redox reactor gas outlet stream comprises higher hydrocarbons.

[0020] FIG. 12 is a schematic diagram of an example embodiment of a chemical looping system comprising a regeneration reactor (R2).

[0021] FIG. 13 is a schematic diagram of another example embodiment of a chemical looping system comprising a regeneration reactor (R2).

[0022] FIG. 14 is a schematic diagram of another example embodiment of a chemical looping system comprising a regeneration reactor (R2) wherein the regeneration reactor gas outlet stream comprises syngas.

[0023] FIG. 15 is a schematic diagram of another example embodiment of a chemical looping system comprising a regeneration reactor (R2) and a catalytic riser.

[0024] FIG. 16A is a graph of syngas purity and solid conversion as a function of metal oxide particle flow rate in an experimental example of a system as shown in FIG. 1 and described in Example 1.

[0025] FIG. 16B is a graph of syngas purity as a function of time in a bench-scale experiment described in Example 1.

[0026] FIG. 17A is a chromatogram of the experimental dehydrogenation of ethane into ethylene at 600 °C described in Example 2.

[0027] FIG. 17B is a mass spectrum of the peak at 4.326 min in FIG. 17A.

[0028] FIG. 17C is a mass spectrum of the peak at 5.249 min in FIG. 17A.

[0029] FIG. 18A is a chromatogram of the experimental dehydrogenation of ethane into ethylene at 700 °C described in Example 2.

[0030] FIG. 18B is a mass spectrum of the peak at 3.917 min in FIG. 18A.

[0031] FIG. 18C is a mass spectrum of the peak at 5.516 min in FIG. 18 A.

[0032] FIG. 19A is a chromatogram of the experimental dehydrogenation of ethane intoAttorney Docket No. 029784-0012-W001ethylene at 750 °C described in Example 2.

[0033] FIG. 19B is a mass spectrum of the peak at 4.323 min in FIG. 19A.

[0034] FIG. 19C is a mass spectrum of the peak at 6.394 min in FIG. 19A.

[0035] FIG. 20A is a chromatogram of the experimental dehydrogenation of ethane into ethylene at 800 °C described in Example 2.

[0036] FIG. 20B is a mass spectrum of the peak at 7.426 min in FIG. 20A.DETAILED DESCRIPTION

[0037] The present disclosure relates to chemical looping systems and methods. Exemplary chemical looping systems may comprise metal oxide particles moving through a redox reactor, wherein the metal oxide particles are reduced to a lower oxidation state, and a catalytic reactor, wherein the metal oxide particles with lower oxygen content catalyze a reaction or transformation to convert a catalytic reactor feed to a catalytic reactor gas outlet stream comprising a value-added chemical. The metal oxide particles then proceed to a regeneration reactor, wherein they are reoxidized to the first (higher) oxidation state, and back to the redox reactor, completing the loop. Methods of operating a chemical looping system are also disclosed.

[0038] The metal oxide particles at the core of any chemical looping technology release their lattice oxygen in the reducer and consequently attain a lower oxidation state. The reduced metal oxide particles are regenerated back to their completely oxidized state by air combustion in the fluidized bed combustor and returned to the reducer to complete the loop. The high-purity syngas generated during gasification in the reducer section is processed downstream to adjust the H2:CO ratio and make it suitable for the various processes in producing commodity chemicals.

[0039] The combustion of carbonaceous fuel in the moving bed reducer produces sequestration-ready CO2, and thermal heat energy is generated simultaneously in the redox reactor or in the catalytic reactor. The metal oxide particles can be sent into an additional oxidizer reactor to generate H2 from steam, thereby partially oxidizing the metal oxide particles. The partially oxidized metal oxide particles are sent into the fluidized bed combustor to be regenerated entirely back to a fully oxidized state.

[0040] The metal oxide particles typically have a strong oxidizing ability and catalytic properties. They can easily give out oxygen and, at the same time, catalytically convert heavy hydrocarbons present in carbonaceous fuel. Carbonaceous fuels form heavy tar during syngasAttorney Docket No. 029784-0012-W001generation, which is hard to crack because of its higher hydrocarbon content. Hence, the in-situ catalytic ability of the metal oxide particles is utilized, which breaks the compound into lower hydrocarbons, which can be easily oxidized into carbon monoxide and hydrogen, increasing syngas purity. Similarly, the catalytic abilities of the metal oxide particles can also be used in the reforming and combustion of carbonaceous fuels to enhance the efficiency of the process and increase the selectivity of the products.

[0041] The metal oxide particles coming out of the reducer lose almost all of their oxygen. However, they do not lose any catalytic ability. The catalytic ability of the metal oxide particles is an inherent property of the metal oxide particles because of their composition. Hence, the reduced metal oxide particles with very low oxygen content can still be used for catalytic reactions, which might not be possible in the presence of oxygen.I. Definitions

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0043] The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms “a,” “an” and “the” include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments “comprising,” “consisting of’ and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not.

[0044] For the recitation of numeric ranges herein, each intervening number therebetween with the same degree of precision is contemplated. For example, for the range of 6-9, the numbers 7 and 8 are contemplated in addition to 6 and 9, and for the range 6.0-7.0, the numbers 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are contemplated. For another example, when a pressure range is described as being between ambient pressure and another pressure, a pressure that isAttorney Docket No. 029784-0012-W001ambient pressure is expressly contemplated.

[0045] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this disclosure, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75thEd., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5thEdition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rdEdition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.IL Exemplary Materials

[0046] Exemplary systems and methods utilize various materials. Various aspects of exemplary metal oxide particles and feed materials are described below.A. Exemplary Metal Oxide Particles

[0047] Exemplary systems, methods, and techniques disclosed and contemplated herein may use various metal oxide particles. Metal oxide particles described herein comprise a metal or a metal oxide which may have a plurality of oxidation states. The metal oxide particles described herein have catalytic activity. “Catalytic,” as used herein, refers to the ability of a metal oxide particle to promote a reaction or transformation under conditions wherein the reaction or transformation would not take place in the absence of the metal oxide particle and wherein the composition of the metal oxide particle does not change. Aspects of different metal oxide particles used in the various embodiments are described below.

[0048] Broadly, exemplary systems and methods utilize metal oxide particles. Exemplary metal oxide particles are capable of undergoing reduction / oxidation reactions that change the oxidation state of one or more species, or reactions that change the solid phase of one or more species. Exemplary metal oxide particles may be metal oxides, metal carbonates, metal alloys, or combinations thereof. Certain design considerations for exemplary metal oxide particles canAttorney Docket No. 029784-0012-W001include reactivity, recyclability and mechanical strength, along with oxygen / NOx capacity.

[0049] Exemplary metal oxide composites may have at least one of the active metals as iron. Exemplary mixed metal composites can be one single phase or can be a mixture of several active phases. The composite can comprise more than one active metal capable of a change in oxidation state under reducing or oxidizing environments, or that undergoes phase change under a partial pressure of CO2.

[0050] Other transition metal oxides such as nickel oxide, copper oxide, cobalt oxide, and manganese oxide can be an active metal oxide in conjunction with iron. Nickel oxide, copper oxide, and other transition metal oxides appear to be particularly suited because of their high oxygen carrying capacity and good reactivity among all the transition metal oxide candidates. Group I and II metal oxides such as MgO, CaO, Na2O etc. can also be considered as active metals / metal oxides.

[0051] The recyclability of exemplary metal oxide particles can be promoted by adding supportive oxides, also termed support materials, which may also affect the lattice oxygen ion diffusivity. The support material can be any support material known and used in the art. Nonlimiting examples of support materials include, but are not limited to, silica, magnesia, alumina, ceria, titania, zirconia, or a combination comprising two or more of the aforementioned supports such as MgAhC . The amount of support material can be 20% to 80% by weight (wt%) of the metal oxide particle. In various implementations, exemplary metal oxide particles may comprise 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or any value therebetween.

[0052] Inert carbonate materials such as K2CO3 can also be included as a part of the overall composite solid which can later combine with the carbonate phase to form a mixed metal carbonate.

[0053] In some implementations, metal oxide reactivity can be enhanced by low concentration dopant modification. One or more dopants may comprise 0 wt% to about 5 wt% of the metal oxide particles. In various instances, metal oxide particles may comprise 0 wt% to 5 wt%; 1 wt% to 5 wt%; 2 wt% to 5 wt%; 3 wt% to 5 wt%; 1 wt% to 4 wt%; 1 wt% to 3 wt%; 1 wt% to 2 wt%; 2 wt% to 3 wt%; 3 wt% to 4 wt%; or 4 wt% to 5 wt% dopant.

[0054] Exemplary dopants can have one or more of the following impacts in reactivity enhancement of cyclic chemical looping redox reactions. Exemplary catalytic dopants can provide extra reaction sites during NOx capture and hydrocarbon conversion in addition to the hostAttorney Docket No. 029784-0012-W001transition metal oxides such as iron oxide. The nature of aliovalent dopants, such as Cu2+, Co2+, Ni2+vs Fe3+, may result in an increase of oxygen vacancies, which may promote oxygen ion transport in methane partial oxidation and improve the syngas quality. Exemplary catalytic dopants can lower the reaction energy barrier of CO2 capture and C-H activation with the host transition metal oxide materials. Example catalytic transition metal dopants include, but are not limited to, Ni, Co, Cu, Sc, Ti, V, Cr, Mn, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, and Au.

[0055] In some instances, the metal oxide particles comprise a nickel species. In some instances, the nickel species is nickel ferrite. In certain implementations, the metal oxide particles may comprise NiFe2O4, NiZnFe4O4, or a mixture of one or more iron oxides with one or more nickel oxides.

[0056] In some instances, the metal oxide particles comprise FeTiCh, FeTiOs, or a combination thereof.

[0057] Metal oxide particles described herein may have a plurality of oxidation states. In some aspects, the metal oxide particles are provided at a first oxidation state and subsequently reduced to a second oxidation state, wherein the second oxidation state is more reduced than the first oxidation state, and wherein the metal oxide particles have a lower oxygen content in the second oxidation state than in the first oxidation state.

[0058] In other aspects, the metal oxide particles are provided at a first oxidation state and subsequently oxidized to a second oxidation state, wherein the second oxidation state is more oxidized than the first oxidation state, and wherein the metal oxide particles have a higher oxygen content in the second oxidation state than in the first oxidation state.

[0059] In other aspects, the metal oxide particles may be provided at further oxidation states, such as a third oxidation state or a fourth oxidation state. Metal oxide particles at a lower oxidation state typically have a lower oxygen content. Metal oxide particles at a higher oxidation state typically have a higher oxygen content. “Higher oxidation state” may refer to a more oxidized state, higher oxygen content, or higher oxidation number. “Lower oxidation state” may refer to a more reduced state, lower oxygen content, or lower oxidation number.B. Exemplary Feed Materials

[0060] Broadly, the chemical looping systems described herein may be configured to receiveAttorney Docket No. 029784-0012-W001a variety of feeds.

[0061] In some implementations, a reactor feed comprises a carbonaceous feed. In one aspect, the carbonaceous feed is a gaseous carbonaceous feed. In another aspect, the carbonaceous feed is a solid carbonaceous feed.

[0062] In one aspect, a portion of the solid carbonaceous feed is vaporized, whereby a vapor travels counter-current to the metal oxide particles. In another aspect, a portion of the solid carbonaceous feed is vaporized, whereby a vapor travels co-current to the metal oxide particles.

[0063] In some implementations, the carbonaceous feed comprises biogas. In some implementations, the carbonaceous feed comprises methane. In some implementations, the carbonaceous feed comprises biomass. In some implementations, the carbonaceous feed comprises coal. In some implementations, the carbonaceous feed comprises plastics. In some implementations, the carbonaceous feed comprises municipal solid waste. In some implementations, the carbonaceous feed comprises any suitable carbonaceous feed known in the art.

[0064] In some implementations, a catalytic reactor feed comprises one or more C2-C4 alkanes. In some implementations, the catalytic reactor feed comprises ethane (C2H6). In some implementations, the catalytic reactor feed comprises propane (CsHs). In some implementations, the catalytic reactor feed comprises butane (C4H10). In another aspect, the catalytic reactor feed comprises a mixture of two or more of: ethane, propane, and butane.

[0065] In some implementations, a reactor feed comprises flue gas. In one aspect, the flue gas comprises NOx. The flue gas can be from any industrial process such as cement making, steel mill, methanol, bulk chemical synthesis, or any other process which produces a gas stream comprising NOx.

[0066] In some implementations, a reactor feed comprises a reactant comprising CO, CO2, H2O, H2, ethane, ethylene, or a combination thereof.III. Exemplary Chemical Looping Systems

[0067] FIG. 1-FIG. 15 schematically show various exemplary chemical looping systems with metal oxide particles. As shown, the metal oxide particles are referred to as MaOxor MaOy, where Ma, a=l,2,3.... N, where Mi refers to single metallic oxide, M2 refers to bi-metallic oxides, andAttorney Docket No. 029784-0012-W001M3 refers to tri-metallic oxides, etc.

[0068] Exemplary chemical looping systems may be broadly characterized into systems for processing carbonaceous and alkane feed streams, systems for processing carbonaceous feed and flue gas, systems for processing multiple carbonaceous feeds, and deposition removal systems. Various aspects of each are discussed below.

[0069] Although not shown, any of the exemplary systems disclosed herein may further comprise a riser. The riser may be configured to receive metal oxide particles from any reactor or system component disclosed herein via a riser solids inlet. The riser may be configured to provide metal oxide particles to any reactor or system component disclosed herein via a riser solids outlet.A. Exemplary Systems for Processing Carbonaceous and Alkane Feed Streams

[0070] FIG. 1 is a schematic diagram of an example embodiment of a chemical looping system for syngas (CO + Fb) and alkene generation. As shown in FIG. 1, the exemplary system includes a redox reactor Rl, a catalytic reactor R2, and a regeneration reactor R3. Other embodiments may include more or fewer components.

[0071] As shown, in the redox reactor Rl, the carbonaceous feed flows co-current to the metal oxide particles. As shown, in the catalytic reactor R2, the catalytic reactor feed flows co-current to the metal oxide particles. As shown, in the regeneration reactor R3, air flows co-current to the metal oxide particles. As shown, the redox reactor feed inlet may be located at or near a top of the redox reactor Rl .

[0072] In the redox reactor Rl, a carbonaceous feed is fed from the top of the redox reactor Rl along with the metal oxide particles (MaOx) co-currently. As the metal oxide particles and carbonaceous feed mixture travel down the redox reactor Rl, the metal oxide particles donate their lattice oxygen to the fuel for syngas generation, i.e., CO + H2. Hence, the metal oxide particles (MaOy) attain a lower oxidation state. In some implementations, the redox reactor Rl is a moving bed reducer reactor.

[0073] Either H2O or CO2 can be sent into the redox reactor Rl as an enhancer gas to convert the carbon or char formed from the carbonaceous feed into CO. Without being bound by a particular theory, it is believed that the use of H2O or CO2 does not prevent the change in the phase of metal oxide particles in the redox reactor Rl because of the scale of change of oxygen contentAttorney Docket No. 029784-0012-W001in the metal oxide particles in redox reactor R1. Tn such a process, H2O or CO2 are primarily used to convert the carbon deposited on the metal oxide particles. Hence, H2O and CO2 would prefer to react with the carbon, converting the carbon into CO or CO and H2. The amount of steam to be sent may be modulated such that the metal oxide particles are not oxidized or minimally oxidized without changing the phase of the metal oxide particles. Thus, H2O or CO2 may not be able to supply all the oxygen lost by the metal oxide particles.

[0074] These lower oxidation state metal oxide particles move to the second moving bed catalytic reactor R2, where a stream of higher hydrocarbons is fed co-currently. The metal oxide particles are at a lower oxidation state and contain mostly metallic sites at this stage. These metallic sites catalytically break down the higher hydrocarbon chain to lower hydrocarbons. One such example of this is ethane catalytic cracking to ethylene. The metal oxide particles (MaOy) in reactor R2 do not donate any oxygen and maintain their phase.

[0075] H2O or CO2 can be added into catalytic reactor R2 to prevent carbon deposition. However, it is also possible that metal oxide particles (MaOy) in reactor R2 become converted into a purely metallic form by donating oxygen. In such cases, H2O / CO2 is varied such that the oxidation state of the metal oxide particles is maintained. Hence, in scenarios where the metal oxide particles start donating oxygen in reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in reactor R2, enabling either a redox or a catalytic process.

[0076] These metal oxide particles (MaOy) move to the third reactor, R3, where air is used to replenish the oxygen lost by the metal oxide particles. The fully oxidized metal oxide particles then move to the first redox reactor Rl, completing the loop.

[0077] In some implementations, the catalytic reactor outlet stream comprises ethylene. In some implementations, the catalytic reactor outlet stream comprises propylene. In some implementations, the catalytic reactor outlet stream comprises butylene. In some implementations, the catalytic reactor outlet stream comprises lower hydrocarbons.

[0078] FIG. 2 is a schematic diagram of another example embodiment of a chemical looping system for processing gaseous carbonaceous and alkane feedstocks. The exemplary system shown in FIG. 2 comprises a redox reactor Rl, a catalytic reactor R2, and a regeneration reactor R3. The exemplary system shown in FIG. 2 may be used for generating alkenes and the combustion ofAttorney Docket No. 029784-0012-W001gaseous fuels in sequestration-ready CO2.

[0079] As shown in FIG. 2, the redox reactor feed comprises a gaseous carbonaceous feed which flows counter-current to the metal oxide particles. As shown in FIG. 2, the catalytic reactor feed flows co-current to the metal oxide particles. As shown in FIG. 2, air flows co-current to the metal oxide particles in the regeneration reactor R3. As shown in FIG. 2, the redox reactor feed inlet is located at or near a bottom of the redox reactor.

[0080] In the redox reactor Rl, a gaseous carbonaceous feed is fed from the bottom of the redox reactor Rl while the metal oxide particles (MaOx) move down into the redox reactor Rl counter-currently. As the metal oxide particles move through redox reactor Rl, the metal oxide particles donate their lattice oxygen to the fuel for fuel combustion into energy in the form of steam (H2O) and CO2. Hence, the metal oxide particles (MaOy) attain a lower oxidation state. In some implementations, the redox reactor Rl is a moving bed reducer reactor.

[0081] A small amount of H2O or CO2, such as about 5-10 vol% of the carbonaceous feed, may be sent into the redox reactor Rl as an enhancer gas to convert the carbon or char formed from the carbonaceous feed into CO. Without being bound by a particular theory, it is believed that the use of H2O or CO2 does not prevent the change in the phase of metal oxide particles in the redox reactor Rl because of the scale of the change of oxygen content in the metal oxide particles in Rl. In such a process, H2O or CO2 are primarily used to convert the carbon deposited on the metal oxide particles. Hence, H2O and CO2 would prefer to react with the carbon, converting the carbon into CO or CO and H2. The amount of steam to be sent may be modulated such that the metal oxide particles are not oxidized or minimally oxidized without changing the phase of the metal oxide particles. Thus, H2O or CO2 may not be able to supply all the oxygen lost by the metal oxide particles.

[0082] These lower oxidation state metal oxide particles move to the second moving bed catalytic reactor R2, where a stream of higher hydrocarbons is fed co-currently. The metal oxide particles are at a lower oxidation state and contain mostly metallic sites with some oxygen content at this stage. These metallic sites catalytically break down the higher hydrocarbon chain into lower hydrocarbons.

[0083] One example of this is ethane catalytic cracking to ethylene. Without being bound by a particular theory, it is believed that the metal oxide particles (MaOy) in reactor R2 do not donate any oxygen and maintain their phase. H2O or CO2 can be added into catalytic reactor R2 to preventAttorney Docket No. 029784-0012-W001carbon deposition. However, it is also possible that metal oxide particles (MaOy) in reactor R2 get converted into a purely metallic form by donating oxygen.

[0084] In such cases, the amount of H2O / CO2 provided is varied such that the oxidation state of the metal oxide particles is maintained. Hence, in scenarios where the metal oxide particles start donating oxygen in reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in reactor R2, enabling either a redox or a catalytic process.

[0085] These metal oxide particles (MaOy) are provided to the regeneration reactor R3, where air is used to replenish the oxygen lost by metal oxide particles. The fully oxidized metal oxide particles then move to the first redox reactor Rl, completing the loop.

[0086] FIG. 3 is a schematic diagram of another example embodiment of a three reactor chemical looping system for processing carbonaceous and alkane feeds. The exemplary system of FIG. 3 may be used for generating alkenes and thermal heat energy. The system in FIG. 3 comprises a catalytic reactor R2, a redox reactor Rl, and a regeneration reactor R3.

[0087] As shown in FIG. 3, the redox reactor feed inlet is located at or near a middle of the redox reactor Rl. In other embodiments, the redox reactor feed inlet may be located at a different position on the redox reactor Rl .

[0088] As shown in FIG. 3, solid carbonaceous feed 1 is provided through a side injection in the redox reactor Rl, whereby the solid carbonaceous feed is converted into volatiles and char in the redox reactor Rl . The volatiles, being gases, move upwards while the char moves downwards. In some implementations, the redox reactor Rl is a moving bed reducer reactor.

[0089] As shown in FIG. 3, the catalytic reactor feed flows co-current to the metal oxide particles. As shown in FIG. 3, air flows co-current to the metal oxide particles in the regeneration reactor R3.

[0090] A small amount of H2O or CO2, such as about 5-10 vol% of the carbonaceous feed, may be added to the bottom of the redox reactor as an enhancer gas to convert the char into gaseous CO, which moves from the bottom to the top of the redox reactor. Hence, the volatile and gaseous CO move upward in the redox reactor Rl. The metal oxide particles (MaOx), with the highest oxygen-donating capacity are also introduced counter current to the volatiles and gases in the moving bed reducer reactor, wherein the metal oxide particles provide oxygen to combust the feed and produce energy in the form of steam (H2O) and generate capture ready CO2. Without beingAttorney Docket No. 029784-0012-W001bound by a particular theory, it is believed that adding H2O or CO2 as an enhancer gas in the bottom of the redox reactor R1 does not prevent the change in the phase of metal oxide particles in the redox reactor R1 because of the scale of the change in oxygen content in the metal oxide particles. In such a process, H2O or CO2 are primarily used to convert the carbon deposited on the metal oxide particles. Hence, H2O and CO2 would prefer to react with the carbon, converting the carbon into CO or CO and H2. The amount of steam to be sent may be modulated such that the metal oxide particles are not oxidized or minimally oxidized without changing the phase of the metal oxide particles. Hence, a change of phase is seen in the metal oxide particles because of a change in their oxygen amount.

[0091] These lower oxidation state metal oxide particles move to the second moving bed catalytic reactor R2, where a stream of higher hydrocarbons is fed co-currently. The metal oxide particles are at a lower oxidation state and contain mostly metallic sites at this stage. These metallic sites catalytically break down the higher hydrocarbon chains to lower hydrocarbons.

[0092] One example of this is ethane catalytic cracking to ethylene. Without being bound by a particular theory, it is believed that the metal oxide particles (MaOy) in reactor R2 do not donate any oxygen and maintain their phase. H2O or CO2 can be added into catalytic reactor R2 to prevent carbon deposition. However, it is also possible that metal oxide particles (MaOy) in reactor R2 get converted into a purely metallic form by donating oxygen. In such cases, H2O / CO2 is varied such that the oxidation state of the metal oxide particles is maintained. Hence, in scenarios where the metal oxide particles start donating oxygen in reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in reactor R2, enabling either a redox or a catalytic process.

[0093] These metal oxide particles (MaOy) move to the third reactor, R3, where air is used to replenish the oxygen lost by metal oxide particles. The fully oxidized metal oxide particles then move to the first redox reactor Rl, completing the loop.

[0094] In some aspects, the catalytic reactor feed comprises ethane. In some aspects, the catalytic reactor feed comprises propane. In some aspects, the catalytic reactor feed comprises butane.

[0095] In some aspects, the catalytic reactor outlet stream comprises ethylene. In some aspects, the catalytic reactor outlet stream comprises propylene. In some aspects, the catalytic reactor outlet stream comprises butylene. In some aspects, the catalytic reactor feed comprises a first alkane andAttorney Docket No. 029784-0012-W001the catalytic reactor outlet stream comprises an alkane with a lower chain length than the first alkane.B. Exemplary Systems for Processing Carbonaceous Feed and Flue Gas

[0096] Another implementation of a chemical looping system is a NOx removal system. Exemplary NOx removal systems include a redox reactor, a catalytic reactor, and a regeneration reactor. In exemplary NOx removal systems, the redox reactor feed comprises a carbonaceous feed and the catalytic reactor feed comprises flue gas.

[0097] In some implementations, the catalytic reactor gas outlet stream is substantially free of NOx. In some implementations, the concentration of NOx in the catalytic reactor gas outlet stream is lower than the concentration of NOx in the catalytic reactor feed. The NOx removal system is capable of removing NOx from flue gas. In some instances, the catalytic reactor gas outlet stream comprises no more than 5 mole percent (mol%) flue gas, no more than 1 mol% flue gas, no more than 0.5 mol% flue gas, or no more than 0.1 mol% flue gas.

[0098] In some aspects, the system may further comprise a heat exchanger. In some aspects, the heat exchanger is used to recover heat from the catalytic reactor outlet stream.

[0099] In some aspects, the catalytic reactor outlet stream is substantially free of NOx. In some aspects, the concentration of NOx in the catalytic reactor outlet stream is lower than the concentration of NOx in the catalytic reactor feed. In some aspects, the system may further comprise a heat exchanger. In some aspects, the heat exchanger is used to recover heat from the catalytic reactor outlet stream.

[0100] FIG. 4 is a schematic diagram of an example embodiment of a three-reactor moving bed system for processing carbonaceous feed and flue gas. The system shown in FIG. 4 is a three reactor chemical looping system for flue gas NOx cleanup and syngas generation. The system shown in FIG. 4 comprises a redox reactor Rl, a catalytic reactor R2, and a regeneration reactor R3, where air flows co-current to the metal oxide particles. As shown in FIG. 4, the flow of the metal oxide particles is co-current with flow of each reactor feed.

[0101] In some implementations, the redox reactor Rl is a moving bed reducer reactor. In the first redox reactor Rl, a carbonaceous feed is provided at or near a top of the redox reactor. Metal oxide particles (Ma0x) are also provided at or near a top of the redox reactor in a co-current manner. The metal oxide particles and carbonaceous feed descend through the first redox reactor RlAttorney Docket No. 029784-0012-W001wherein the metal oxide particles transfer lattice oxygen to the fuel to produce syngas (CO+H2).

[0102] H2O or CO2 can be sent in co-currently in redox reactor R1 as enhancer gas to convert char or carbon into CO. Without being bound by a particular theory, it is believed that the use of H2O or CO2 does not prevent the change in the phase of metal oxide particles in the redox reactor R1 because of the scale of the change of oxygen content. In such a process, H2O or CO2 are primarily used to convert the carbon deposited on the metal oxide particles. Hence, H2O and CO2 would prefer to react with the carbon, converting the carbon into CO or CO and H2. The amount of steam to be sent may be modulated such that the metal oxide particles are not oxidized or minimally oxidized without changing the phase of the metal oxide particles. H2O or CO2inay not be able to supply all the oxygen lost by the metal oxide particles. Hence, H2O or CO2 may be used as an enhancer gas to convert the carbon or char in the redox reactor R1 into CO.

[0103] When the lattice oxygen of the metal oxide particles (MaOy) is depleted, the metal oxide particles reach a lower oxidation state. These lower oxidation state metal oxide particles are then transferred to the second catalytic moving bed reactor R2, where a flue gas stream is provided in a co-current manner. At this stage, the metal oxide particles are in a lower oxidation state and possess metallic primary sites. These metallic sites react with the impurities in the flue gas, producing a clean gas stream. Without being bound by a particular theory, it is believed that the metal oxide particles in reactor R2 do not change their phase by not donating or taking in any oxygen. Hence, the metal oxide particles catalytically convert the flue stream with NOx into a N0x-free flue stream.

[0104] Subsequently, these metal oxide particles (MaOy) move to the regeneration reactor R3, where air is utilized to restore the lost oxygen in the metal oxide particles. The fully oxidized metal oxide particles are then circulated back to the first redox reactor Rl, completing the cycle.

[0105] It is also possible that metal oxide particles (MaOy) in reactor R2 get converted into a purely metallic form by donating oxygen. In such cases, H2O / CO2 is varied such that the oxidation state of the metal oxide particles is maintained. Thus, in scenarios where the metal oxide particles start donating oxygen in reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in reactor R2, enabling either a redox or a catalytic process. The change in oxygen content in the metal oxide particles in reactor R2 is minimal, and can be prevented by adding H2O or CO2. The metal oxide particles (MaOy) exiting catalytic reactor R2 can then be sent to regeneration reactor R3, where they react with the air to return to theirAttorney Docket No. 029784-0012-W001original state.

[0106] FIG. 5 is a schematic diagram of another example embodiment of a chemical looping system for removing NOx from flue gas wherein the catalytic reactor feed inlet is located on a side of the redox reactor R1. FIG. 5 shows a three reactor system for flue gas NOx cleanup and thermal heat energy generation. The system shown in FIG. 5 comprises a catalytic reactor R2, a redox reactor Rl, and a regeneration reactor R3. In some implementations, the redox reactor R1 is a moving bed reducer reactor.

[0107] As shown in FIG. 5, the catalytic reactor R2 feed flows co-current to the metal oxide particles, and a regeneration reactor R3, wherein air flows co-current to the metal oxide particles. As shown in FIG. 5, the redox reactor Rl feed inlet is located at or near a middle of the redox reactor Rl.

[0108] In FIG. 5, the solid carbonaceous feed 1 is provided through a side injection in the redox reactor Rl, whereby the solid carbonaceous feed is converted into volatiles and char in the redox reactor Rl. The volatiles, being gases, move upwards and the char moves downwards.

[0109] A small amount of FbO or CO2, such as about 5-10 vol% of the carbonaceous feed, may be added to the bottom of the redox reactor Rl as an enhancer gas to convert the char into gaseous CO, and the CO moves from the bottom to the top of the redox reactor Rl. Hence, the volatile and gaseous CO move upward in the redox reactor Rl . In some implementations, the redox reactor Rl is a moving bed reducer reactor.

[0110] The metal oxide particles with the highest oxygen-donating capacity (MaOx) are introduced counter current to the volatiles and gases in the moving bed reducer reactor, wherein they provide oxygen to combust the feed and produce energy in the form of steam (H2O) and generate capture ready CO2. Adding H2O or CO2 as an enhancer gas in the bottom of the redox reactor Rl is not believed to prevent the change in the phase of metal oxide particles in the redox reactor Rl because of the scale of the change in oxygen content in the metal oxide particles. Hence, a change of phase is seen in the metal oxide particles because of a change in the oxygen amount of the metal oxide particles.

[0111] The reduced metal oxide particles (MaOy) with depleted lattice oxygen reach a lower oxidation state. These lower oxidation state metal oxide particles are then transferred to the second catalytic moving bed reactor R2, where a flue gas stream is provided in a co-current manner. At this stage, the metal oxide particles are in a lower oxidation state and possess metallic primaryAttorney Docket No. 029784-0012-W001sites. These metallic sites react with the impurities in the flue gas, producing a clean gas stream. The metal oxide particles in reactor R2 do not change their phase by not donating or taking in any oxygen. Hence, they catalytically convert the flue stream with NOx into NOx-free flue stream. Subsequently, these metal oxide particles (MaOy) move to the third reactor, R3, where air is utilized to restore the lost oxygen in the metal oxide particles. The fully oxidized metal oxide particles then circulate back to the first redox reactor Rl, completing the cycle.

[0112] FIG. 6 is a schematic diagram of an example embodiment of a three-reactor moving bed system to generate syngas and abate NOx-containing pollutants. The system shown in FIG. 6 may be used for gas cleanup and syngas generation. As shown in FIG. 6, the exemplary NOx removal system comprises a catalytic reactor Rl, a redox reactor R2, and a regeneration reactor R3.

[0113] As shown in FIG. 6, the catalytic reactor feed flows co-current to the metal oxide particles. As shown in FIG. 6, the carbonaceous feed flows co-current to the metal oxide particles. As shown in FIG. 6, air flows co-current to the metal oxide particles in regeneration reactor R3. As shown in FIG. 6, the redox reactor feed inlet is located at or near a top of the redox reactor R2.

[0114] In the system shown in FIG. 6, NOx-containing pollutant gases are fed into the first moving bed catalytic reactor Rl of the system along with the metal oxide particles (MaOx). The metal oxide particles catalytically clean up the incoming flue gas to deliver a NOx-free flue gas stream while maintaining their original metal oxide phase (MaOx).

[0115] In the second moving bed redox reactor R2, carbonaceous feed is provided to the catalytic reactor R2 along with the addition of steam (H2O) or carbon dioxide (CO2). Adding steam (H2O) or carbon dioxide (CO2) as an enhancer gas may be needed to convert the char or carbon into CO because of lower kinetics between the char and metal oxide particles. The metal oxide particles (MaOx) traveling co-currently downwards into redox reactor R2 from catalytic reactor Rl donate lattice oxygen to the feed to produce syngas (H2 + CO) in R2. During this step, the metal oxide particles donate their lattice oxygen to the feedstock and get converted into a reduced state. Hence, there is a change of phase observed from MaOx to MaOyin the metal oxide particles.

[0116] Without being bound by a particular theory, it is believed that the use of H2O or CO2 does not prevent the metal oxide particles from changing phase in the redox reactor R2 because of the scale of the change of oxygen content in the metal oxide particles in redox reactor R2. In such a process, H2O or CO2 are primarily used to convert the carbon deposited on the metal oxideAttorney Docket No. 029784-0012-W001particles. Hence, H2O and CO2 would prefer to react with the carbon, converting the carbon into CO or CO and H2. The amount of steam to be sent may be modulated such that the metal oxide particles are not oxidized or are minimally oxidized without changing the phase of the metal oxide particles. Thus, adding H2O or C02may not supply all the oxygen lost by the metal oxide particles. Subsequently, the metal oxide particles (MaOy) move to the final stage, reactor R3, where the air oxidizes the reduced particles back to their original oxidation state. These particles are then circulated back to the first redox reactor Rl, thus completing the loop.

[0117] FIG. 7 is a schematic diagram of another example embodiment of a three-reactor moving bed system to generate syngas and abate NOx-containing pollutants. The system shown in FIG. 7 is a three reactor system for the thermal heat energy generation and flue gas cleanup.

[0118] As shown in FIG. 7, the redox reactor feed inlet is located on the side of the redox reactor R2. As shown in FIG. 7, the redox reactor feed inlet is located at or near a middle of the redox reactor R2.

[0119] As shown in FIG. 7, the metal oxide particles are provided to the catalytic reactor Rl at the first oxidation state. As shown in FIG. 7, the catalytic reactor feed flows co-current to the metal oxide particles. As shown in FIG. 7, air flows co-current to the metal oxide particles in the regeneration reactor R3.

[0120] In the first moving bed catalytic reactor Rl, NOx-containing pollutant gases are fed into the system along with the metal oxide particles (MaOx). Because of the catalytic behavior of the metal oxide particles, the NOx-containing flue gas is cleaned up, and the product is NOx-free flue gas without the metal oxide particles losing or gaining any oxygen amount and maintaining their phase (MaOx).

[0121] In the second moving bed redox reactor R2, the solid carbonaceous feed 1 is provided through a side injection in the moving bed redox reactor R2, which is converted into volatiles and char. The volatiles, being gases, move upwards while the char moves downwards. A small amount of H2O or CO2, such as about 5-10 vol% of the carbonaceous feed, may be added to the bottom of the redox reactor to convert the char into gaseous CO, which moves from the bottom to the top of the redox reactor. Hence, the volatile and gaseous CO move upward in the redox reactor.

[0122] The metal oxide particles (MaOx), with the highest oxygen-donating capacity, are also introduced counter current to the volatiles and gases in the moving bed redox reactor R2, wherein they provide oxygen to combust the feed and produce energy in the form of steam (H2O) andAttorney Docket No. 029784-0012-W001generate capture ready CO2. Adding H2O or CO2 as an enhancer gas in the bottom of the redox reactor R2 is not thought to prevent the change in the phase of metal oxide particles in the redox reactor R2 because of the scale of the change in oxygen content in the metal oxide particles. Hence, a change of phase is seen in the metal oxide particles because of a change in their oxygen amount. Thus, adding H2O or CO2 may not supply all the oxygen lost by the metal oxide particles.

[0123] However, the metal oxide particles can be sent to minimize the carbon deposition in R2. Further, the metal oxide particles (MaOy) move to the final stage, reactor R3, where the metal oxide particles are re-oxidized to their original oxidation state. These particles are then circulated back to the first redox reactor Rl, thus completing the loop.

[0124] FIG. 8 is a schematic diagram of an example embodiment of a chemical looping system comprising a first catalytic reactor Rl, a redox reactor R2, a second catalytic reactor R3, and a regeneration reactor R4. The system of FIG. 8 is a four reactor system for enhanced syngas generation from multiple feedstocks and gas cleanup.

[0125] As shown in FIG. 8, the first catalytic reactor feed flows co-current to the metal oxide particles. The redox reactor feed flows co-current to the metal oxide particles. In the regeneration reactor R4 of FIG. 8, air flows co-current to the metal oxide particles.

[0126] The exemplary system shown in FIG. 8 is a moving bed configuration with 4 reactors wherein two reactors, catalytic reactor Rl and catalytic reactor R3, exhibit catalytic conversion of the feed. In contrast, redox reactor R2 reduces the metal oxide particles to form syngas (H2+CO) from carbonaceous feed 2. The fourth reactor involves the re-oxidation of metal oxide particles.

[0127] Catalytic reactor Rl is a co-current catalytic reactor, where the carbonaceous feed is injected, which moves along with the metal oxide particles (MaOx) downwards to generate syngas. The metal oxide particles are not thought to change phase in reactor Rl, i.e. the oxygen content of the metal oxide particles remains the same.

[0128] The metal oxide particles from catalytic reactor Rl further enter moving bed redox reactor R2, where a carbonaceous feed 2 is provided. Carbonaceous feed 2 moves co-currently downwards along with metal oxide particles to generate partial oxidation products, i.e., syngas. The carbonaceous feeds can be selected based on their compositions, the residence time of catalytic reactor Rl, the residence time of redox reactor R2, char gasification time, etc. In redox reactor R2, a phase change is observed in metal oxide particles, with the metal oxide particles losing latticeAttorney Docket No. 029784-0012-W001oxygen content.

[0129] The catalytic reactor R3 is shown in FIG. 8 as a co-current catalytic reactor, where flue gas containing NOx can be fed. The flue gas reacts with the reduced metal oxide particles to generate NOx-free flue gas. The NOx-free flue gas can be sent into the atmosphere after passing through a heat exchanger for heat recovery. The catalytic reactor R3 is a catalytic reactor, so no phase change of the metal oxide particles in reactor R3 is observed. The metal oxide particles (MaOy) are then sent to regeneration reactor R4, wherein the metal oxide particles react with air to return to a higher oxidation state.

[0130] The reduced metal oxide particles show greater syngas selectivity in redox reactor R2 than in catalytic reactor Rl. Hence, the choice of fuels can be made such that fuels containing higher oxygen can be sent to redox reactor R2. In contrast, fuel with a lower oxygen can be sent to catalytic reactor Rl. H2O or CO2 can be sent into catalytic reactor Rl and redox reactor R2 to prevent carbon deposition formation in these reactors, whereby the carbon would get converted into CO. H2O or CO2 may be added into catalytic reactor Rl and redox reactor R2 to prevent carbon deposition.C. Exemplary Systems for processing multiple carbonaceous feeds

[0131] FIG. 9 is a schematic diagram of an example embodiment of a three reactor system for processing multiple carbonaceous feeds. As shown in FIG. 9, the redox reactor feed and catalytic reactor feed each independently comprise a carbonaceous feed. As shown, each reactor feed flows co-current to the metal oxide particles.

[0132] In the system shown in FIG. 9, the redox reactor Rl receives the metal oxide particles at a first oxidation state and provides the metal oxide particles to the catalytic reactor R2 at a second oxidation state, wherein the second oxidation state is more reduced than the first oxidation state. As shown in FIG. 9, the catalytic reactor R2 provides the metal oxide particles to the regeneration reactor R3 at the second oxidation state. As shown in FIG. 9, the regeneration reactor R3 provides the metal oxide particles to the redox reactor Rl at the first oxidation state.

[0133] In FIG. 9, the carbonaceous feed is provided into the redox reactor Rl . The metal oxide particles (Ma0x), with the highest oxygen-donating capacity, are also introduced co-currently in the moving bed reducer reactor, wherein they release lattice oxygen to gasify the feed into syngas (H2 + CO). In some implementations, the redox reactor Rl is a moving bed reducer reactor.

[0134] H2O or CO2 can be added as an enhancer gas to promote unconverted char or carbonAttorney Docket No. 029784-0012-W001conversion into CO. Adding H2O or CO2 is not thought to prevent the change in the phase of metal oxide particles in the redox reactor R1 because of the scale of the change in oxygen content in the metal oxide particles. Hence, a phase change is seen in the metal oxide particles because of a change in their lattice oxygen amount.

[0135] The reduced metal oxide particles are sent into the moving bed catalytic reactor R2, where carbonaceous feed 2, such as biogas or methane, is provided. The metal oxide particles (MaOy) move down the catalytic reactor R2 co-currently with carbonaceous feed 2, which is converted catalytically into valuable chemicals like hydrogen or syngas depending on the reaction conditions and the material used, with the metal oxide particles maintaining their phase without donating any oxygen.

[0136] The metal oxide particles (MaOy) are then sent into regeneration reactor R3 for regeneration with air. The regenerated metal oxide particles (MaOx) are sent back into the reducer to complete the loop. Hence, syngas can be produced from gaseous and solid carbonaceous fuels in a single chemical looping system.

[0137] To prevent any carbon deposition in catalytic reactor R2, H2O or CO2 can be fed into the moving bed catalytic reactor R2 to remove carbon deposition during the reaction. However, this step may be omitted when there is no carbon deposition. In another scenario, it is also possible that metal oxide particles (MaOy) in catalytic reactor R2 get converted into a purely metallic form by donating oxygen. In such cases, H2O / CO2 is varied such that the oxidation state of the metal oxide particles is maintained. Hence, in scenarios where the metal oxide particles start donating oxygen in catalytic reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in catalytic reactor R2, enabling either a redox or a catalytic process. The change in oxygen content in the metal oxide particles in catalytic reactor R2 is minimal and can be prevented by adding H2O or CO2.

[0138] FIG. 10 is a schematic diagram of a three reactor system for sequestration-ready CO2 and syngas generation.

[0139] As shown in FIG. 10, the redox reactor feed inlet is located at or near a middle of the redox reactor Rl. In FIG. 10, the solid carbonaceous feed 1 is provided through a side injection in the redox reactor Rl and becomes converted into volatiles and char in the redox reactor Rl. The volatiles, being gases, move upwards while the char moves downwards in the redox reactor Rl . InAttorney Docket No. 029784-0012-W001some implementations, the redox reactor R1 is a moving bed reducer reactor.

[0140] A small amount of H2O or CO2, such as about 5-10 vol% of the carbonaceous feed, may be added to the bottom of the redox reactor R1 as an enhancer gas to convert the char into gaseous CO, which moves from the bottom to the top of the redox reactor Rl. Hence, the volatile and gaseous CO moves upward in the redox reactor Rl. The metal oxide particles (MaOx), with the highest oxy gen-donating capacity, are also introduced counter current to the volatiles and gases in the moving bed reducer reactor, wherein the metal oxide particles provide oxygen to combust the feed, produce energy in the form of steam (H2O), and generate capture ready CO2. Adding H2O or CO2 as an enhancer gas in the bottom of the redox reactor Rl is not thought to prevent the change in the phase of metal oxide particles in the redox reactor Rl because of the scale of the change in oxygen content in the metal oxide particles. Hence, a change of phase is seen in the metal oxide particles because of a change in their oxygen amount.

[0141] The reduced metal oxide particles are sent into the moving bed catalytic reactor R2, where carbonaceous feed 2 is provided. The metal oxide particles (MaOy), along with carbonaceous feed 2, move co-currently downwards, where the carbonaceous feed is catalytically converted into syngas, with the metal oxide particles maintaining their phase without donating any oxygen. The metal oxide particles (MaOy) are then sent into regeneration reactor R3 for regeneration with air. The regenerated metal oxide particles (Ma0x) are sent back into the reducer to complete the loop.

[0142] To prevent any carbon deposition in catalytic reactor R2, H2O or CO2 can be sent in the moving bed catalytic reactor R2 to remove carbon deposition during the reaction. However, this step may be omitted in case of no carbon deposition. In another scenario, it is also possible that metal oxide particles (MaOy) in catalytic reactor R2 becomes converted into a purely metallic form by donating oxygen. In such cases, H2O / CO2 is varied such that the oxidation state of the metal oxide particles is maintained. Hence, in scenarios where the metal oxide particles start donating oxygen in catalytic reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in catalytic reactor R2, enabling either a redox or a catalytic process. The change in oxygen content in the metal oxide particles in R2 is minimal, which can be prevented by adding H2O or CO2.

[0143] FIG. 11 is a schematic diagram of another example embodiment of a chemical looping system wherein the redox reactor gas outlet stream further comprises higher hydrocarbons. FIG.11 shows a three reactor system for enhanced syngas generation from multiple feedstocks. TheAttorney Docket No. 029784-0012-W001system of FIG. 11 is a 3-reactor moving bed configuration wherein syngas can be obtained in both reactors. The system of FIG. 11 can be used specifically for syngas cleanup using the catalytic ability of the metal oxide particles. In some implementations, the redox reactor R1 is a moving bed reducer reactor.

[0144] In the system of FIG. 11, the first redox reactor R1 involves the reduction of metal oxide particles by carbonaceous fuel 1, which is then converted to syngas along with the presence of impurities and higher hydrocarbons because of the extraction of lattice oxygen from the metal oxide particles (MaOx). The use of H2O or CChis not thought to prevent the change in the phase of metal oxide particles in the redox reactor R1 because of the scale of the change of oxygen content here. H2O or CO2 may not be able to supply all the oxygen lost by the metal oxide particles. Hence, H2O or CO2 may be used as an enhancer gas to convert the carbon or char in the redox reactor R1 into CO.

[0145] This product gas mixture can be sent into the second moving bed catalytic reactor R2, where additional carbonaceous fuel 2 is added with the reduced metal oxide particles (MaOy) from redox reactor Rl. Here, the oxygen-donating ability of the metal oxide particles is less since the metal oxide particles have already lost a significant amount of oxygen in redox reactor Rl . Hence, the metal oxide particles maintain their phase by not donating any oxygen, and the impure syngas stream with higher hydrocarbons entering R2 is catalytically converted to a pure syngas stream.

[0146] In another scenario, it is possible that metal oxide particles (MaOy) in catalytic reactor R2 becomes converted into a purely metallic form by donating oxygen. In such cases, H2O / CO2 is varied such that the oxidation state of the metal oxide particles is maintained. Thus, in scenarios where the metal oxide particles start donating oxygen in catalytic reactor R2, depending on the input of H2O or CO2, the oxidation states of the metal oxide particles may or may not change in catalytic reactor R2, enabling either a redox or a catalytic process. The change in oxygen content in the metal oxide particles in catalytic reactor R2 is minimal, which can be prevented by adding H2O or CO2.

[0147] Both redox reactor Rl and catalytic reactor R2 are in moving bed configuration, which helps achieve conditions close to the thermodynamic limits of the system. The metal oxide particles (MaOy) exiting catalytic reactor R2 can then be sent to regeneration reactor R3, where they react with the air to return to a higher oxidation state.Attorney Docket No. 029784-0012-W001D. Exemplary Deposition Removal Systems

[0148] Another implementation of a chemical looping system is a deposition removal system. Exemplary deposition removal systems comprise a catalytic reactor and a regeneration reactor comprising a regeneration reactor.

[0149] FIG. 12 is a schematic diagram of a catalytic chemical looping system for syngas generation. FIG. 12 shows an exemplary chemical looping system wherein the regeneration reactor R2 is a fluidized bed regenerator reactor.

[0150] In the system shown in FIG. 12, the catalytic reactor feed comprises FbO. In the system shown in FIG. 12, the catalytic reactor outlet stream comprises H2. In the system shown in FIG.12, the regeneration reactor feed comprises CO2. In the system shown in FIG. 12, the regeneration reactor outlet stream comprises CO.

[0151] In FIG. 12, a catalytic chemical looping process features a catalytic material MaOx. The catalytic material may comprise metals or metal oxides. In some instances, the catalytic material may comprise transition metals such as Cu, Fe, Co, or V. In some instances, the catalytic material may comprise precious metals such as Pt, Rh, or Ru. FIG. 12 shows a catalytic chemical looping process featuring the catalytic material Ma0xlooping between two reactors: the catalytic reactor R1 and the fluidized bed regeneration reactor R2. The catalytic material descends into the moving bed catalytic reactor R1 from the top while catalyzing the conversion of the steam into hydrogen gas. Upon exiting catalytic reactor Rl, MaOx is directed to a regeneration reactor R2 where CO2 is converted to CO. Use of catalytic material in moving bed catalytic reactor Rl results in carbon deposition on the surface of the material. Hence, CO2 reacts with deposited carbon in regeneration reactor R2, forming CO according to Boudouard's reaction in regeneration reactor R2. The regenerated material is then transported back to catalytic reactor Rl, thus completing the loop. A pneumatic system may be used to convey the regenerated material back to catalytic reactor Rl.

[0152] In another implementation, the reactant can be sent in from the bottom of the catalytic reactor Rl counter-current to the catalytic material, whereas the product can be obtained at the top of the catalytic moving bed catalytic reactor Rl, keeping all other operating conditions the same (not shown). Hence, this scheme can generate syngas autothermally and remove carbon deposition from the material.

[0153] FIG. 13 is a schematic diagram of another example embodiment of a chemical looping system comprising a regeneration reactor R2. FIG. 13 is a schematic diagram of a catalyticAttorney Docket No. 029784-0012-W001chemical looping system with carbon deposition removal.

[0154] FIG. 13 shows a catalytic chemical looping process featuring the catalytic material MaOx cycling between two reactors: the catalytic reactor R1 and the regeneration reactor R2.

[0155] The catalytic material descends into the moving bed catalytic reactor R1 from the top while catalyzing the conversion of the reactant stream into products. Upon exiting catalytic reactor Rl, MaOx is directed to a regeneration reactor R2 where air reacts with the carbon deposited in the catalytic material, forming CO2, which comes out with N2 in the outlet stream. The N2 outlet stream is the residual N2 in the air, which remains inert in the regeneration reactor R2. The regenerated material is then pneumatically transported back to catalytic reactor Rl, thus completing the loop.

[0156] In another implementation, the reactant can be sent in from the bottom of the catalytic reactor Rl counter-current to the direction of the catalytic material. In one aspect, the product can be obtained at the top of the catalytic moving bed catalytic reactor Rl, keeping all other operating conditions the same.

[0157] In the system shown in FIG. 13, the catalytic reactor feed comprises a reactant comprising CO, CO2, H2O, H2, ethane, ethylene, or another reactor feed disclosed herein. In the system shown in FIG. 13, the catalytic reactor outlet stream comprises a product comprising CO, CO2, H2O, H2, ethane, ethylene, or another reactor outlet stream disclosed herein. In the system shown in FIG. 13, the regeneration reactor feed comprises air. In the system shown in FIG. 13, the regeneration reactor outlet stream comprises CO2 and N2.

[0158] FIG. 14 is a schematic diagram of a catalytic chemical looping system for syngas generation. In FIG. 14, a catalytic chemical looping process features the catalytic material MaOx cycling between two reactors: the catalytic reactor Rl and the regeneration reactor R2. The catalytic material descends into the moving bed catalytic reactor Rl from the top while catalyzing the conversion of the reactant stream into products. Upon exiting catalytic reactor Rl, MaOx is directed to regeneration reactor R2. In this regeneration reactor R2, the carbon deposited on the catalytic material reacts with H2O to form CO2 and H2 (syngas). The regenerated material is then pneumatically transported back to catalytic reactor Rl, thus completing the loop.

[0159] In another scenario, the reactant can be sent in from the bottom of the catalytic reactor Rl counter-current to the direction of the catalytic material, whereas the product can be obtained at the top of the catalytic moving bed catalytic reactor Rl, keeping all other operating conditionsAttorney Docket No. 029784-0012-W001the same (not shown).

[0160] In various implementations of the system shown in FIG. 14, the catalytic reactor feed comprises a reactant comprising CO, CO2, H2O, H2, ethane, ethylene, or another reactor feed disclosed herein. In various implementations of the system shown in FIG. 14, the catalytic reactor outlet stream comprises a product comprising CO, CO2, H2O, H2, ethane, ethylene, or another reactor outlet stream disclosed herein. In various implementations of the system shown in FIG. 14, the regeneration reactor feed comprises H2O. In various implementations of the system shown in FIG. 14, the regeneration reactor outlet stream comprises H2, CO, syngas, or a combination thereof.

[0161] FIG. 15 is a schematic diagram of a chemical looping catalytic system with catalytic pneumatic cycling. The system of FIG. 15 is a chemical looping system comprising the catalytic material MaOx, a moving bed catalytic reactor Rl, a moving bed carbon remover reactor R2, and a catalytic riser R3.

[0162] In the system of FIG. 15, the catalytic reactor Rl is configured to provide metal oxide particles to the carbon remover reactor R2. In the system of FIG. 15, the carbon remover reactor R2 is configured to provide the metal oxide particles to the catalytic riser R3. In the system of FIG.15, the catalytic riser R3 is configured to provide the metal oxide particles to the catalytic reactor Rl.

[0163] The catalytic material MaOx is sent into the catalytic moving bed reactor Rl through the top with the reactant co-currently producing Pl. The catalytic material is further sent into a moving bed carbon remover reactor R2, wherein H2O is sent co-currently to remove the carbon deposited on the material and syngas is obtained at the outlet. The carbon-free catalytic material is then sent into a catalytic riser R3 that pneumatically conveys the material to the top of the riser R3 and back into the catalytic reactor Rl .

[0164] As shown in FIG. 15, the carbon remover inlet comprises H2O. As shown in FIG. 15, the carbon remover outlet stream comprises syngas. As shown in FIG. 15, reactant 2 comprises a feed described herein. As shown in FIG. 15, product 2 comprises an outlet stream described herein.

[0165] As shown in FIG. 15, reactant 2 is provided into the catalytic riser R3 from the bottom as the carbon-free catalytic material is conveyed to the top producing product 2. In another scenario, reactant 1 can be sent in from the bottom of the catalytic reactor Rl counter-current to the direction of the catalytic material. In this aspect, product 1 can be obtained at the top of theAttorney Docket No. 029784-0012-W001catalytic moving bed reactor Rl, keeping all other operating conditions the same (not shown).IV. Exemplary Methods of Operation

[0166] Various methods may be employed to operate exemplary chemical looping systems contemplated herein. Exemplary input feeds and metal oxide particles used in the methods contemplated herein are described in greater detail above. Various aspects of operating exemplary systems are discussed above and selected aspects are discussed below.A. Exemplary Methods of Processing Carbonaceous and Alkane Feed Streams

[0167] Example methods of processing carbonaceous and alkane feed streams may comprise various operations. In some instances, reactor systems shown in FIG. 1 - FIG. 3, and described above, may be used to perform exemplary methods of processing carbonaceous and alkane feed streams.

[0168] An example method may comprise providing metal oxide particles at a first oxidation state to a redox reactor solids inlet and providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet.

[0169] In some implementations, exemplary methods comprise providing metal oxide particles at the first oxidation state comprising FeTiOs and providing metal oxide particles at the second oxidation state comprising FeTiCh.

[0170] In some implementations, exemplary methods comprise providing a redox reactor feed comprising a solid carbonaceous feed. In some implementations, exemplary methods comprise gasifying the solid carbonaceous feed to form a vapor and a char, wherein the vapor flows countercurrent to the metal oxide particles.

[0171] In some implementations, the method comprises providing a redox reactor feed comprising a gaseous carbonaceous feed and the gaseous carbonaceous feed flows co-current to the metal oxide particles.

[0172] Exemplary methods also comprise providing a redox reactor gas outlet stream comprising Ik and CO via a redox reactor gas outlet; discharging the metal oxide particles from a redox reactor solids outlet to a catalytic reactor solids inlet, wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the secondAttorney Docket No. 029784-0012-W001oxidation state is more reduced than the first oxidation state.

[0173] Exemplary methods also comprise providing a catalytic reactor feed comprising one or more hydrocarbons to a catalytic reactor feed inlet.

[0174] In some implementations, exemplary methods comprise providing a catalytic reactor feed comprising one or more C2-C4 alkanes. In some implementations, exemplary methods comprise collecting a catalytic reactor gas outlet stream comprising one or more C2-C4 alkenes.

[0175] Exemplary methods may comprise operating the catalytic reactor at a temperature of 600 to 800 °C, 600 to 775 °C, 600 to 750 °C, 600 to 725 °C, 600 to 700 °C, 600 to 675 °C, 600 to 650 °C, 625 to 800 °C, 650 to 800 °C, 675 to 800 °C, 700 to 800 °C, 725 to 800 °C, 750 to 800 °C, or 775 to 800 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no less than 600 °C, no less than 625 °C, no less than 650 °C, no less than 675 °C, no less than 700 °C, no less than 725 °C, no less than 750 °C, no less than 775 °C, or no less than 800 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no greater than 800 °C, no greater than 775 °C, no greater than 750 °C, no greater than 725 °C, no greater than 700 °C, no greater than 675 °C, no greater than 650 °C, no greater than 625 °C, or no greater than 600 °C.

[0176] Exemplary methods may comprise operating the catalytic reactor at a pressure of 0.10 to 3.04 MPa, 0.10 to 2.74 MPa, 0.10 to 2.43 MPa, 0.10 to 2.13 MPa, 0.10 to 1.82 MPa, 0.10 to 1.52 MPa, 0.10 to 1.22 MPa, 0.10 to 0.91 MPa, 0.10 to 0.61 MPa, 0.10 to 0.30 MPa, 0.41 to 3.04 MPa, 0.71 to 3.04 MPa, 1.01 to 3.04 MPa, 1.32 to 3.04 MPa, 1.62 to 3.04 MPa, 1.93 to 3.04 MPa, 2.23 to 3.04 MPa, 2.53 to 3.04 MPa, 0.30 to 2.84 MPa, 0.51 to 2.64 MPa, 0.71 to 2.43 MPa, 0.91 to 2.23 MPa, 1.12 to 2.03 MPa, 1.32 to 1.82 MPa, or 1.52 to 1.62 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no less than 3.04 MPa, no less than 2.84 MPa, no less than 2.64 MPa, no less than 2.43 MPa, no less than 2.23 MPa, no less than 2.03 MPa, no less than 1.82 MPa, no less than 1.62 MPa, no less than 1.42 MPa, no less than 1.22 MPa, no less than 1.01 MPa, no less than 0.81 MPa, no less than 0.61 MPa, no less than 0.41 MPa, no less than 0.20 MPa, or no less than 0.10 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no greater than 3.04 MPa, no greater than 2.84 MPa, no greater than 2.64 MPa, no greater than 2.43 MPa, no greater than 2.23 MPa, no greater than 2.03 MPa, no greater than 1.82 MPa, no greater than 1.62 MPa, no greater than 1.42 MPa, no greater than 1.22 MPa, no greater than 1.01 MPa, no greater than 0.81 MPa, no greater than 0.61Attorney Docket No. 029784-0012-W001MPa, no greater than 0.41 MPa, no greater than 0.20 MPa, or no greater than 0.10 MPa.

[0177] Exemplary methods also comprise providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor; providing air to the regeneration reactor, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.

[0178] Other embodiments may include more or fewer operations.B. Exemplary Methods of Processing Carbonaceous Feed and Flue Gas

[0179] Exemplary methods of processing carbonaceous feed and flue gas comprise various operations. In some instances, reactor systems shown in FIG. 4 - FIG. 9, and described above, may be used to perform exemplary methods of processing carbonaceous feed and flue gas.

[0180] An example method may comprise providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet; providing a redox reactor gas outlet stream comprising H2 and CO via a redox reactor gas outlet; and discharging the metal oxide particles from a redox reactor solids outlet of the redox reactor to a catalytic reactor solids inlet. The metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state.

[0181] In some implementations, method comprises providing a redox reactor feed comprising a solid carbonaceous feed. In some implementations, the method further comprises gasifying the solid carbonaceous feed to form a vapor and a char, wherein the vapor flows counter-current to the metal oxide particles.

[0182] In some implementations, the method comprises providing a redox reactor feed comprising a gaseous carbonaceous feed and the gaseous carbonaceous feed flows co-current to the metal oxide particles.

[0183] In some implementations, the method comprises providing metal oxide particles comprising nickel ferrite.

[0184] Exemplary methods may comprise providing a catalytic reactor feed comprising flue gas to a catalytic reactor feed inlet.

[0185] Exemplary methods may comprise operating the catalytic reactor at a temperature ofAttorney Docket No. 029784-0012-W001600 to 1000 °C, 600 to 975 °C, 600 to 950 °C, 600 to 925 °C, 600 to 900 °C, 600 to 875 °C, 600 to 850 °C, 600 to 825 °C, 600 to 800 °C, 600 to 775 °C, 600 to 750 °C, 600 to 725 °C, 600 to 700 °C, 600 to 675 °C, 600 to 650 °C, 625 to 1000 °C, 650 to 1000 °C, 675 to 1000 °C, 700 to 1000 °C, 725 to 1000 °C, 750 to 1000 °C, 775 to 1000 °C, 800 to 1000 °C, 825 to 1000 °C, 850 to 1000 °C, 875 to 1000 °C, 900 to 1000 °C, 925 to 1000 °C, or 950 to 1000 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no less than 600 °C, no less than 625 °C, no less than 650 °C, no less than 675 °C, no less than 700 °C, no less than 725 °C, no less than 750 °C, no less than 775 °C, no less than 800 °C, no less than 825 °C, no less than 850 °C, no less than 875 °C, no less than 900 °C, no less than 925 °C, no less than 950 °C, no less than 975 °C, or no less than 1000 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no greater than 1000 °C, no greater than 975 °C, no greater than 950 °C, no greater than 925 °C, no greater than 900 °C, no greater than 875 °C, no greater than 850 °C, no greater than 825 °C, no greater than 800 °C, no greater than 775 °C, no greater than 750 °C, no greater than 725 °C, no greater than 700 °C, no greater than 675 °C, no greater than 650 °C, or no greater than 625 °C, or no greater than 600 °C.

[0186] Exemplary methods may comprise operating the catalytic reactor at a pressure of 0.10 to 3.04 MPa, 0.10 to 2.74 MPa, 0.10 to 2.43 MPa, 0.10 to 2.13 MPa, 0.10 to 1.82 MPa, 0.10 to 1.52 MPa, 0.10 to 1.22 MPa, 0.10 to 0.91 MPa, 0.10 to 0.61 MPa, 0.10 to 0.30 MPa, 0.41 to 3.04 MPa, 0.71 to 3.04 MPa, 1.01 to 3.04 MPa, 1.32 to 3.04 MPa, 1.62 to 3.04 MPa, 1.93 to 3.04 MPa, 2.23 to 3.04 MPa, 2.53 to 3.04 MPa, 0.30 to 2.84 MPa, 0.51 to 2.64 MPa, 0.71 to 2.43 MPa, 0.91 to 2.23 MPa, 1.12 to 2.03 MPa, 1.32 to 1.82 MPa, or 1.52 to 1.62 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no less than 3.04 MPa, no less than 2.84 MPa, no less than 2.64 MPa, no less than 2.43 MPa, no less than 2.23 MPa, no less than 2.03 MPa, no less than 1.82 MPa, no less than 1.62 MPa, no less than 1.42 MPa, no less than 1.22 MPa, no less than 1.01 MPa, no less than 0.81 MPa, no less than 0.61 MPa, no less than 0.41 MPa, no less than 0.20 MPa, or no less than 0.10 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no greater than 3.04 MPa, no greater than 2.84 MPa, no greater than 2.64 MPa, no greater than 2.43 MPa, no greater than 2.23 MPa, no greater than 2.03 MPa, no greater than 1.82 MPa, no greater than 1.62 MPa, no greater than 1.42 MPa, no greater than 1.22 MPa, no greater than 1.01 MPa, no greater than 0.81 MPa, no greater than 0.61Attorney Docket No. 029784-0012-W001MPa, no greater than 0.41 MPa, no greater than 0.20 MPa, or no greater than 0.10 MPa.

[0187] Exemplary methods also comprise providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet, wherein the catalytic reactor gas outlet stream is substantially free of NOX; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor; providing air to the regeneration reactor via a regeneration reactor air inlet, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.

[0188] In another implementation, the method further comprises providing the catalytic reactor outlet to a heat exchanger.C. Exemplary Methods of processing multiple carbonaceous feeds

[0189] Exemplary methods of processing multiple carbonaceous feeds comprise various operations. In some instances, reactor systems shown in FIG. 9, FIG. 10, and FIG. 11, and described above, may be used to perform exemplary methods of processing multiple carbonaceous feeds.

[0190] An example method comprises providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet; providing a redox reactor gas outlet stream comprising H2 and CO via a redox reactor gas outlet; and discharging the metal oxide particles from a redox reactor solids outlet of the redox reactor to a catalytic reactor solids inlet, wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state.

[0191] Example methods further comprise providing a catalytic reactor feed comprising a carbonaceous feed to a catalytic reactor feed inlet.

[0192] Exemplary methods may comprise operating the catalytic reactor at a temperature of 600 to 800 °C, 600 to 775 °C, 600 to 750 °C, 600 to 725 °C, 600 to 700 °C, 600 to 675 °C, 600 to 650 °C, 625 to 800 °C, 650 to 800 °C, 675 to 800 °C, 700 to 800 °C, 725 to 800 °C, 750 to 800 °C, or 775 to 800 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no less than 600 °C, no less than 625 °C, no less than 650 °C, no less than 675 °C, no less than 700 °C, no less than 725 °C, no less than 750 °C, no less than 775 °C, or no less than 800 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature noAttorney Docket No. 029784-0012-W001greater than 800 °C, no greater than 775 °C, no greater than 750 °C, no greater than 725 °C, no greater than 700 °C, no greater than 675 °C, no greater than 650 °C, no greater than 625 °C, or no greater than 600 °C.

[0193] Exemplary methods may comprise operating the catalytic reactor at a pressure of 0.10 to 3.04 MPa, 0.10 to 2.74 MPa, 0.10 to 2.43 MPa, 0.10 to 2.13 MPa, 0.10 to 1.82 MPa, 0.10 to 1.52 MPa, 0.10 to 1.22 MPa, 0.10 to 0.91 MPa, 0.10 to 0.61 MPa, 0.10 to 0.30 MPa, 0.41 to 3.04 MPa, 0.71 to 3.04 MPa, 1.01 to 3.04 MPa, 1.32 to 3.04 MPa, 1.62 to 3.04 MPa, 1.93 to 3.04 MPa, 2.23 to 3.04 MPa, 2.53 to 3.04 MPa, 0.30 to 2.84 MPa, 0.51 to 2.64 MPa, 0.71 to 2.43 MPa, 0.91 to 2.23 MPa, 1.12 to 2.03 MPa, 1.32 to 1.82 MPa, or 1.52 to 1.62 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no less than 3.04 MPa, no less than 2.84 MPa, no less than 2.64 MPa, no less than 2.43 MPa, no less than 2.23 MPa, no less than 2.03 MPa, no less than 1.82 MPa, no less than 1.62 MPa, no less than 1.42 MPa, no less than 1.22 MPa, no less than 1.01 MPa, no less than 0.81 MPa, no less than 0.61 MPa, no less than 0.41 MPa, no less than 0.20 MPa, or no less than 0.10 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no greater than 3.04 MPa, no greater than 2.84 MPa, no greater than 2.64 MPa, no greater than 2.43 MPa, no greater than 2.23 MPa, no greater than 2.03 MPa, no greater than 1.82 MPa, no greater than 1.62 MPa, no greater than 1.42 MPa, no greater than 1.22 MPa, no greater than 1.01 MPa, no greater than 0.81 MPa, no greater than 0.61 MPa, no greater than 0.41 MPa, no greater than 0.20 MPa, or no greater than 0.10 MPa.

[0194] Example methods further comprise providing a catalytic reactor gas outlet stream comprising H2 and CO via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor; providing air to the regeneration reactor via a regeneration reactor air inlet, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.D. Exemplary Deposition Removal Systems

[0195] Exemplary methods of operating a deposition removal system comprise various operations. In some instances, reactor systems shown in FIG. 12 - FIG. 15, and described above, may be used to perform exemplary methods of processing multiple carbonaceous feeds.

[0196] An example method comprises providing metal oxide particles to a catalytic reactorAttorney Docket No. 029784-0012-W001solids inlet positioned near a top of the catalytic reactor; providing a catalytic reactor feed comprising a solid carbonaceous feed to a catalytic reactor feed inlet, wherein the catalytic reactor feed reacts within the catalytic reactor to deposit a solid onto a surface of the metal oxide particles.

[0197] Exemplary methods may comprise operating the catalytic reactor at a temperature of 600 to 800 °C, 600 to 775 °C, 600 to 750 °C, 600 to 725 °C, 600 to 700 °C, 600 to 675 °C, 600 to 650 °C, 625 to 800 °C, 650 to 800 °C, 675 to 800 °C, 700 to 800 °C, 725 to 800 °C, 750 to 800 °C, or 775 to 800 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no less than 600 °C, no less than 625 °C, no less than 650 °C, no less than 675 °C, no less than 700 °C, no less than 725 °C, no less than 750 °C, no less than 775 °C, or no less than 800 °C. Exemplary methods may comprise operating the catalytic reactor at a temperature no greater than 800 °C, no greater than 775 °C, no greater than 750 °C, no greater than 725 °C, no greater than 700 °C, no greater than 675 °C, no greater than 650 °C, no greater than 625 °C, or no greater than 600 °C.

[0198] Exemplary methods may comprise operating the catalytic reactor at a pressure of 0.10 to 3.04 MPa, 0.10 to 2.74 MPa, 0.10 to 2.43 MPa, 0.10 to 2.13 MPa, 0.10 to 1.82 MPa, 0.10 to 1.52 MPa, 0.10 to 1.22 MPa, 0.10 to 0.91 MPa, 0.10 to 0.61 MPa, 0.10 to 0.30 MPa, 0.41 to 3.04 MPa, 0.71 to 3.04 MPa, 1.01 to 3.04 MPa, 1.32 to 3.04 MPa, 1.62 to 3.04 MPa, 1.93 to 3.04 MPa, 2.23 to 3.04 MPa, 2.53 to 3.04 MPa, 0.30 to 2.84 MPa, 0.51 to 2.64 MPa, 0.71 to 2.43 MPa, 0.91 to 2.23 MPa, 1.12 to 2.03 MPa, 1.32 to 1.82 MPa, or 1.52 to 1.62 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no less than 3.04 MPa, no less than 2.84 MPa, no less than 2.64 MPa, no less than 2.43 MPa, no less than 2.23 MPa, no less than 2.03 MPa, no less than 1.82 MPa, no less than 1.62 MPa, no less than 1.42 MPa, no less than 1.22 MPa, no less than 1.01 MPa, no less than 0.81 MPa, no less than 0.61 MPa, no less than 0.41 MPa, no less than 0.20 MPa, or no less than 0.10 MPa. In some implementations, the method comprises operating the catalytic reactor at a pressure no greater than 3.04 MPa, no greater than 2.84 MPa, no greater than 2.64 MPa, no greater than 2.43 MPa, no greater than 2.23 MPa, no greater than 2.03 MPa, no greater than 1.82 MPa, no greater than 1.62 MPa, no greater than 1.42 MPa, no greater than 1.22 MPa, no greater than 1.01 MPa, no greater than 0.81 MPa, no greater than 0.61 MPa, no greater than 0.41 MPa, no greater than 0.20 MPa, or no greater than 0.10 MPa.

[0199] An example method comprises providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solidsAttorney Docket No. 029784-0012-W001outlet positioned near a bottom of the catalytic reactor to a regeneration reactor solids inlet; providing a regeneration reactor feed to a regeneration reactor feed inlet, wherein the regeneration reactor feed reacts with the solid on the surface of the metal oxide particles to remove the solid from the surface; providing a regeneration reactor gas outlet stream via a regeneration reactor gas outlet; and discharging the metal oxide particles from a regeneration reactor solids outlet.

[0200] In one implementation, the method comprises providing the metal oxide particles discharged from the regeneration reactor solids outlet to the catalytic reactor solids inlet.

[0201] In another implementation, the method comprises providing a regeneration reactor feed comprising air, CO2, H2O, or a combination thereof and collecting a regeneration reactor gas outlet stream comprising air, H2, CO, CO2, N2, or a combination thereof.

[0202] In another implementation, the method further comprises providing the metal oxide particles to a riser, the riser comprising: a riser solids inlet positioned near a bottom of the riser; a riser solids outlet positioned near a top of the riser; a riser gas inlet; and a riser gas outlet. In one aspect, the method further comprises providing the metal oxide particles discharged from the regeneration reactor solids outlet to the riser solids inlet; providing a riser gas inlet stream to the riser gas inlet, whereby the metal oxide particles are conveyed co-current to the riser solids outlet; providing a riser gas outlet stream via the riser gas outlet; and discharging the metal oxide particles from the riser solids outlet to the catalytic reactor solids inlet.V. Experimental Examples

[0203] Various experimental examples were conducted and the results are discussed below.A. Methane Reduction Example

[0204] An experimental example explored using reduced metal oxides for the dehydrogenation of ethane into ethylene. The ethane dehydrogenation into ethylene used metal oxides with lower oxygen-donating ability and higher catalytic ability compared to the use of fresh, fully oxidized oxygen carriers, which are feasible for the generation of syngas. The experimental example used carbonaceous fuel to reduce the metal oxides, producing syngas at the redox reactor outlet. A cocurrent moving bed reactor was employed, where fuel and particles move downward together intoAttorney Docket No. 029784-0012-W001the redox reactor, generating the syngas at the outlet.

[0205] FIG. 16A shows the syngas formation and solid conversion percentage from the first operation through reforming of methane using the co-current moving bed reactor. FIG. 16B shows the syngas purity from the experimental bench-scale study for methane reduction into syngas.B. Ethane to Ethylene Dehydrogenation Examples

[0206] From the first operation in Example 1A, the metal oxide particles were reduced to around 46% and the reduced metal oxides were used to perform a series of experimental tests for the dehydrogenation of ethane into ethylene. In the first case, the reduced metal oxides were tested at three different temperatures of 600 °C, 700 °C, 750 °C and 700 °C for the dehydrogenation of ethane into ethylene.

[0207] The gas chromatogram (GC)-mass spectra (MS) data for the experiments are shown in FIGS. 17A-20B, showing the formation of ethane and ethylene and their mass spectrum obtained. These results show that, for the experimental configuration, a temperature of 700 °C obtained maximum yield / selectivity of ethylene from ethane. A trend is observed and followed typically in any dehydrogenation reaction: an increase in temperature typically increases the ethane or higher hydrocarbon dehydrogenation rate and conversion. However excessive temperature can lead to a drop in the ethylene selectivity. At 600 °C, the ethylene formed is minimal in this case, but a high amount of ethane remains unconverted, as shown in FIGS. 17A-17C. As the operating temperature increased to 700 °C, we see a rise in the ethylene formation and an increase in ethane conversion, marked by a decrease in the ethane peak area obtained in GC-MS, as shown in FIGS. 18A-18C. At an operating temperature of 750 °C, not much change is seen in the ethylene formation or ethane conversion, as shown in FIGS. 19A-19C. At an operating temperature of 800 °C, we see no formation of ethylene and the ethane is completely converted, marked by no peak detection in GC-MS, as shown in FIGS. 20A-20B. Hence, the experimentally observed maximum ethylene formation was at an operating temperature of 700 °C. As the temperature further increases, the ethylene conversion decreases, whereas the ethane conversion shows an increasing trend as the operating temperature is increased from 600 °C to 800 °C.Attorney Docket No. 029784-0012-W001Embodiments:

[0208] For reasons of completeness, the following Embodiments are provided.Embodiment 1. A method of operating a chemical looping system comprising a redox reactor, a catalytic reactor, and a regeneration reactor, the method comprising:providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet;providing a redox reactor gas outlet stream comprising H2 and CO via a redox reactor gas outlet;discharging the metal oxide particles from a redox reactor solids outlet to a catalytic reactor solids inlet,wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state;providing a catalytic reactor feed comprising one or more hydrocarbons to a catalytic reactor feed inlet;providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor;providing air to the regeneration reactor,wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.Embodiment 2. The method according to embodiment 1, wherein the catalytic reactor feed comprises a C2-C4 alkane, the catalytic reactor gas outlet stream comprises one or more of a C2-C4 alkene or a product alkane with a shorter chain length than the C2-C4 alkane, the method further comprising operating the catalytic reactor at a temperature of 600-800 °C and a pressure of 1-30 atm.Attorney Docket No. 029784-0012-W001Embodiment 3. The method according to embodiment 1 or 2, whereinthe metal oxide particles at the first oxidation state comprise FeTiOs or an oxide of calcium (Ca), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), magnesium (Mg), sodium (Na), potassium (K), lithium (Li), strontium (Sr), or barium (Ba); andthe metal oxide particles at the second oxidation state comprise FeTiCh or an oxide of calcium (Ca), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), magnesium (Mg), sodium (Na), potassium (K), lithium (Li), strontium (Sr), or barium (Ba).Embodiment 4. The method according to any one of embodiments 1-3, wherein the redox reactor feed comprises a solid carbonaceous feed, the method further comprising:gasifying the solid carbonaceous feed to form a vapor and a char, wherein the vapor flows counter-current to the metal oxide particles.Embodiment 5. The method according to any one of embodiments 1-4, wherein the redox reactor feed comprises a gaseous carbonaceous feed and the gaseous carbonaceous feed flows co-current to the metal oxide particles.Embodiment 6. A method of operating a chemical looping system comprising a redox reactor, a catalytic reactor, and a regeneration reactor, the method comprising:providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet;providing a redox reactor gas outlet stream comprising H2 and CO via a redox reactor gas outlet;discharging the metal oxide particles from a redox reactor solids outlet of the redox reactor to a catalytic reactor solids inlet,wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state;providing a catalytic reactor feed comprising flue gas to a catalytic reactor feed inlet;Attorney Docket No. 029784-0012-W001providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet, wherein the catalytic reactor gas outlet stream is substantially free of NOX; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor;providing air to the regeneration reactor via a regeneration reactor air inlet, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.Embodiment 7. The method according to embodiment 6, wherein the redox reactor feed comprises a solid carbonaceous feed, the method further comprising:gasifying the solid carbonaceous feed to form a vapor and a char, wherein the vapor flows counter-current to the metal oxide particles.Embodiment 8. The method according to embodiment 6, wherein the redox reactor feed comprises a gaseous carbonaceous feed and the gaseous carbonaceous feed flows co-current to the metal oxide particles.Embodiment 9. The method according to any one of embodiments 6-8, wherein the metal oxide particles comprise nickel ferrite or an oxide of calcium (Ca), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), magnesium (Mg), sodium (Na), potassium (K), lithium (Li), strontium (Sr), or barium (Ba).Embodiment 10. The method according to any one of embodiments 6-9, wherein the chemical looping system further comprises a heat exchanger and at least one of the catalytic reactor gas outlet stream or the redox reactor gas outlet stream is provided to the heat exchanger.Embodiment 11. The method according to any one of embodiments 6-10, wherein the method further comprises operating the catalytic reactor at a temperature of 600-1000 °C and a pressure of 1-30 atm.Attorney Docket No. 029784-0012-W001Embodiment 12. A method of removing carbon deposition in a chemical looping system comprising a catalytic reactor and a regeneration reactor, the method comprising:providing metal oxide particles to a catalytic reactor solids inlet positioned near a top of the catalytic reactor;providing a catalytic reactor feed comprising a solid carbonaceous feed to a catalytic reactor feed inlet,wherein the catalytic reactor feed reacts within the catalytic reactor to deposit a solid onto a surface of the metal oxide particles;providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet positioned near a bottom of the catalytic reactor to a regeneration reactor solids inlet;providing a regeneration reactor feed to a regeneration reactor feed inlet,wherein the regeneration reactor feed reacts with the solid on the surface of the metal oxide particles to remove the solid from the surface;providing a regeneration reactor gas outlet stream via a regeneration reactor gas outlet; anddischarging the metal oxide particles from a regeneration reactor solids outlet.Embodiment 13. The method according to embodiment 12, whereinthe metal oxide particles discharged from the regeneration reactor solids outlet are provided to the catalytic reactor solids inlet.Embodiment 14. The method according to embodiment 12 or 13, wherein the regeneration reactor feed comprises air, CO2, H2O, or a combination thereof and the regeneration reactor gas outlet stream comprises air, H2, CO, CO2, N2, or a combination thereof.Embodiment 15. The method according to any one of embodiments 12-14, wherein the chemical looping system further comprises a riser, the riser comprising:a riser solids inlet positioned near a bottom of the riser;a riser solids outlet positioned near a top of the riser;Attorney Docket No. 029784-0012-W001a riser gas inlet; anda riser gas outlet; the method further comprising:providing the metal oxide particles discharged from the regeneration reactor solids outlet to the riser solids inlet;providing a riser gas inlet stream to the riser gas inlet, whereby the metal oxide particles are conveyed co-current to the riser solids outlet;providing a riser gas outlet stream via the riser gas outlet; anddischarging the metal oxide particles from the riser solids outlet to the catalytic reactor solids inlet.Embodiment 16. A chemical looping system, comprising:a redox reactor comprising:a redox reactor solids inlet positioned near a top of the redox reactor and arranged to receive metal oxide particles,wherein the metal oxide particles enter the redox reactor at a first oxidation state;a redox reactor feed inlet arranged to receive a redox reactor feed;a redox reactor gas outlet configured to provide a redox reactor gas outlet stream; anda redox reactor solids outlet positioned near a bottom of the redox reactor and configured to provide metal oxide particles,wherein the metal oxide particles exit the redox reactor at a second oxidation state and the second oxidation state is more reduced than the first oxidation state;a catalytic reactor comprising:a catalytic reactor solids inlet positioned near a top of the catalytic reactor and arranged to receive metal oxide particles;a catalytic reactor feed inlet arranged to receive a catalytic reactor feed;a catalytic reactor gas outlet configured to provide a catalytic reactor gas outlet stream; andAttorney Docket No. 029784-0012-W001a catalytic reactor solids outlet positioned near a bottom of the catalytic reactor and configured to provide metal oxide particles,wherein the metal oxide particles received at the catalytic reactor solids inlet are at the same oxidation state as the metal oxide particles provided at the catalytic reactor solids outlet; anda regeneration reactor, comprising:a regeneration reactor air inlet configured to provide air to the regeneration reactor;a regeneration reactor solids inlet positioned near a top of the regeneration reactor and arranged to receive metal oxide particles,wherein the metal oxide particles enter the regeneration reactor at the second oxidation state; anda regeneration reactor solids outlet positioned near a bottom of the regeneration reactor and configured to provide metal oxide particles,wherein the metal oxide particles exit the regeneration reactor at the first oxidation state;wherein the metal oxide particles at the second oxidation state react with air to provide metal oxide particles at the first oxidation state; andwherein the redox reactor is configured to provide the metal oxide particles to the catalytic reactor solids inlet, the catalytic reactor is configured to provide the metal oxide particles to the regeneration reactor solids inlet, and the regeneration reactor is configured to provide the metal oxide particles to the redox reactor solids inlet.Embodiment 17. The system according to embodiment 16, wherein the catalytic reactor feed comprises a C2-C4 alkane and the catalytic reactor gas outlet stream comprises a C2-C4 alkene.Embodiment 18. The system according to embodiment 16 or 17, wherein the catalytic reactor is configured to be heated to 600-800 °C.Embodiment 19. The system according to any one of embodiments 16-18, wherein the catalytic reactor feed comprises one or more higher hydrocarbons and the catalytic reactor gas outletAttorney Docket No. 029784-0012-W001stream comprises a one or more lower hydrocarbons.Embodiment 20. The system according to any one of embodiments 16-19, wherein the catalytic reactor feed comprises flue gas and the catalytic reactor gas outlet stream is substantially free of NOx.Embodiment 21. The system according to any one of embodiments 16-20, further comprising:a heat exchanger, wherein the heat exchanger is fluidly connected to the catalytic reactor gas outlet; ora riser, wherein the riser is fluidly connected to the redox reactor solids outlet, the catalytic reactor solids outlet, or a regeneration reactor solids outlet.

Claims

Attorney Docket No. 029784-0012-W001CLAIMS1. A method of operating a chemical looping system comprising a redox reactor, a catalytic reactor, and a regeneration reactor, the method comprising:providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet;providing a redox reactor gas outlet stream comprising H2 and CO via a redox reactor gas outlet;discharging the metal oxide particles from a redox reactor solids outlet to a catalytic reactor solids inlet,wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state;providing a catalytic reactor feed comprising one or more hydrocarbons to a catalytic reactor feed inlet;providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor;providing air to the regeneration reactor,wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.

2. The method of claim 1, wherein the catalytic reactor feed comprises a C2-C4 alkane, the catalytic reactor gas outlet stream comprises one or more of a C2-C4 alkene or a product alkane with a shorter chain length than the C2-C4 alkane, the method further comprising operating the catalytic reactor at a temperature of 600-800 °C and a pressure of 1-30 atm.

3. The method of claim 1, whereinthe metal oxide particles at the first oxidation state comprise FeTiOs or an oxide ofAttorney Docket No. 029784-0012-W001calcium (Ca), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), magnesium (Mg), sodium (Na), potassium (K), lithium (Li), strontium (Sr), or barium (Ba); andthe metal oxide particles at the second oxidation state comprise FeTiCh or an oxide of calcium (Ca), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), magnesium (Mg), sodium (Na), potassium (K), lithium (Li), strontium (Sr), or barium (Ba).

4. The method of claim 1, wherein the redox reactor feed comprises a solid carbonaceous feed, the method further comprising:gasifying the solid carbonaceous feed to form a vapor and a char, wherein the vapor flows counter-current to the metal oxide particles.

5. The method of claim 1, wherein the redox reactor feed comprises a gaseous carbonaceous feed and the gaseous carbonaceous feed flows co-current to the metal oxide particles.

6. A method of operating a chemical looping system comprising a redox reactor, a catalytic reactor, and a regeneration reactor, the method comprising:providing metal oxide particles at a first oxidation state to a redox reactor solids inlet; providing a redox reactor feed comprising a carbonaceous feed to a redox reactor feed inlet;providing a redox reactor gas outlet stream comprising FL and CO via a redox reactor gas outlet;discharging the metal oxide particles from a redox reactor solids outlet of the redox reactor to a catalytic reactor solids inlet,wherein the metal oxide particles discharged from the redox reactor solids outlet are at a second oxidation state and the second oxidation state is more reduced than the first oxidation state;providing a catalytic reactor feed comprising flue gas to a catalytic reactor feed inlet; providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet, wherein the catalytic reactor gas outlet stream is substantially free of NOX; discharging the metal oxide particles from a catalytic reactor solids outlet to the regeneration reactor;Attorney Docket No. 029784-0012-W001providing air to the regeneration reactor via a regeneration reactor air inlet, wherein the metal oxide particles at the second oxidation state react with air in the regeneration reactor to provide metal oxide particles at the first oxidation state; and discharging the metal oxide particles from a regeneration reactor solids outlet to the redox reactor solids inlet.

7. The method of claim 6, wherein the redox reactor feed comprises a solid carbonaceous feed, the method further comprising:gasifying the solid carbonaceous feed to form a vapor and a char, wherein the vapor flows counter-current to the metal oxide particles.

8. The method of claim 6, wherein the redox reactor feed comprises a gaseous carbonaceous feed and the gaseous carbonaceous feed flows co-current to the metal oxide particles.

9. The method of claim 6, wherein the metal oxide particles comprise nickel ferrite or an oxide of calcium (Ca), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), magnesium (Mg), sodium (Na), potassium (K), lithium (Li), strontium (Sr), or barium (Ba).

10. The method of claim 6, wherein the chemical looping system further comprises a heat exchanger and at least one of the catalytic reactor gas outlet stream or the redox reactor gas outlet stream is provided to the heat exchanger.

11. The method of claim 6, wherein the method further comprises operating the catalytic reactor at a temperature of 600-1000 °C and a pressure of 1-30 atm.

12. A method of removing carbon deposition in a chemical looping system comprising a catalytic reactor and a regeneration reactor, the method comprising:providing metal oxide particles to a catalytic reactor solids inlet positioned near a top of the catalytic reactor;providing a catalytic reactor feed comprising a solid carbonaceous feed to a catalytic reactor feed inlet,Attorney Docket No. 029784-0012-W001wherein the catalytic reactor feed reacts within the catalytic reactor to deposit a solid onto a surface of the metal oxide particles;providing a catalytic reactor gas outlet stream via a catalytic reactor gas outlet; discharging the metal oxide particles from a catalytic reactor solids outlet positioned near a bottom of the catalytic reactor to a regeneration reactor solids inlet;providing a regeneration reactor feed to a regeneration reactor feed inlet,wherein the regeneration reactor feed reacts with the solid on the surface of the metal oxide particles to remove the solid from the surface;providing a regeneration reactor gas outlet stream via a regeneration reactor gas outlet; anddischarging the metal oxide particles from a regeneration reactor solids outlet.

13. The method of claim 12, whereinthe metal oxide particles discharged from the regeneration reactor solids outlet are provided to the catalytic reactor solids inlet.

14. The method of claim 12, wherein the regeneration reactor feed comprises air, CO2, H2O, or a combination thereof and the regeneration reactor gas outlet stream comprises air, H2, CO, CO2, N2, or a combination thereof.

15. The method of claim 12, wherein the chemical looping system further comprises a riser, the riser comprising:a riser solids inlet positioned near a bottom of the riser;a riser solids outlet positioned near a top of the riser;a riser gas inlet; anda riser gas outlet; the method further comprising:providing the metal oxide particles discharged from the regeneration reactor solids outlet to the riser solids inlet;providing a riser gas inlet stream to the riser gas inlet, whereby the metal oxide particles are conveyed co-current to the riser solids outlet;providing a riser gas outlet stream via the riser gas outlet; andAttorney Docket No. 029784-0012-W001discharging the metal oxide particles from the riser solids outlet to the catalytic reactor solids inlet.

16. A chemical looping system, comprising:a redox reactor comprising:a redox reactor solids inlet positioned near a top of the redox reactor and arranged to receive metal oxide particles,wherein the metal oxide particles enter the redox reactor at a first oxidation state;a redox reactor feed inlet arranged to receive a redox reactor feed;a redox reactor gas outlet configured to provide a redox reactor gas outlet stream; anda redox reactor solids outlet positioned near a bottom of the redox reactor and configured to provide metal oxide particles,wherein the metal oxide particles exit the redox reactor at a second oxidation state and the second oxidation state is more reduced than the first oxidation state;a catalytic reactor comprising:a catalytic reactor solids inlet positioned near a top of the catalytic reactor and arranged to receive metal oxide particles;a catalytic reactor feed inlet arranged to receive a catalytic reactor feed;a catalytic reactor gas outlet configured to provide a catalytic reactor gas outlet stream; anda catalytic reactor solids outlet positioned near a bottom of the catalytic reactor and configured to provide metal oxide particles,wherein the metal oxide particles received at the catalytic reactor solids inlet are at the same oxidation state as the metal oxide particles provided at the catalytic reactor solids outlet; anda regeneration reactor, comprising:a regeneration reactor air inlet configured to provide air to the regeneration reactor;Attorney Docket No. 029784-0012-W001a regeneration reactor solids inlet positioned near a top of the regeneration reactor and arranged to receive metal oxide particles,wherein the metal oxide particles enter the regeneration reactor at the second oxidation state; anda regeneration reactor solids outlet positioned near a bottom of the regeneration reactor and configured to provide metal oxide particles,wherein the metal oxide particles exit the regeneration reactor at the first oxidation state;wherein the metal oxide particles at the second oxidation state react with air to provide metal oxide particles at the first oxidation state; andwherein the redox reactor is configured to provide the metal oxide particles to the catalytic reactor solids inlet, the catalytic reactor is configured to provide the metal oxide particles to the regeneration reactor solids inlet, and the regeneration reactor is configured to provide the metal oxide particles to the redox reactor solids inlet.

17. The system of claim 16, wherein the catalytic reactor feed comprises a C2-C4 alkane and the catalytic reactor gas outlet stream comprises a C2-C4 alkene.

18. The system of claim 17, wherein the catalytic reactor is configured to be heated to 600-800 °C.

19. The system of claim 16, wherein the catalytic reactor feed comprises one or more higher hydrocarbons and the catalytic reactor gas outlet stream comprises a one or more lower hydrocarbons.

20. The system of claim 16, wherein the catalytic reactor feed comprises flue gas and the catalytic reactor gas outlet stream is substantially free of NOX.

21. The system of claim 16, further comprising:a heat exchanger, wherein the heat exchanger is fluidly connected to the catalytic reactor gas outlet; orAttorney Docket No. 029784-0012-W001a riser, wherein the riser is fluidly connected to the redox reactor solids outlet, the catalytic reactor solids outlet, or a regeneration reactor solids outlet.

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