WO2025043102A1

WO2025043102A1 - Systems, methods, and techniques for processing solid fuels in chemical looping systems

Info

Publication number: WO2025043102A1
Application number: PCT/US2024/043463
Authority: WO
Inventors: Liang-Shih Fan; Rushikesh Kishor JOSHI; Shekhar SHINDE; Ishani Karki KUDVA; Dawei Wang
Original assignee: Ohio State Innovation Foundation
Priority date: 2023-08-23
Filing date: 2024-08-22
Publication date: 2025-02-27

Abstract

Exemplary systems and methods process solid fuels. Exemplary reactor systems may include a solid carbonaceous feedstock source, a thermochemical system, a separation unit, and a reactor. Exemplary methods may include providing solid fuel to a thermochemical unit, generating raw gas and solid byproducts in the thermochemical unit, collecting the solid byproducts, separating particulates from the raw gas, and providing reactor input gas to a gas inlet of a reactor.

Description

SYSTEMS, METHODS, AND TECHNIQUES FOR PROCESSING SOLID FUELS IN CHEMICAL LOOPING SYSTEMS

CROSS-REFERENCE TO RELATED APPLICATION(S)

[0001] This application claims priority to U.S. Provisional Patent Application No.

63/578,307, filed on August 23, 2023, the entire contents of which are incorporated herein by reference.

TECHNICAL FIELD

[0002] The present disclosure relates to systems, methods, and techniques for processing solid fuels.

INTRODUCTION

[0003] Hydrogen (H2) has emerged as an attractive option for reducing greenhouse gas emissions, in part because of a high heating value (HHV) and water as the only combustion product. Various technologies have been developed over the years to produce hydrogen (H2) from different sources. Most hydrogen is produced using Steam Methane Reforming (SMR). SMR converts natural gas, which is mostly methane (CH4), into syngas (a mixture of carbon monoxide and hydrogen) which is sent to the water gas shift reactor to form carbon dioxide (CO2) and hydrogen (H2). The hydrogen is further separated from the gaseous mixture, and pure hydrogen is produced. After SMR, coal is the second major source of hydrogen. Specifically, coal may gasify to provide syngas (CO and H2). This syngas is further treated similarly as in SMR using a water- gas shift reaction. Both SMR and coal gasification rely on fossil fuels.

[0004] Chemical looping is a technology that aims to produce high-purity hydrogen along with CO2 capture. Chemical looping technologies are centered on the use of lattice oxygen to oxidize various fuels. The lattice oxygen is obtained from particles termed oxygen carrier particles. These oxygen carrier particles comprise one or more active metal oxides that undergo cyclic redox reactions.

[0005] Chemical looping processes have been well developed for gaseous fuels, but numerous challenges are faced when using solid fuels. Solid fuels contain three major components: volatile matter, char (i.e., fixed carbon) and ash. While dealing with solid fuels in a chemical looping reactor, char and the components of ash, such as silicates, salts of sodium and potassium, etc., may react with oxygen carrier particles and render them unusable.

SUMMARY

[0006] In one aspect, a method of operating a reactor system is disclosed. The method may comprise receiving solid fuel in a thermochemical unit; generating raw gas and solid byproducts in the thermochemical unit, the solid byproducts comprising ash and/or char; collecting the solid byproducts from the thermochemical unit; collecting the raw gas from the thermochemical unit; separating particulates from the raw gas, thereby generating reactor input gas; and providing the reactor input gas to a gas inlet of a reactor, the reactor input gas having a temperature of at least 500 °C. The reactor input gas may comprise less than 1 weight percent (wt%) ash and less than 1 wt% char. The reactor may be configured as a fixed bed reactor comprising oxygen carrier particles.

[0007] In another aspect, a reactor system is disclosed. The reactor system may comprise a thermochemical unit, comprising: a solid fuel inlet configured to receive solid fuel, the solid fuel inlet being in communication with a solid carbonaceous feedstock source; a raw gas outlet configured to provide a raw gas stream; and a solid byproducts outlet configured to discharge solid byproducts, the solid byproducts comprising ash and/or char; a separation unit configured to receive the raw gas stream and separate particulates from the raw gas stream, the separation unit comprising a separation unit inlet in fluid communication with the raw gas outlet; a particulates outlet configured to discharge particulates; and a separation unit gas outlet configured to discharge reactor input gas; and a chemical looping system, comprising: a reactor comprising: a fixed bed of oxygen carrier particles; a reactor gas inlet configured to receive a reactor input gas stream from the separation unit, the reactor gas inlet being in fluid communication with the separation unit gas outlet; and a product gas outlet configured to provide product gas generated within the reactor. The chemical looping system may be a fixed bed chemical looping system.

[0008] Before any embodiments of the disclosure are explained in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The disclosure is capable of other embodiments and of being practiced or of being carried out in various ways. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIG. l is a schematic depiction of an exemplary reactor system.

[0010] FIG. 2 is a schematic depiction of an exemplary indirect thermochemical system.

[0011] FIG. 3 is a schematic depiction of an exemplary fluidized bed thermochemical system.

[0012] FIG. 4 is a schematic depiction of a first example fixed bed reactor system.

[0013] FIG. 5 is a schematic depiction of a second example fixed bed reactor system.

[0014] FIG. 6 is a schematic depiction of a third example fixed bed reactor system.

[0015] FIG. 7 is a schematic depiction of a fourth example fixed bed reactor system.

[0016] FIG. 8 is a schematic depiction of an example fixed bed reactor and combustor reactor configuration.

[0017] FIG. 9 is a schematic depiction of a first example moving bed reactor system.

[0018] FIG. 10 is a schematic depiction of a second example moving bed reactor system.

[0019] FIG. 11 is a schematic depiction of a third example moving bed reactor system.

[0020] FIG. 12 shows a flowchart of an exemplary method for operating a reactor system.

[0021] FIG. 13 is a graph showing gas concentration percentages (carbon dioxide (CO2) by volume percent (vol%) and carbon monoxide (CO) vol%), and temperature over time for an example bench-scale reactor system processing biomass.

DETAILED DESCRIPTION

[0022] Systems, methods, and techniques disclosed and contemplated herein relate to processing solid fuels. Exemplary systems for processing solid fuels may be configured as a chemical looping system. In some implementations, the chemical looping system may be a fixed bed system comprising one or more fixed bed reactors. In other implementations, the chemical looping system may be a moving bed system comprising one or more moving bed reactors.

I. Definitions

[0023] 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.

[0024] 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. [0025] The modifiers “about” or “approximately” used in connection with a quantity are inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the quantity). These modifiers should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11%, and “about 1” may mean from 0.9-1.1. Other meanings of “about” may be apparent from the context, such as rounding off, so, for example “about 1” may also mean from 0.5 to 1.4.

[0026] For the recitation of numeric ranges herein, each intervening number there between 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 is ambient pressure is expressly contemplated.

[0027] 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, 104^th Ed., inside cover, and specific functional groups are defined as described therein.

[0028] As used herein, the term “fluidized bed reactor” means a reactor where fluid is passed through catalyst material at a sufficient speed to suspend the solid catalyst material. Typically, oxygen carrier particles may move in any direction, bounded by the walls of the reactor. [0029] As used herein, the term “fixed bed reactor” means defined as a reactor where catalyst material is fixed in a packed bed. Fluid is passed through catalyst material, but the fluid does not suspend the catalyst material, as in a fluidized bed reactor.

[0030] As used herein, the term “moving bed reactor” means a reactor where catalytic material flows in a single direction, generally, from top to bottom. The fluid material can flow in the same direction as the catalytic material (co-current movement). The fluid material can flow in an opposite direction as the catalytic material (countercurrent movement).

IL Exemplary Materials

[0031] Exemplary reactor systems may receive, process, and generate various materials. Exemplary materials may include solid fuels, raw gases, reactor input gases, oxygen carrier particles, and product gases. In some instances, exemplary materials may further comprise fluidized media. Various aspects of exemplary solid fuels, raw gases, reactor input gases, oxygen carrier particles, product gases, and fluidized media are discussed below.

A. Exemplary Solid Fuels

[0032] Exemplary systems and methods disclosed herein may comprise receiving and processing various exemplary solid fuels. Exemplary solid fuels may be received from a solid carbonaceous feedstock source. As used herein, the term “solid carbonaceous feedstock” means a raw carbonaceous material in solid form. The solid carbonaceous feedstock may comprise a solid fuel.

[0033] Exemplary solid fuels may comprise various heavy hydrocarbons. As used herein, the term “heavy hydrocarbons” means hydrocarbons containing more than 6 carbon atoms. At ambient temperature and pressure, heavy hydrocarbons are typically solid or viscous. Heavy hydrocarbons may have molecular weights of up to 2,000,000.

[0001] In various instances, the solid fuel may comprise 0.001 % by weight (wt%) to 95 wt% heavy hydrocarbons. In various instances, the solid fuel may comprise heavy hydrocarbons at an amount of 0.01 % by weight (wt%) to 90 wt%; 0.1 wt% to 85 wt%; 1 wt% to 80 wt%; 5 wt% to 75 wt%; 10 wt% to 70 wt%; 15 wt% to 65 wt%; 20 wt% to 60 wt%; 25 wt% to 55 wt%; 30 wt% to 50 wt%; or 35 wt% to 45 wt%. In various instances, the solid fuel may comprise heavy hydrocarbons at an amount no greater than 95 wt%; no greater than 90 wt%; no greater than 85 wt% no greater than 80 wt%; no greater than 75 wt%; no greater than 70 wt%; no greater than 65 wt%; no greater than 60 wt%; no greater than 55 wt%; no greater than 50 wt%; no greater than 45 wt%; no greater than 40 wt%; no greater than 35 wt%; no greater than 30 wt%; no greater than 25 wt%; no greater than 20 wt%; no greater than 15 wt%; no greater than 10 wt%; no greater than 5 wt%; no greater than 1 wt%; no greater than 0.1%; or no greater than 0.01 wt%. In various instances, the solid fuel may comprise heavy hydrocarbons at an amount of no less than 0.001 wt%; no less than 0.01 wt%; no less than 0.1 wt%; no less than 1 wt%; no less than 5 wt%; no less than 10 wt%; no less than 15 wt%; no less than 20 wt%; no less than 25 wt%; no less than 30 wt%; no less than 35 wt%; no less than 40 wt%; no less than 45 wt%; no less than 50 wt%; no less than 55 wt%; no less than 60 wt%; no less than 65 wt%; no less than 70 wt%; no less than 75 wt%; no less than 80 wt%; no less than 85 wt%; or no less than 90 wt%.

[0002] Exemplary solid fuels may further comprise non-hydrocarbon elements such as oxygen

(O), nitrogen (N), sulfur (S), chlorine (Cl), mercury (Hg), arsenic (As), silicon (Si), phosphorus

(P), potassium (K), and sodium (Na). In various instances, non-hydrocarbon elements may be present in the solid fuel at an amount of 0 wt% to 15 wt%. In some instances, non-hydrocarbon elements may be present in the solid fuel at an amount of 1 wt% to 14 wt%; 2 wt% to 13 wt%; 3 wt% to 12 wt%; 4 wt% to 11 wt%; 5 wt% to 10 wt%; 6 wt% to 9 wt%; or 7 wt% to 8 wt%. In some instances, non-hydrocarbon elements may be present in the solid fuel at an amount of no greater than 15 wt%; no greater than 14 wt%; no greater than 13 wt%; no greater than 12 wt%; no greater than 11 wt%; no greater than 10 wt%; no greater than 9 wt%; no greater than 8 wt%; no greater than 7 wt%; no greater than 6 wt% no greater than 5 wt%; no greater than 4 wt%; no greater than 3 wt%; no greater than 2 wt%; or no greater than 1 wt%. In some instances, non-hydrocarbon elements may be present in the solid fuel at an amount of no less than 1 wt%; no less than 2 wt%; no less than 3 wt%; no less than 4 wt%; no less than 5 wt%; no less than 6 wt%; no less than 7 wt%; no less than 8 wt%; no less than 9 wt%; no less than 10 wt%; no less than 11 wt%; no less than 12 wt%; or no less than 13 wt%.

[0003] Example solid fuels may include various types of coals, biomasses, peats, and cokes. In some instances, the solid fuel may comprise a coal or a biomass. Various aspects of exemplary coals and biomasses are discussed below. 1. Coals

[0004] Exemplary coals may comprise one or more coal types. Example coal types include anthracite, bituminous, subbituminous, and lignite. Exemplary coals may comprise volatile matter, char, and ash at various amounts.

[0005] In various instances, the coal may comprise volatile matter at an amount of 20 wt% to 50 wt%. In some instances, the coal may comprise volatile matter at an amount of 22 wt% to 48 wt%; 25 wt% to 45 wt%; 28% to 42 wt%; 30 wt% to 40 wt%; 32 wt% to 38 wt%; or 34 wt% to 36 wt%. In some instances, the coal may comprise volatile matter at an amount of no greater than about 50 wt%; no greater than about 48 wt%; no greater than about 45 wt%; no greater than about 42 wt%; no greater than about 40 wt%; no greater than about 38 wt%; no greater than about 35 wt%; no greater than about 32 wt%; no greater than about 30 wt%; no greater than about 28 wt%; no greater than about 25 wt%; or no greater than about 22 wt%. In some instances, the coal may comprise volatile matter at an amount of no less than about 20 wt%; no less than about 22 wt%; no less than about 25 wt%; no less than about 28 wt%; no less than about 30 wt%; no less than about 32 wt%; no less than about 35 wt%; no less than about 38 wt%; no less than about 40 wt%; no less than about 42 wt%; no less than about 45 wt%; or no less than about 48 wt%.

[0006] In various instances, the coal may comprise char at an amount of 20 wt% to 50 wt%. In some instances, the coal may comprise char at an amount of 22 wt% to 48 wt%; 25 wt% to 45 wt%; 28% to 42 wt%; 30 wt% to 40 wt%; 32 wt% to 38 wt%; or 34 wt% to 36 wt%. In some instances, the coal may comprise char at an amount of no greater than about 50 wt%; no greater than about 48 wt%; no greater than about 45 wt%; no greater than about 42 wt%; no greater than about 40 wt%; no greater than about 38 wt%; no greater than about 35 wt%; no greater than about 32 wt%; no greater than about 30 wt%; no greater than about 28 wt%; no greater than about 25 wt%; or no greater than about 22 wt%. In some instances, the coal may comprise char at an amount of no less than about 20 wt%; no less than about 22 wt%; no less than about 25 wt%; no less than about 28 wt%; no less than about 30 wt%; no less than about 32 wt%; no less than about 35 wt%; no less than about 38 wt%; no less than about 40 wt%; no less than about 42 wt%; no less than about 45 wt%; or no less than about 48 wt%.

[0007] In some instances, the coal may comprise ash at an amount of 5 wt% to 15 wt%. In some instances, the coal may comprise ash at an amount of 6 wt% to 14 wt%; 7 wt% to 13 wt%; 8 wt% to 12 wt%; or 9 wt% to 11 wt%. In some instances, the coal may comprise ash at an amount of no greater than about 15 wt%; no greater than about 14 wt%; no greater than about 13 wt%; no greater than about 12 wt%; no greater than about 11 wt; no greater than about 10 wt%; no greater than about 9 wt%; no greater than about 8 wt%; no greater than about 7 wt%; or no greater than about 6 wt%. In some instances, the coal may comprise ash at an amount of no less than about 5 wt%; no less than about 6 wt%; no less than about 7 wt%; no less than about 8 wt%; no less than about 9 wt%; no less than about 10 wt%; no less than about 11 wt%; no less than about 12 wt%; no less than about 13 wt%; or no less than about 14 wt%.

2. Biomasses

[0008] Exemplary biomasses may comprise at least one type of biomass. Example biomass types include wood-based materials and agricultural waste. Exemplary biomasses may comprise volatile matter, char, and ash at various amounts.

[0009] In various instances, the biomass may comprise volatile matter at an amount of 20 wt% to 80 wt%. In some instances, the biomass may comprise volatile matter at an amount of 25 wt% to 75 wt%; 30 wt% to 70 wt%; 35 wt% to 65 wt%; 40 wt% to 60 wt%; 35 wt% to 55 wt%; or 40 wt% to 50 wt%. In some instances, the biomass may comprise volatile matter at an amount of no greater than about 80 wt%; no greater than about 75 wt%; no greater than about 70 wt%; no greater than about 65 wt%; no greater than about 60 wt%; no greater than about 55 wt%; no greater than about 50 wt%; no greater than about 45 wt%; no greater than about 40 wt%; no greater than about 35 wt%; no greater than about 30 wt%; or no greater than about 25 wt%. In some instances, the biomass may comprise volatile matter at an amount of no less than about 20 wt%; no less than about 25 wt%; no less than about 30 wt%; no less than about 35 wt%; no less than about 40 wt%; no less than about 45 wt%; no less than about 50 wt%; no less than about 55 wt%; no less than about 60 wt%; no less than about 65 wt%; no less than about 70 wt%; or no less than about 75 wt%.

[0010] In various instances, the biomass may comprise char at an amount of 10 wt% to 50 wt%. In various instances, the biomass may comprise char at an amount of 15 wt% to 45 wt%; 17 wt% to 43 wt%; 20 wt% to 40 wt%; 22 wt% to 38 wt%; 25 wt% to 35 wt%; 28 wt% to 33 wt%; or 29 wt% to 32 wt%. In various instances, the biomass may comprise char at an amount of no greater than about 50 wt%; no greater than about 45 wt%; no greater than about 40 wt%; no greater than about 35 wt%; no greater than about 30 wt%; no greater than about 25 wt%; no greater than about 20 wt%; or no greater than about 15 wt%. In various instances, the biomass may comprise char at an amount of no less than about 10 wt%; no less than about 15 wt%; no less than about 20 wt%; no less than about 25 wt%; no less than about 30 wt%; no less than about 35 wt%; no less than about 40 wt%; or no less than about 45 wt%.

[0011] In various instances, the biomass may comprise ash at an amount of 0 wt% to 10 wt%. In some instances, the biomass may comprise ash at an amount of 1 wt% to 9 wt%; 2 wt% to 8 wt%; 3 wt% to 7 wt%; or 4 wt% to 6 wt%. In some instances, the biomass may comprise ash at an amount of no greater than about 10 wt%; no greater than about 9 wt%; no greater than about 8 wt%; no greater than about 7 wt%; no greater than about 6 wt%; no greater than about 5 wt%; no greater than about 4 wt%; no greater than about 3 wt%; no greater than about 2 wt%; or no greater than about 1 wt%. In some instances, the biomass may comprise ash at an amount of no less than about 1 wt%; no less than about 2 wt%; no less than about 3 wt%; no less than about 4 wt%; no less than about 5 wt%; no less than about 6 wt%; no less than about 7 wt%; no less than about 8 wt%; or no less than about 9 wt%.

B. Exemplary Raw Gases and Solid Byproducts

[0019] Exemplary systems and methods disclosed herein may generate and process various exemplary raw gases and solid byproducts. As discussed in greater detail below, exemplary thermochemical units generate raw gases and solid byproducts from solid fuel. Exemplary solid byproducts may comprise ash and/or char.

[0020] Exemplary raw gases may comprise heavy hydrocarbons. Heavy hydrocarbons may be present in the raw gas at an amount of 0 wt% to 10 wt%. In some instances, heavy hydrocarbons may be present in the raw gas at an amount of 1 wt% to 9 wt%; 2 wt% to 8 wt%; 3 wt% to 7 wt%; 4 wt% to 6 wt%. In some instances, heavy hydrocarbons may be present in the raw gas at an amount of no greater than 10 wt%; no greater than 9 wt%; no greater than 8 wt%; no greater than 7 wt%; no greater than 6 wt%; no greater than 5 wt%; no greater than 4 wt%; no greater than 3 wt%; no greater than 2 wt%; or no greater than 1 wt%. In some instances, heavy hydrocarbons may be present in the raw gas at an amount of no less than 1 wt%; no less than 2 wt%; no less than 3 wt%; no less than 4 wt%; no less than 5 wt%; no less than 6 wt%; no less than 7 wt%; no less than 8 wt%; or no less than 9 wt%.

[0021] Exemplary raw gases may further comprise particulates. Particulates may be present in the raw gas at an amount of 0 wt% to 10 wt%. In some instances, particulates may be present in the raw gas at an amount of 1 wt% to 9 wt%; 2 wt% to 8 wt%; 3 wt% to 7 wt%; 4 wt% to 6 wt%. In some instances, particulates may be present in the raw gas at an amount of no greater than 10 wt%; no greater than 9 wt%; no greater than 8 wt%; no greater than 7 wt%; no greater than 6 wt%; no greater than 5 wt%; no greater than 4 wt%; no greater than 3 wt%; no greater than 2 wt%; or no greater than 1 wt%. In some instances, particulates may be present in the raw gas at an amount of no less than 1 wt%; no less than 2 wt%; no less than 3 wt%; no less than 4 wt%; no less than 5 wt%; no less than 6 wt%; no less than 7 wt%; no less than 8 wt%; or no less than 9 wt%.

C. Exemplary Reactor Input Gases

[0022] Exemplary systems and methods disclosed herein may generate and process various exemplary reactor input gases.

[0023] Exemplary reactor input gases may comprise heavy hydrocarbons.

[0024] Exemplary reactor input gases may be substantially free of particulates.

[0025] In various instances, exemplary reactor input gases may comprise less than 1 weight percent (wt%) ash. In various instances, exemplary reactor input gases may comprise less than 0.9 wt% ash; less than 0.8 wt% ash; less than 0.7 wt% ash; less than 0.6 wt% ash; less than 0.5 wt% ash; less than 0.4 wt% ash; less than 0.3 wt% ash; less than 0.2 wt% ash; or less than 0. 1 wt% ash. [0026] In various instances, exemplary reactor input gases may comprise less than 1 wt% char. In various instances, exemplary reactor input gases may comprise less than 0.9 wt% char; less than 0.8 wt% char; less than 0.7 wt% char; less than 0.6 wt% char; less than 0.5 wt% char; less than 0.4 wt% char; less than 0.3 wt% char; less than 0.2 wt% char; or less than 0.1 wt% char.

[0027] In some instances, the reactor input gas is clean reactor gas. Exemplary clean reactor gas may be substantially free of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As).

D. Exemplary Oxygen Carrier Particles

[0028] Exemplary systems and methods disclosed herein may use various exemplary oxygen carrier particles. Exemplary oxygen carrier particles may include one or more active metal oxides and inert material.

[0029] Exemplary oxygen carrier particles may have multiple oxidation states. Accordingly, exemplary active metal oxides may be capable of undergoing multiple cyclic redox reactions. In various instances, exemplary active metal oxides may have multiple oxidation states. Exemplary active metal oxides may include zinc oxide (ZnO), tin (IV) oxide (SnCh), iron (II, III) oxide (FesCU), nickel (II) oxide (NiO), manganese (IV) oxide (MnCh), cobalt (II) oxide (CoO), and chromium (III) oxide (CnCh).

[0030] Exemplary inert materials may include silicon dioxide (SiCh), silicon carbide (SiC), aluminum oxide (AI2O3), magnesium oxide (MgO), calcium oxide (CaO), titanium oxide (TiCh), magnesium aluminum oxide (MgAhCh), zirconium dioxide (ZrCh), yttria-stabilized ZrCh, alumina-silicates, clay supports such as kaolin and bentonite, alumina-zirconia-silica, and combinations thereof.

[0031] Exemplary oxygen carrier particles may comprise various amounts of the one or more active metal oxides and inert material. In various instances, the one or more active metal oxides may be present at 5 weight percent (wt%) to 95 wt% of the total weight of the exemplary oxygen carrier particles. In various implementations, the one or more active metal oxides may comprise 10 wt% to 95 wt%; 15 wt% to 95 wt%; 20 wt% to 95 wt%; 25 wt% to 95 wt%; 30 wt% to 95 wt%;

35 wt% to 95 wt%; 40 wt% to 95 wt%; 45 wt% to 95 wt%; 50 wt% to 95 wt%; 55 wt% to 95 wt%;

60 wt% to 95 wt%; 65 wt% to 95 wt%; 70 wt% to 95 wt%; 75 wt% to 95 wt%; 80 wt% to 95 wt%;

85 wt% to 95 wt%; 90 wt% to 95 wt%; 5 wt% to 90 wt%; 5 wt%; to 85 wt%; 10 wt% to 85 wt%;

15 wt% to 85 wt%; 20 wt% to 85 wt%; 20 wt% to 80 wt%; 25 wt% to 80 wt%; 25 wt% to 75 wt%;

30 wt% to 75 wt%; 30 wt% to 70 wt%; 35 wt% to 70 wt%; 35 wt% to 65 wt%; 40 wt% to 65 wt%;

40 wt% to 60 wt%; 45 wt% to 60 wt%; 45 wt% to 55 wt%; or about 50 wt% of the total weight of the exemplary oxygen carrier particles. In various implementations, the one or more active metal oxides may comprise no less than 5 wt%; no less than 15 wt%; no less than 25 wt%; no less than 35 wt%; no less than 45 wt%; no less than 55 wt%; no less than 65 wt%; no less than 75 wt%; or no less than 85 wt% of the total weight of the exemplary oxygen carrier particles. In various implementations, the one or more active metal oxides may comprise no greater than 95 wt%; no greater than 90 wt%; no greater than 80 wt%; no greater than 70 wt%; no greater than 60 wt%; no greater than 50 wt%; no greater than 40 wt%; no greater than 30 wt%; no greater than 20 wt%; or no greater than 10 wt% of the total weight of the exemplary oxygen carrier particles.

[0032] In various implementations, the inert material may comprise 5 wt% to 95 wt% of the total weight of the exemplary oxygen carrier particles. In various implementations, the inert material may comprise 10 wt% to 95 wt%; 15 wt% to 95 wt%; 20 wt% to 95 wt%; 25 wt% to 95 wt%; 30 wt% to 95 wt%; 35 wt% to 95 wt%; 40 wt% to 95 wt%; 45 wt% to 95 wt%; 50 wt% to 95 wt%; 55 wt% to 95 wt%; 60 wt% to 95 wt%; 65 wt% to 95 wt%; 70 wt% to 95 wt%; 75 wt% to 95 wt%; 80 wt% to 95 wt%; 85 wt% to 95 wt%; 90 wt% to 95 wt%; 5 wt% to 90 wt%; 5 wt%; to 85 wt%; 10 wt% to 85 wt%; 15 wt% to 85 wt%; 20 wt% to 85 wt%; 20 wt% to 80 wt%; 25 wt% to 80 wt%; 25 wt% to 75 wt%; 30 wt% to 75 wt%; 30 wt% to 70 wt%; 35 wt% to 70 wt%; 35 wt% to 65 wt%; 40 wt% to 65 wt%; 40 wt% to 60 wt%; 45 wt% to 60 wt%; 45 wt% to 55 wt%; or about 50 wt% of the total weight of the exemplary oxygen carrier particles. In various implementations, the inert material may comprise no less than 5 wt%; no less than 15 wt%; no less than 25 wt%; no less than 35 wt%; no less than 45 wt%; no less than 55 wt%; no less than 65 wt%; no less than 75 wt%; or no less than 85 wt% of the total weight of the exemplary oxygen carrier particles. In various implementations, the inert material may comprise no greater than 95 wt%; no greater than 90 wt%; no greater than 80 wt%; no greater than 70 wt%; no greater than 60 wt%; no greater than 50 wt%; no greater than 40 wt%; no greater than 30 wt%; no greater than 20 wt%; or no greater than 10 wt% of the total weight of the exemplary oxygen carrier particles.

E. Exemplary Product Gases

[0033] Exemplary systems and methods disclosed herein may generate various exemplary product gases. Exemplary product gases may comprise complete oxidation product gases and/or partial oxidation product gases. Exemplary complete oxidation product gases include carbon dioxide (CO2) and/or steam (H2O). Exemplary partial oxidation product gases include hydrogen (H2), carbon monoxide (CO), and syngas (a mixture H2 and CO).

[0034] Exemplary product gases may comprise steam, carbon dioxide (CO2), carbon monoxide (CO), and/or hydrogen (H2) at various amounts.

[0035] In various instances, the product gas may comprise 10% by volume (vol%) 50 vol% steam. In various instances, the product gas may comprise steam at an amount of 12 vol% to 43 vol%; 15 vol% to 45 vol%; 17 vol% to 43 vol%; 20 vol% to 40 vol%; 22 vol% to 38 vol%; 25 vol% to 35 vol%; or 27 vol% to 33 vol%. In various instances, the product gas may comprise steam at an amount of no greater than 50 vol%; no greater than 45 vol%; no greater than 40 vol%; no greater than 35 vol%; no greater than 30 vol%; no greater than 25 vol%; no greater than 20 vol%; or no greater than 15 vol%. In various instances, the product gas may comprise steam at an amount of no less than 10 vol%; no less than 15 vol%; no less than 20 vol%; no less than 25 vol%; no less than 30 vol%; no less than 35 vol%; no less than 40 vol%; or no less than 45 vol%. [0036] In various instances, the product gas may comprise 0 vol% to 10 vol% CO2. In various instances, the product gas may comprise CO2 at an amount of 1 vol% to 9 vol%; 2 vol% to 8 vol%; 3 vol% to 7 vol%; or 4 vol% to 6 vol%. In various instances, the product gas may comprise CO2 at an amount of no greater than 10 vol%; no greater than 9 vol%; no greater than 8 vol%; no greater than 7 vol%; no greater than 6 vol%; no greater than 5 vol%; no greater than 4 vol%; no greater than 3 vol%; no greater than 2 vol%; or no greater than 1 vol%. In various instances, the product gas may comprise CO2 at an amount of no less than 1 vol%; no less than 2 vol%; no less than 3 vol%; no less than 4 vol%; no less than 5 vol%; no less than 6 vol%; no less than 7 vol%; no less than 8 vol%; or no less than 9 vol%.

[0037] In various instances, the product gas may comprise 5 vol% to 95 vol% CO. In various instances, the product gas may comprise CO at an amount of 10 vol% to 90 vol%; 15 vol% to 85 vol%; 20 vol% to 80 vol%; 25 vol% to 75 vol%; 30 vol% to 70 vol%; 35 vol% to 65 vol%; 40 vol% to 60 vol%; or 45 vol% to 55 vol%. In various instances, the product gas may comprise CO at an amount of no greater than 95 vol%; no greater than 85 vol%; no greater than 75 vol%; no greater than 65 vol%; no greater than 55 vol%; no greater than 45 vol%; no greater than 35 vol%; no greater than 25 vol%; no greater than 15 vol%; or no greater than 10 vol%. In various instances, the product gas may comprise CO at an amount of no less than 5 vol%; no less than 15 vol%; no less than 25 vol%; no less than 35 vol%; no less than 45 vol%; no less than 55 vol%; no less than 65 vol%; no less than 75 vol%; no less than 85 vol%; or no less than 90 vol%.

[0038] In various instances, the product gas may comprise 5 vol% to 95 vol% H2. In various instances, the product gas may comprise H2 at an amount of 10 vol% to 90 vol%; 15 vol% to 85 vol%; 20 vol% to 80 vol%; 25 vol% to 75 vol%; 30 vol% to 70 vol%; 35 vol% to 65 vol%; 40 vol% to 60 vol%; or 45 vol% to 55 vol%. In various instances, the product gas may comprise H2 at an amount of no greater than 95 vol%; no greater than 85 vol%; no greater than 75 vol%; no greater than 65 vol%; no greater than 55 vol%; no greater than 45 vol%; no greater than 35 vol%; no greater than 25 vol%; no greater than 15 vol%; or no greater than 10 vol%. In various instances, the product gas may comprise H2 at an amount of no less than 5 vol%; no less than 15 vol%; no less than 25 vol%; no less than 35 vol%; no less than 45 vol%; no less than 55 vol%; no less than 65 vol%; no less than 75 vol%; no less than 85 vol%; or no less than 90 vol%. F. Exemplary Fluidized Media

[0039] Exemplary systems and methods disclosed herein may implement various types of fluidized media. The type of fluidized media and/or its specific use may depend on the specific reactor system. Exemplary fluidized media types include sand, quartz, hematite, and/or magnetite. In some instances, exemplary fluidized media may comprise a sand, such as olivine sand.

[0040] In some instances, exemplary fluidized media may in the form of a fixed bed. In other instances, exemplary fluidized media may be present as a free-flowing material that is capable of circulating throughout different units in of a reactor system.

[0041] In some instances, exemplary fluidized media may be inert. In various instances, exemplary fluidized media may possess catalytic activity to enhance the gasification rates and have tar cracking tendency. In some instances, exemplary fluidized media may contain a sacrificial material that may trap impurities, thereby providing in-situ purification of the raw gases. For example, exemplary fluidized media may comprise calcium oxide (CaO). The CaO may react with the sulfur present in the solid fuel, thereby generating calcium sulfate (CaSCh), and capturing the sulfur within the fluidized media itself.

[0042] In some instances, the fluidized media may be heat transfer media. Heat transfer media may be any type of fluidized media capable of supplying heat to a reactor or unit. In some instances, exemplary heat transfer media may be in the form of solids, referred to as “heat transfer media solids.” Exemplary heat transfer media may further include non-solids, such as hot gases and hot oils. Exemplary hot gases may include hot flue gas.

III. Exemplary Systems

[0043] Various reactor systems may be used to perform exemplary methods and techniques described herein. FIG. 1 is a schematic illustration of an exemplary reactor system 100. Reactor system 100 may be configured to process solid fuel and generate product gas. In some instances, reactor 100 is configured for autothermal operation.

[0044] Broadly, reactor system 100 comprises a solid carbonaceous feedstock source 102, a thermochemical system 104, a separation unit 106, and a reactor HOcz. Optional components are shown in dotted outline. Exemplary optional components may include a gas cleanup system 108. Other embodiments may include more or fewer components. Other implementations may include one or more of the units shown in FIG. 1 arranged and operating in parallel. Various aspects of exemplary reactor system components and configurations are discussed below.

A. Exemplary System Components

[0012] As shown in FIG. 1, exemplary reactor system 100 may comprise a solid carbonaceous feedstock source 102 in communication with thermochemical system 104. The solid carbonaceous feedstock source 102 is configured to provide a solid fuel to thermochemical system 104. The solid carbonaceous feedstock source 102 may be any suitable source containing solid carbonaceous feedstock. In some instances, the solid carbonaceous feedstock source 102 may be a coal source, such as a coal mine. In other instances, the solid carbonaceous feedstock source 102 may be a biomass source, such as an agricultural waste pit.

[0045] Thermochemical system 104 comprises a thermochemical unit 104a In some instances, the thermochemical unit 104a may be in fluid communication with an optional combustor reactor 104/>. In some instances, thermochemical system 104 may be configured for autothermal operation, wherein heat generated by the optional combustor reactor 104b is provided to the thermochemical unit 104a.

[0013] Thermochemical unit 104a receives solid fuel and generates raw gas and solid byproducts. Broadly, thermochemical unit 104a comprises a solid fuel inlet, a gas inlet, a solid byproducts outlet, and a raw gas outlet.

[0014] The solid fuel inlet of thermochemical unit 104a is in fluid communication with solid carbonaceous feedstock source 102 and is configured to receive solid fuel from the solid carbonaceous feedstock source 102. In some instances, the solid fuel inlet may be positioned adjacent a top portion of the thermochemical unit 104a.

[0015] The gas inlet is in fluid communication with a gas source, not shown in FIG. 1. In some instances, the gas inlet is configured to receive oxygen (Ch) or steam (H2O) and carbon dioxide (CO2) from the gas source. In other instances, the gas inlet is configured to receive an inert gas, such as argon (Ar) or nitrogen (N2) from the gas source. In various instances, the gas inlet may be positioned adjacent the top portion of the thermochemical unit 104a.

[0046] Upon receiving the solid fuel, the thermochemical unit 104a is further configured to generate raw gases and solid byproducts. Exemplary raw gases may comprise heavy hydrocarbons and particulates. Exemplary solid byproducts may comprise ash and/or char. [0047] The thermochemical unit 104a raw gas outlet is in fluid communication with separation unit 106 and is configured to provide a raw gas stream to a separation unit inlet. The raw gas outlet may be positioned adjacent the bottom portion of the thermochemical unit 104a.

[0048] The solid byproducts outlet is positioned adjacent a bottom portion of the thermochemical unit 104a and is configured to discharge the solid byproducts. In some instances, the solid byproducts outlet is configured to provide the solid byproducts to a solid byproducts inlet of optional combustor reactor 104Z).

[0049] Combustor reactor 104/? receives and generates heat from the solid byproducts received from the thermochemical unit 104a. Broadly, combustor reactor 104Z> comprises a solid byproducts inlet and a combustion products outlet. In some implementations, the optional combustor reactor 1042? further comprises a solids inlet and a solids outlet. The solid byproducts inlet is in fluid communication with thermochemical unit 104a and is configured to receive the solid byproducts from the solid byproducts outlet. In various instances, the solid byproducts inlet may be positioned adjacent a top portion of the combustor reactor 1046. In some implementations, the combustion products outlet may be in fluid communication with thermochemical unit 104a and may be configured to provide heat, in the form of hot air, to a hot air inlet of thermochemical unit 104a.

[0050] Separation unit 106 removes particulates from raw gases and generates reactor input gases. Broadly, separation unit 106 comprises a separation unit inlet and a separation unit gas outlet. The separation unit inlet is in fluid communication with thermochemical unit 104a and is configured to receive a raw gas stream from the raw gas outlet. Upon receiving the raw gas, separation unit 106 is further configured to remove various particulates from the raw gas, thereby generating reactor input gas.

[0051] Exemplary reactor input gases may comprise heavy hydrocarbons and be substantially- free of particulates. In some implementations, the separation unit gas outlet is in fluid communication with reactor 110a and is configured to provide a reactor input gas stream directly to a reactor gas inlet of reactor 110a. In other implementations, the separation unit gas outlet is in fluid communication with optional gas cleanup system 108 and is configured to provide a reactor input gas stream to an inlet of the gas cleanup system 108.

[0052] Gas cleanup system 108 receives reactor input gases and generates clean reactor input gas. Broadly, the gas cleanup system 108 comprises a gas cleanup system inlet and a clean gas outlet. The gas cleanup system inlet is in fluid communication with the separation unit 106 and is configured to receive a reactor input gas stream from the separation unit gas outlet.

[0053] Upon receiving the reactor input gas stream, gas cleanup system 108 is configured to remove at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) from the reactor input gas, thereby generating clean reactor input gas.

[0054] The clean gas outlet is in fluid communication with reactor 110a and is configured to provide a clean reactor gas stream to a reactor gas inlet of reactor 110a. Any suitable gas cleanup system known in the art may be used for the optional gas cleanup system 108. As examples, the gas cleanup system 108 may be a cyclone, a candle filter, a zinc bed, or another suitable adsorbent system.

[0055] Reactor 110a receives reactor input gases and generates product gases. Reactor 110a may comprise more than one reactor operating in parallel or series. Reactor 110a may comprise a chemical looping reactor system.

[0056] Broadly, the reactor 110a comprises a reactor gas inlet and a product gas outlet. In some instances, the reactor gas inlet is in fluid communication with the separation unit 106 and is configured to receive a reactor input gas stream from the separation unit gas outlet. In other instances, the reactor gas inlet is in fluid communication with the gas cleanup system 108 and is configured to receive a clean reactor input gas stream from the clean gas outlet. In some instances, the reactor gas inlet is positioned adjacent a top portion of the reactor 110a.

[0057] Upon receiving the reactor input gas, reactor 110a is further configured to generate product gas. Exemplary product gases may comprise steam (H2O), carbon dioxide (CO2), carbon monoxide (CO), and/or hydrogen (H2).

[0058] The constituents of the product gas may vary depending on the type of reactor and the conditions applied to the reactor 110a. In various instances, the reactor 110a comprises oxygen carrier particles. In some instances, the reactor 110a is configured as a fixed bed reactor. In other instances, the reactor 110a is configured as a moving bed reactor.

[0059] In some instances, reactor 110a may further comprise a solids outlet in fluid communication with the solids inlet of optional combustor reactor 104/> and a solids inlet in fluid communication with the solids outlet of optional combustor reactor 104A In some instances, during operation, oxygen carrier particles may circulate through the solids inlets and outlets of reactor 110a and optional combustor reactor 104/x B. Exemplary Thermochemical System Configurations

[0060] Exemplary thermochemical system 104 may be implemented in various configurations. For instance, exemplary thermochemical system may include indirect thermochemical systems and fluidized bed thermochemical systems. Various aspects of exemplary indirect thermochemical systems and fluidized bed thermochemical systems are discussed below.

1. Indirect Thermochemical Systems

[0061] FIG. 2 shows an example indirect thermochemical system 204. Broadly, indirect thermochemical system 204 includes a thermochemical unit 204a and a combustor reactor 204Z>. In some implementations, indirect thermochemical system 204 may be combined with a fixed bed chemical looping system (FBCL).

[0062] In the embodiment shown, indirect thermochemical system 204 may cycle heat transfer media solids between reactors. The heat transfer media solids may be inert or may possess catalytic characteristics. The heat transfer media solids may be made up of active material, supports, promoters and dopants.

[0063] The solid fuel may be fed into the thermochemical unit 204a along with steam (H2O), where the solid fuel is decomposed into raw gases and solid byproducts comprising char. The char may then be transferred to the combustor reactor 204Z> and burned in the presence of air supplied externally.

[0064] The raw gases from the thermochemical unit 204a are directed towards the fixed bed chemical looping (FBCL) system. An advantage of using an indirect thermochemical system, such as thermochemical system 204, is that the heat is supplied into the system through char combustion, thereby making the system autothermal. The air sent to the combustor reactor 204Z> may be preheated using the outlet stream from the system or any other heat source available for use. In some instances, instead of air, pure O2 may be sent from an external air separation unit into the combustor reactor 204Z>, thereby generating flue gases having high CO2 concentration.

2. Fluidized Bed Thermochemical System

[0065] FIG. 3 shows an example fluidized bed thermochemical system 304. Broadly, indirect fluidized bed thermochemical system 304 includes a thermochemical unit 304a and a combustor reactor 3046. In the embodiment shown, solid fuel enters thermochemical unit 304a, whereupon the solid fuel is decomposed into raw gases and solid byproducts.

[0066] Optionally, in some configurations, the raw gases from the thermochemical unit 304a may be sent to a fixed bed chemical looping system, where some amount of spent syngas generated in a reduction step of the fixed bed chemical looping system is supplied to the combustor reactor 3046. The heat generated by burning spent syngas in the combustor reactor 304b may be used within the integrated process, thus making the process autothermal.

[0067] In certain configurations, the thermochemical unit 304c? may be enclosed within the combustor reactor 3046 to supply the necessary heat to the system. Optionally, in some implementations, heat may be supplied by burning spent syngas generated in the chemical looping system with oxygen or air to generate heat and supply to the endothermic gasification/pyrolysis reactions.

[0068] In certain configurations, the steam may be sent to the thermochemical unit 304a to assist the reactions and supply heat to the system. The steam may be heated using solar energy or any other type of renewable/nonrenewable source of heat. The optional heat transfer media shown in FIG. 3 may be any type of fluidized media that is capable of supplying heat to a reactor system, including hot flue gas from any source or process steam or hot oil from any processes of interest. [0069] In some instances, the temperature and pressure of thermochemical unit 304a may be controlled to leverage better kinetics and may be dependent on the fuel used in the system. The fluidization regime may be controlled by controlling the gas flowrates and the size and shape of the reactor. As described above, exemplary fluidized media, such as heat transfer media solids, may possess catalytic activity to enhance the gasification rates and have tar cracking tendency. The fluidized media may also contain a sacrificial material that may trap certain impurities within themselves and thus cause in-situ cleaning of the reactor input gases.

C. Example System Configurations

[0070] Exemplary reactor system 100 may be implemented in various configurations. In some instances, reactor system 100 may be configured as part of a fixed bed reactor system. In other instances, reactor system 100 may be configured as part of a moving bed reactor system. Various aspects of exemplary fixed bed reactor systems and moving bed thermochemical systems are discussed below. 1. Fixed Bed Systems

[0071] FIG. 4 is a schematic depiction of a first exemplary fixed bed reactor system 400. As shown, fixed bed reactor system 400 includes a thermochemical unit 404a, a first fixed bed reactor 410a, and a second fixed bed reactor 4106. The first fixed bed reactor 410c/ is a reducer reactor comprising oxygen carrier particles. As used herein, the term “reducer reactor” means a reactor where oxygen carrier particles are reduced. The second fixed bed reactor 410b is an oxidizer reactor comprising oxygen carrier particles. As used herein, the term “oxidizer reactor” means a reactor where oxygen carrier particles are oxidized.

[0072] In the embodiment shown, solid fuel is co-injected with a stream comprising carbon dioxide (CO2) and steam into the thermochemical unit 404a. The solid fuel then reacts with steam and CO2 in the thermochemical unit 404a, thereby generating syngas (carbon monoxide (CO) and hydrogen (H2)). The syngas may be then sent to a reactor gas inlet of the first fixed bed reactor 410a whereupon the oxygen carrier particles are reduced, and CO2 is released at the product gas outlet of the first fixed bed reactor 410a. Steam is then provided through a reactor gas inlet of the second fixed bed reactor 410b whereupon reduced oxygen carrier particles undergo steam oxidation and hydrogen is generated.

[0073] FIG. 5 is a schematic depiction of a second exemplary fixed bed reactor system 500. As shown, fixed bed reactor system 500 includes a thermochemical unit 504a, a first fixed bed reactor 510a, a second fixed bed reactor 510b, and a third fixed bed reactor 510c. The first fixed bed reactor 510a is a reducer reactor comprising oxygen carrier particles. The second fixed bed reactor 510Z> and the third fixed bed reactor 510c are oxidizer reactors comprising oxygen carrier particles.

[0074] In the embodiment shown, solid fuel, steam, and CO2 are fed into a thermochemical unit 504a to generate intermediate syngas. This intermediate syngas is introduced into the reactor gas inlet of the first fixed bed reactor 510a for reduction of oxygen carrier particles. Steam may be introduced into the reactor gas inlet of the second fixed bed reactor 510Z> to generate hydrogen (H2). Then, air oxidation may be carried out in the third fixed bed reactor 510c to regenerate oxygen carrier particles. The air oxidation step in the third fixed bed reactor 510c is used to balance the heat taken up by the reduction step carried out in the first fixed bed reactor 510a. [0075] FIG. 6 is a schematic depiction of a third exemplary fixed bed reactor system 600. As shown, fixed bed reactor system 600 includes a thermochemical unit 604a, a first fixed bed reactor 610a, a second fixed bed reactor 6106, and a third fixed bed reactor 610c. The first fixed bed reactor 610a is a reducer reactor comprising oxygen carrier particles. The second fixed bed reactor 6106 and the third fixed bed reactor 610c are oxidizer reactors comprising oxygen carrier particles. [0076] In the embodiment shown, solid fuel, steam, and CO2 are fed into the thermochemical unit 604a, thereby generating syngas. The syngas generated by thermochemical unit 604a is then injected into the reactor gas inlet of the first fixed bed reactor 610a whereupon the oxygen carrier particles are reduced, thereby converting syngas to CO2. Steam is then injected into the reactor gas inlet of second fixed bed reactor 6106 to generate hydrogen via steam oxidation. In some instances, the fixed bed reactors 610a-t/ are divided into multiple stages such that in different stages, the oxygen carrier particles have different oxidation states. By alternating the injection points and product outlets of the reactor system, as depicted in FIG. 6, the fixed bed reactor system 600 may be capable of continuous operation with stable products.

[0077] FIG. 7 schematically illustrates a fourth exemplary fixed bed reactor system 700. As shown, fixed bed reactor system 700 includes a thermochemical unit 704a, a first fixed bed reactor 710a, a second fixed bed reactor 7106, a third fixed bed reactor 710c, and a fourth fixed bed reactor 71 Or/. The first fixed bed reactor 710a and the second fixed bed reactor 7106 are reducer reactors. The third fixed bed reactor 710c and the fourth fixed bed reactor 71 Qd are oxidizer reactors comprising oxygen carrier particles.

[0078] In the embodiment shown, the solid fuel, steam, and CO2 are fed into thermochemical unit 704a, thereby generated syngas. Then, the syngas generated by thermochemical unit 704a is provided to the reactor gas inlet of the first fixed bed reactor 710a via a staged injection. The staged injection allows for a controlled reduction in the first fixed bed reactor 710a. Furthermore, product gas from the product gas outlet of first fixed bed reactor 710a is then sent to the reactor gas inlet of the second fixed bed reactor 7106 to ensure complete combustion of the gases, thereby providing product gas comprising CO2 and steam. System 700 requires four fixed bed reactors (fixed bed reactors 7 I Oa-t/) to generate hydrogen and a pure stream of CO2 for capture.

[0079] In any one of fixed bed reactor systems 400-700, discussed above, the combustor reactor 8046 and the fixed bed reactor may be integrated for heat management. As shown in FIG. 8, the combustor reactor 8046 and a fixed bed reactor 810a may be designed as a double layered configuration such that the combustor reactor 804Z> is the outer layer, and the fixed bed reactor 810a is the inner layer. The heat generated from the combustor reactor 8046 may be used to maintain the temperature of the fixed bed reactor 810a. In some instances, multiple combustor reactors 8046 may also be configured as tubes passing through the fixed bed reactor 810a to provide better heat transfer, as shown in FIG. 8.

2. Moving Bed Systems

[0080] FIG. 9 schematically illustrates a first exemplary moving bed reactor system 900. As shown, moving bed reactor system 900 includes a first moving bed reactor 910a, a second moving bed reactor 910b, a bypass standpipe, a combustor reactor 904b, and a primary particle separator (PPS) unit. The first moving bed reactor 910a is a reducer reactor comprising oxygen carrier particles. The second moving bed reactor 910b is an oxidizer reactor comprising oxygen carrier particles. The combustor reactor 9046 is a fluidized bed combustor reactor.

[0081] In the embodiment shown, solid fuel is injected into the middle of the first moving bed reactor 910a at a high temperature, e.g., a temperature of approximately 800-850 °C. At high temperatures, the solid fuel may be decomposed into raw gases and solid byproducts comprising char. The raw gases may then travel upwards to the reactor inlet of the first moving bed reactor 910a, where the gases react with fully oxidized oxygen carrier particles, thereby generating reduced oxygen carrier particles, CO2, and steam. As further shown, enhancer gas may be injected through a bottom gas inlet of the first moving bed reactor 910a to ensure complete gasification of char. Exemplary enhancer gases may comprise CO2 and/or steam. The reduced oxygen carrier particles then travel downwards to the second moving bed reactor 9106. Steam is fed into the reactor gas inlet of the second moving bed reactor 9106 to react with the oxygen carrier particles and generate high purity H2. Oxygen carrier particles may then be regenerated with air in the combustor reactor 9046. These fully regenerated oxygen carrier particles may be pneumatically conveyed back to the first moving bed reactor 910a through the riser and PPS unit. However, in the addition of solid fuels in the middle of the first moving bed reactor 910a leads to the generation of solid byproducts comprising char and ash, that travels downwards in the moving bed.

[0082] Apart from the char and ash, there may be additional fines that are generated in the process which may be also present in the moving bed. While travelling from the first moving bed reactor 910a to the second moving bed reactor 9106, the oxygen carrier particles must pass through a transient section, wherein the gas velocities may be higher the gas velocities in the remaining bed. Similarly, the standpipe may have a zone seal gas to prevent the mixing of the gases from the first moving bed reactor 91 Oa and the second moving bed reactor 91 Ob. In these sections, the gas velocities may exceed the terminal velocities of the ash, char, and fines, and as a result, they may accumulate in the bottom part of the first fixed bed reactor 910a. To counter for this phenomenon, an additional bypass standpipe may be incorporated into the system. The reduced particles along with fines may be directly diverted into the combustor reactor 9046, thereby ensuring its proper functioning.

[0083] The solids flowrate through the by-pass may be controlled by use of the gas-solid flowrate controlling devices such as L-valve, J-valve, Loop-seal, or any other suitable gas-solid flowrate controlling device known in the art. It is possible to regulate the flow of solids in order to divert a particular amount of reduced oxygen carrier particles directly into the combustor reactor 9046. This process enables the oxygen carrier particles to generate heat through exothermic oxidation.

[0084] FIG. 10 schematically illustrates a second exemplary moving bed reactor system 1000. As shown, moving bed reactor system 1000 includes a thermochemical unit 1004a a first moving bed reactor 1010a, a second moving bed reactor 10106, a combustor reactor 10046, and a primary particle separator (PPS) unit.

[0085] In the embodiment shown, the thermochemical unit 1004a is included in the moving bed system configuration to avoid problems associated with mixing of different size of solid fuel and oxygen carrier particles. In the thermochemical unit 1004a, solid fuel may be decomposed into raw gas and solid byproducts, such as char. The decomposition process may be assisted by heat. In various instances, the heat may be supplied using a solar source and/or by electrically heating the thermochemical unit 1004a. The raw gases from the thermochemical unit 1004a may then be injected into the first moving bed reactor 1010a where the oxygen carrier particles lose their lattice oxygen. This reaction may generate CO2 and steam.

[0086] The reduced oxygen carrier particles then move downwards to the second moving bed reactor 10106, wherein steam reacts with the oxygen carrier particles, thereby producing pure H2 stream. The oxygen carrier particles move into the fluidized bed combustor and completely oxidize in the presence of air. Some amount of heat in the system is contributed by burning char from thermochemical unit 1004a in the combustor reactor 10046. The oxygen carrier particles from the combustor reactor 10046 are sent back pneumatically to the first moving bed reactor 1010a.

[0087] FIG. 11 schematically illustrates a third exemplary moving bed reactor system 1100. As shown, moving bed reactor system 1100 includes a thermochemical unit 1104a, a moving bed reactor 1110a, a combustor reactor 1 1046, and a primary particle separator (PPS) unit. The moving bed reactor 1110a is a reducer reactor.

[0088] In the embodiment shown, partial oxidation occurs in moving bed reactor 1110a, thus generating syngas i.e., CO and H2. In some instances, heat generated in the combustor reactor 11046 may be integrated with the thermochemical unit 1104a to compensate for the endothermic heat requirement of the thermochemical unit 1104a. The hot depleted air stream from the combustor reactor 11046 may be sent to the heating section of the thermochemical unit 1104a to supply heat to the thermochemical unit 1104a. The heat supplied by combustor reactor 11046 may be sufficient for gasification or pyrolysis. In some instances, combustor reactor 11046 may be a fluidized bed combustor that encloses the thermochemical unit 1104a within itself and supply the heat through the wall of the thermochemical unit 1104a.

IV. Exemplary Methods

[0089] Exemplary methods of operating a reactor system may comprise various operations. Exemplary systems described above may be used to implement one or more of the methods described below.

[0090] FIG. 12 shows an exemplary method 1200 for operating a reactor system. Broadly, method 1200 includes receiving solid fuel in a thermochemical unit (operation 1202), generating raw gas and solid byproducts (operation 1204), collecting the solid byproducts (operation 1206), separating particulates from the raw gas (operation 1210), and providing the reactor input gas to a gas inlet of a reactor (operation 1216). Various optional operations are shown in dotted outline in FIG. 12. Other embodiments may comprise more or fewer operations than those discussed below. [0091] In various instances, receiving solid fuel in a thermochemical unit (operation 1202) may comprise providing input solid fuel from a solid carbonaceous feedstock source to a thermochemical unit. In some instances, the input solid fuel may be provided from the solid carbonaceous feedstock source to the thermochemical unit through a solid fuel inlet of the thermochemical unit. [0092] In various instances, the thermochemical unit may be air-free. For example, in some instances, the thermochemical unit may receive a constant stream of argon (Ar) or nitrogen (N2), thereby maintaining an inert atmosphere.

[0093] In other instances, the thermochemical unit may receive oxygen (O2) or steam (H2O) and carbon dioxide (CO2). In some instances, receiving solid fuel in the thermochemical unit (operation 1202) may occur concurrently with receiving oxygen (O2) or steam (H2O) and carbon dioxide (CO2) in the thermochemical unit.

[0094] In various instances, the steam (H2O) received by the thermochemical unit may have a temperature of 400 °C to 800 °C. In various instances, the steam (H2O) received by the thermochemical unit may have a temperature of 425 °C to 775 °C; 450 °C to 750 °C; 475 °C to 725 °C; 500 °C to 700 °C; 525 °C to 675 °C; 550 °C to 650 °C; or 575 °C to 625 °C. In various instances, the steam (H2O) received by the thermochemical unit may have a temperature of no greater than 800 °C; no greater than 750 °C; no greater than 700 °C; no greater than 650 °C; no greater than 600 °C; no greater than 550 °C; no greater than 500 °C; or no greater than 450 °C. In various instances, the steam (H2O) received by the thermochemical unit may have a temperature of no less than 400 °C; no less than 450 °C; no less than 500 °C; no less than 550 °C; no less than 600 °C; no less than 650 °C; no less than 700 °C; or no less than 750 °C.

[0095] After receiving solid fuel in the thermochemical unit (operation 1202), exemplary method 1200 may further comprise generating raw gas and solid byproducts (operation 1204). Broadly, exemplary raw gases and solid byproducts may be generated in the in the thermochemical unit via thermal decomposition. Exemplary thermal decomposition methods include gasification and pyrolysis. Exemplary raw gases generated by operation 1202 may comprise heavy hydrocarbons and particulates. Exemplary solid byproducts generated by operation 1202 may comprise ash and/or char.

[0096] Example method 1200 may further include operating the thermochemical unit at a temperature of 300 °C to 1,500 °C. In various instances, the thermochemical unit may be operated at a temperature of 350 °C to 1400 °C; 400 °C to 1300 °C; 450 °C to 1200 °C; 500 °C to 1100 °C; 550 °C to 1000 °C; 600 °C to 900 °C; 650 °C to 850 °C; or 700 °C to 800 °C. In various instances, the thermochemical unit may be operated at a temperature of no greater than 1500 °C; no greater than 1400 °C; no greater than 1300 °C; no greater than 1200 °C; no greater than 1100 °C; no greater than 1000 °C; no greater than 900 °C; no greater than 800 °C; no greater than 700 °C; no greater than 600 °C; no greater than 500 °C; or no greater than 400 °C. In various instances, the thermochemical unit may be operated at a temperature of no less than 300 °C; no less than 400 °C; no less than 500 °C; no less than 600 °C; no less than 700 °C; no less than 800 °C; no less than 900 °C; no less than 1000 °C; no less than 1100 °C; no less than 1200 °C; no less than 1300 °C; or no less than 1400 °C.

[0097] Example method 1200 may further include operating the thermochemical unit at atmospheric pressure.

[0098] Upon generating raw gas and solid byproducts (operation 1204), exemplary method 1200 may further comprise collecting the solid byproducts (operation 1206). Collecting the solid byproducts (operation 1206) may comprise discharging the solid byproducts from the thermochemical unit. In some instances, example method 1200 may further comprise transferring char to a combustor reactor (operation 1207). In some instances, the char may be transferred through a solid byproducts outlet of the thermochemical unit and into a solid byproducts inlet of a combustor reactor.

[0099] Upon generating raw gas and solid byproducts (operation 1204), exemplary method 1200 may further comprise collecting the raw gas (operation 1208) from the thermochemical unit. In various instances, collecting the raw gas may comprise providing a raw gas stream from the thermochemical unit to a separation unit. Specifically, the raw gas stream may be provided from a raw gas outlet of the thermochemical unit, through a separation unit inlet of the separation unit. Exemplary raw gas may comprise heavy hydrocarbons and particulates. In various instances, collecting the raw gas (operation 1208) and collecting the solid byproducts (operation 1206) may occur concurrently.

[0100] Exemplary method 1200 may further comprise separating particulates from the raw gas (operation 1210), thereby generating reactor input gas. In various instances, separating particulates from the raw gas (operation 1210), may occur in a separation unit where particulates are separated by volume expansion and application of a centrifugal force on the particulates. Exemplary separation units may induce volume expansion and may apply a centrifugal force on the particulates. Exemplary separation units include cyclone-type units. Exemplary reactor input gas generated by operation 1210 may comprise less than 1 weight percent (wt%) ash and less than 1 wt% char. Moreover, exemplary reactor input gas generated by operation 1210 may be substantially free of particulates. [0101] Exemplary method 1200 may further comprise providing the reactor input gas to a gas inlet of a reactor (operation 1216). In various instances, providing the reactor input gas to a gas inlet of a reactor (operation 1216) may comprise providing a reactor input gas stream from a separation unit to a reactor. Specifically, the reactor input gas stream may be provided from a separation unit gas outlet through a reactor gas inlet.

[0102] In some instances, before providing the reactor input gas to the gas inlet of the reactor (operation 1216), the reactor input gas may be provided to a gas cleanup system (operation 1212). By providing the reactor input gas to the gas cleanup system, at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) may be removed from the reactor input gas, thereby generating clean reactor input gas (operation 1214). In various instances, generating clean reactor input gas (operation 1211), may comprise removing at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) by absorption or a chemical reaction. In various instances, the gas cleanup system may be operated such that the reactor input gases do not condense.

[0103] In various instances, the reactor input gas or clean reactor input gas may have a temperature of 500 °C to 900 °C. In some instances, the reactor input gas or clean reactor input gas may have a temperature of 525 °C to 875 °C; 550 °C to 850 °C; 575 °C to 825 °C; 600 °C to 800 °C; 625 °C to 775 °C; 650 °C to 750 °C; or 675 °C to 725 °C. In some instances, the reactor input gas or clean reactor input gas may have a temperature of no greater than 900 °C; no greater than 850 °C; no greater than 800 °C; no greater than 750 °C; no greater than 700 °C; no greater than 650 °C; no greater than 600 °C; or no greater than 550 °C. In some instances, the reactor input gas or clean reactor input gas may have a temperature of no less than 500 °C; no less than 550 °C; no less than 600 °C; no less than 650 °C; no less than 700 °C; no less than 750 °C; no less than 800 °C; or no less than 850 °C.

[0104] In various instances, the reactor may comprise oxygen carrier particles. In various instances, the reactor may be configured as a fixed bed reactor. In other instances, the reactor may be configured as a moving bed reactor.

[0105] Product gas is generated within the reactor. In some instances, exemplary method 1200 may further comprise collecting product gas from the reactor. V. Experimental Examples

[0106] A ’A-inch diameter ceramic tube was heated in a furnace at 800 °C to pyrolyze the biomass. Corncobs were used as biomass for the experiments. Seven batches of 5 grams of the corncobs was prepared. Once the furnace heated up to 800 °C, these batches were put into the heated tube using a lock hopper system.

[0016] The 2.5 kWth bench scale reactor was a two-inch diameter reactor equipped with clamshell heaters. The reactor was heated to 950 °C with oxygen carrier particles to simulate a fixed bed reactor.

[0017] As soon as the corn cobs entered the heated ceramic tube, they pyrolyzed, and the volatiles were sent countercurrently to the bench-scale reactor with the help of a connected tube. The volatiles reacted with the fully oxidized oxygen carrier particles. The product gas, which was pure carbon dioxide (CO2), was analyzed via a Siemens hydrocarbon analyzer. The results are shown in FIG. 13, a graph showing the gas concentration percentage and temperature of the fixed bed bench-scale reactor. The spikes in the graph show the points when biomass is injected, and volatiles react with oxygen carrier particles. The gas concentration of carbon monoxide does not increase, indicating that the volatiles have been fully converted to carbon dioxide.

Exemplary Embodiments

[0018] For reasons of completeness, various aspects of the technology are set out in the following numbered embodiments:

Embodiment 1. A method of operating a reactor system, the method comprising: receiving solid fuel in a thermochemical unit; generating raw gas and solid byproducts in the thermochemical unit, the solid byproducts comprising ash and/or char; collecting the solid byproducts from the thermochemical unit; collecting the raw gas from the thermochemical unit; separating particulates from the raw gas, thereby generating reactor input gas; and providing the reactor input gas to a gas inlet of a reactor, the reactor input gas having a temperature of at least 500 °C; wherein the reactor input gas comprises less than 1 weight percent (wt%) ash and less than 1 wt% char; wherein the reactor is configured as a fixed bed reactor comprising oxygen carrier particles.

Embodiment 2. The method according to embodiment 1, further comprising; before providing the reactor input gas to the gas inlet of the reactor, providing the reactor input gas to a gas cleanup system; removing at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) from the reactor input gas, thereby generating clean reactor input gas; and providing the clean reactor input gas to the gas inlet of the reactor.

Embodiment 3. The method according to embodiment 1 or 2, wherein the thermochemical unit is air-free.

Embodiment 4. The method according to any one of embodiments 1-3, further comprising receiving oxygen (O2) or steam (H2O) and carbon dioxide (CO2) in the thermochemical unit.

Embodiment 5. The method according to any one of embodiments 1-4, further comprising operating the thermochemical unit at a temperature of 300 °C to 1,500 °C.

Embodiment 6. The method according to any one of embodiments 1-5, wherein the solid fuel comprises 0.001 % by weight (wt%) to 95 wt% heavy hydrocarbons.

Embodiment 7. The method according to any one of embodiments 1-6, wherein the solid fuel comprises 20 wt% to 50 wt% char.

Embodiment 8. The method according to any one of embodiments 1-7, wherein the solid fuel comprises 20 wt% to 50 wt% volatile matter, 20 wt% to 50 wt% char, and 5 wt% to 15 wt% ash. Embodiment 9. The method according to any one of embodiments 1-7, wherein the solid fuel comprises 20 wt% to 80 wt% volatile matter, 10 wt% to 50 wt% char, and 0 wt% to 10 wt% ash.

Embodiment 10. The method according to any one of embodiments 1-9, wherein the reactor input gas comprises heavy hydrocarbons.

Embodiment 11. The method according to any one of embodiments 1-10, further comprising transferring the char from a solid byproducts outlet of the thermochemical unit to a solid byproducts inlet of a combustor reactor.

Embodiment 12. A reactor system, comprising: a thermochemical unit, comprising: a solid fuel inlet configured to receive solid fuel, the solid fuel inlet being in communication with a solid carbonaceous feedstock source; a raw gas outlet configured to provide a raw gas stream; and a solid byproducts outlet configured to discharge solid byproducts, the solid byproducts comprising ash and/or char; a separation unit configured to receive the raw gas stream and separate particulates from the raw gas stream, the separation unit comprising: a separation unit inlet in fluid communication with the raw gas outlet; a particulates outlet configured to discharge particulates; and a separation unit gas outlet configured to discharge reactor input gas; and a fixed bed chemical looping system, comprising: a reactor comprising: a fixed bed of oxygen carrier particles; a reactor gas inlet configured to receive a reactor input gas stream from the separation unit, the reactor gas inlet being in fluid communication with the separation unit gas outlet; and a product gas outlet configured to provide product gas generated within the reactor. Embodiment 13. The reactor system according to embodiment 12, further comprising a gas cleanup system, the gas cleanup system comprising: a gas cleanup system inlet in fluid communication with the separation unit gas outlet; and a clean gas outlet in fluid communication with the reactor gas inlet.

Embodiment 14. The reactor system according to embodiment 12 or 13, wherein the gas cleanup system is configured to: remove at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) from the reactor input gas stream, thereby generating clean reactor input gas; and provide the clean reactor input gas to the reactor gas inlet.

Embodiment 15. The reactor system according to any one of embodiments 12-14, the thermochemical unit further comprising a heat transfer media solids inlet configured to receive a stream of heat transfer media solids.

Embodiment 16. The reactor system according to any one of embodiments 12-15, the thermochemical unit further comprising a fluidized media bed.

Embodiment 17. The reactor system according to any one of embodiments 12-16, wherein the product gas comprises carbon monoxide (CO) and hydrogen (H2).

Embodiment 18. The reactor system according to any one of embodiments 12-17, wherein the solid carbonaceous feedstock source comprises coal or biomass.

Embodiment 19. The reactor system according to any one of embodiments 12-18, further comprising a combustor reactor, the combustor reactor comprising: a solid byproducts inlet in fluid communication with the solid byproducts outlet; and a combustion products outlet in fluid communication with an inlet of a unit in the fixed bed chemical looping system. Embodiment 20. The reactor system according to any one of embodiments 12-19, wherein the reactor is configured for autothermal operation.

[0107] It is understood that the foregoing detailed description and accompanying examples are merely illustrative and are not to be taken as limitations upon the scope of the disclosure. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications, including without limitation those relating to the chemical structures, substituents, derivatives, intermediates, syntheses, compositions, formulations, pH and temperature adjustments, separation, recovery, or methods of use, may be made without departing from the spirit and scope of the disclosure.

Claims

1. A method of operating a reactor system, the method comprising: receiving solid fuel in a thermochemical unit; generating raw gas and solid byproducts in the thermochemical unit, the solid byproducts comprising ash and/or char; collecting the solid byproducts from the thermochemical unit; collecting the raw gas from the thermochemical unit; separating particulates from the raw gas, thereby generating reactor input gas; and providing the reactor input gas to a gas inlet of a reactor, the reactor input gas having a temperature of at least 500 °C; wherein the reactor input gas comprises less than 1 weight percent (wt%) ash and less than 1 wt% char; wherein the reactor is configured as a fixed bed reactor comprising oxygen carrier particles.

2. The method according to claim 1, further comprising; before providing the reactor input gas to the gas inlet of the reactor, providing the reactor input gas to a gas cleanup system; removing at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) from the reactor input gas, thereby generating clean reactor input gas; and providing the clean reactor input gas to the gas inlet of the reactor.

3. The method according to claim 1, wherein the thermochemical unit is air-free.

4. The method according to claim 1 , further comprising receiving oxygen (O2) or steam (H2O) and carbon dioxide (CO2) in the thermochemical unit.

5. The method according to claim 1, further comprising operating the thermochemical unit at a temperature of 300 °C to 1,500 °C.

6. The method according to claim 1 , wherein the solid fuel comprises 0.001 % by weight (wt%) to 95 wt% heavy hydrocarbons.

7. The method according to claim 1, wherein the solid fuel comprises 20 wt% to 50 wt% char.

8. The method according to claim 1, wherein the solid fuel comprises 20 wt% to 50 wt% volatile matter, 20 wt% to 50 wt% char, and 5 wt% to 15 wt% ash.

9. The method according to claim 1, wherein the solid fuel comprises 20 wt% to 80 wt% volatile matter, 10 wt% to 50 wt% char, and 0 wt% to 10 wt% ash.

10. The method according to claim 1, wherein the reactor input gas comprises heavy hydrocarbons.

11. The method according to claim 1, further comprising transferring the char from a solid byproducts outlet of the thermochemical unit to a solid byproducts inlet of a combustor reactor.

12. A reactor system, comprising: a thermochemical unit, comprising: a solid fuel inlet configured to receive solid fuel, the solid fuel inlet being in communication with a solid carbonaceous feedstock source; a raw gas outlet configured to provide a raw gas stream; and a solid byproducts outlet configured to discharge solid byproducts, the solid byproducts comprising ash and/or char; a separation unit configured to receive the raw gas stream and separate particulates from the raw gas stream, the separation unit comprising: a separation unit inlet in fluid communication with the raw gas outlet; a particulates outlet configured to discharge particulates; and a separation unit gas outlet configured to discharge reactor input gas; and a fixed bed chemical looping system, comprising: a reactor comprising: a fixed bed of oxygen carrier particles; a reactor gas inlet configured to receive a reactor input gas stream from the separation unit, the reactor gas inlet being in fluid communication with the separation unit gas outlet; and a product gas outlet configured to provide product gas generated within the reactor.

13. The reactor system according to claim 12, further comprising a gas cleanup system, the gas cleanup system comprising: a gas cleanup system inlet in fluid communication with the separation unit gas outlet; and a clean gas outlet in fluid communication with the reactor gas inlet.

14. The reactor system according to claim 13, wherein the gas cleanup system is configured to: remove at least one of sulfur (S), chlorine (Cl), mercury (Hg), and arsenic (As) from the reactor input gas stream, thereby generating clean reactor input gas; and provide the clean reactor input gas to the reactor gas inlet.

15. The reactor system according to claim 12, the thermochemical unit further comprising a heat transfer media solids inlet configured to receive a stream of heat transfer media solids.

16. The reactor system according to claim 12, the thermochemical unit further comprising a fluidized media bed.

17. The reactor system according to claim 12, wherein the product gas comprises carbon monoxide (CO) and hydrogen (H2).

18. The reactor system according to claim 12, wherein the solid carbonaceous feedstock source comprises coal or biomass.

19. The reactor system according to claim 12, further comprising a combustor reactor, the combustor reactor comprising: a solid byproducts inlet in fluid communication with the solid byproducts outlet; and a combustion products outlet in fluid communication with an inlet of a unit in the fixed bed chemical looping system.

20. The reactor system according to claim 12, wherein the reactor is configured for autothermal operation.