Systems, methods and materials for stable phase syngas generation

Abstract

Systems and methods generally involve processing a gaseous reducing agent and a gaseous reforming agent to produce syngas in the presence of a stable-phase change metal-oxide based oxygen carrier. During operation, an oxygen content is measured for a reactor input stream and a reactor output stream. A percent oxygen depletion of the metal oxide is determined using an initial oxygen content of the metal oxide, the oxygen content of the input stream, and the oxygen content of the output stream. Based on the percent oxygen depletion, a mole ratio of reducing gas to oxidant in the input stream may be adjusted accordingly.

Description

TECHNICAL FIELD

The present disclosure relates to systems and methods for syngas generation. More particularly, the present disclosure relates to systems and methods for syngas generation through phase change mediated partial oxidation of methane.

INTRODUCTION

Syngas, a mixture of CO and H₂, is a crucial precursor for various chemicals and liquid fuels. Conventional syngas generation is achieved through methane reforming with an oxidant over a catalyst. Typically, the oxidants used are molecular oxygen, steam or CO₂, where these can be used separately or as mixtures in a process.

Among syngas generation technologies, steam methane reforming (SMR) and autothermal reforming (ATR) are used for hydrogen production and liquid fuel production, respectively. Both systems employ a Ni-based catalyst, using one or more oxidants to control the H₂:CO ratio and methane conversion. ATR process utilizes H₂O and O₂ for partial oxidation of methane, adjusting the ratios of the two oxidants to provide a H₂:CO ratio of ˜2. However, this process requires auxiliary equipment, thus negatively affecting the overall economics of syngas generation.

Improving the economics of syngas generation from methane has tremendous implications towards liquid fuel and chemical production. Commercial gas-to-liquid plants employ air separation units (ASUs) to use molecular oxygen in conjunction with steam to partially oxidize CH₄ to CO and H₂. The catalyst, however, suffers from carbon deposition under lower oxidant concentrations, limiting the operating range of the process. Additionally, an ASU is energy and capital intensive which severely affects the overall economics for syngas generation.

SUMMARY

Generally, the instant disclosure relates to syngas production through stable phase change mediated partial oxidation of a reducing agent.

In one aspect, a method for operating a reactor system is disclosed. The example method includes providing an input stream to the reactor system, where the input stream includes a reducing gas stream and an oxidant stream, determining an initial oxygen content of a metal oxide in the reactor system, measuring an oxygen content of the input stream, measuring an oxygen content of an output stream from the reactor system, calculating a percent oxygen depletion of the metal oxide using the initial oxygen content of the metal oxide, the oxygen content of the input stream, and the oxygen content of the output stream, and, when the percent oxygen depletion of the metal oxide is above a predetermined threshold, adjusting a mole ratio of reducing gas to oxidant gas in the input stream.

In another aspect, another method for operating a reactor system is disclosed. The example method includes providing a first input stream to a first reactor assembly in the reactor system, where the first input stream including reducing gas and oxidant; determining an initial oxygen content of a first metal oxide in the first reactor assembly, measuring a first input stream oxygen content, measuring an oxygen content of an output of the first reactor assembly, calculating a percent oxygen depletion of the first metal oxide using the initial oxygen content of the first metal oxide, the first input stream oxygen content, and the oxygen content of the output of the first reactor assembly, when the percent oxygen depletion of the first metal oxide is above a first predetermined threshold, adjusting a mole ratio of reducing gas to oxidant in the first input stream, providing a second input stream to a second reactor assembly in the reactor system, the second input stream including reducing gas and oxidant, determining an initial oxygen content of a second metal oxide in the second reactor assembly, measuring a second input stream oxygen content, measuring an oxygen content of an output of the second reactor assembly, calculating a percent oxygen depletion of the second metal oxide using the initial oxygen content of the second metal oxide, the second input stream oxygen content, and the oxygen content of the output stream, and, when the percent oxygen depletion of the second metal oxide is above a second predetermined threshold, adjusting a mole ratio of reducing gas to oxidant in the second input stream.

There is no specific requirement that a material, technique or method relating to syngas generation include all of the details characterized herein, in order to obtain some benefit according to the present disclosure. Thus, the specific examples characterized herein are meant to be exemplary applications of the techniques described, and alternatives are possible.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of an example system for syngas generation.

FIG. 2 is a schematic diagram of another example system for syngas generation.

FIG. 3 shows an example method for operating a reactor system.

FIG. 4 shows another example method for operating a reactor system.

FIG. 5 shows thermodynamic data for methane conversion of various systems at 30 atm and 1000° C.

FIG. 6 shows thermodynamic data for methane conversion of various systems at 30 atm and 950° C.

FIG. 7 shows experimental data for a solid conversion profile under CH₄ reduction of FeTiO₃ at various temperatures.

FIG. 8 show exemplary operating modes of example fixed beds for inlet gas composition using H₂O/H₂ mole ratio.

FIG. 9 show exemplary operating modes of example fixed beds for inlet gas composition using CO₂/CO mole ratio.

DETAILED DESCRIPTION

Systems and methods disclosed and contemplated herein relate to syngas generation. Disclosed systems and methods employ stable solid metal oxide phases (termed “stable phase”) during syngas generation, where the metal oxides participate in reactions associated with syngas generation. That is, using a stable phase can eliminate the use of molecular oxygen by efficiently transferring oxygen from reforming agents such as H₂O and CO₂ to gaseous fuels such as CH₄ through stable solid metal oxide phases. The use of a solid phase assisted transfer inherently changes the thermodynamics of the overall system, allowing for higher syngas production efficiencies. This mediation of oxygen is driven by the thermodynamics of the gas-solid reactions and the kinetic rates of reduction and oxidation reactions of the solid metal oxide.

I. Example Reactions

Systems and methods disclosed and contemplated herein generally involve processing a gaseous reducing agent and a gaseous reforming agent to produce syngas in the presence of a stable-phase change metal-oxide based oxygen carrier. In some implementations, the gaseous reducing agent is methane and the gaseous reforming agent includes steam and/or CO₂, although other possibilities are contemplated. Example reaction stoichiometry is provided in Reaction I and Reaction II below, where M is a metal.Fe_xM_yO_z+CH₄-->Fe_xM_yO_z-d+[CO+H₂+CO₂+H₂O]  (I)Fe_xM_yO_z-d+CO₂,H₂O-->Fe_xM_yO_z+[CO+H₂+CO₂+H₂O]  (II)

The gaseous reducing agent abstracts lattice oxygen from the metal-oxide oxygen carrier (as shown in Reaction I), while the oxidizing agents replenish the depleted oxygen (as shown in Reaction II). That is, CH₄ reacts with the metal oxide and abstracts the lattice oxygen to form complete combustion products (CO₂, H₂O) and partial combustion products (CO, H₂). The metal on the lattice surface acts as the catalytic active site for hydrogen (H) abstraction from CH₄. This creates oxygen vacancies on the surface of the metal oxide, which in-turn act as catalytic active sites for CO₂ or H₂O reduction. The CO₂ and H₂O thus oxidize the reduced metal oxide in the same reactor and form CO and H₂, respectively.

Under steady state condition, the oxygen abstraction from CH₄ and the oxygen donation from CO₂/H₂O reach an equilibrium. This equilibrium directly affects the oxidation state of the metal oxide reacting and the gas phase composition. As a result, the metal oxide bed has a stratified oxidation state of the active metal where the net oxidation state of the metal oxide does not change with time. Thus, the overall reaction mimics the catalytic dry reforming or steam methane reforming process but the mechanism for CH₄ and CO₂/H₂O gas-solid reactions follows a different path. This unique activation of CH₄ and CO₂/H₂O with the metal oxide acting as the oxygen mediator adds additional degrees of freedom which helps in producing syngas efficiently.

The mediation of reaction I and II by lattice oxygen from the metal-oxides influences the thermodynamic composition of the syngas that is produced from this system. The variation of the thermodynamic composition because of mediation by the lattice oxygen from the metal-oxide carrier differentiates this system from gas-phase only chemistry. The variables that affect thermodynamic gas product composition for this system include, but are not limited to, the amount of lattice oxygen per amount of metal that participates in the reactions, the composition, crystalline structure and the solid phase of the metals, and the specific mixing and kinetic dynamics.

FIG. 8 and FIG. 9 show two examples that can be used with methods of determining an operating mode of a fixed bed in a reactor system with a given inlet gas composition. The example shown in FIG. 8 uses a gas mixture of H₂O and H₂ as inlet, while the example shown in FIG. 9 uses a gas mixture of CO₂ and CO as inlet. Here H₂ and CO are the reducing gases and H₂O and CO₂ are the oxidizing gases for FIG. 8 and FIG. 9, respectively.

As shown in FIG. 8, when the inlet gas ratio of H₂O/H₂ is greater than the value represented by the curve, the inlet gas is an oxidizing gas and will oxidize Fe in the bed into FeO. When the inlet gas ratio of H₂O/H₂ is less than the value represented by the curve, the inlet gas is a reducing gas and will reduce FeO in the bed into Fe. Therefore, the curve in FIG. 8 represents a critical inlet gas composition that neither reduces nor oxidizes the solid material in the bed. In the example shown in FIG. 9, the CO₂/CO ratio is used as the indicator of whether the gas mixture is an oxidizing or a reducing mixture, in a similar way to the previous example shown in FIG. 8. It is noted that in both examples, the critical inlet gas composition that makes the gas neither reducing nor oxidizing varies with temperature.

II. Example Systems and Configurations

Broadly, example systems disclosed and contemplated herein include 1 reactor/1 reactor system, 2 reactors/2 reactor systems, or more than 2 reactors/reactor systems. Each configuration is discussed below.

A. Exemplary Configurations with One Reactor System

FIG. 1 shows a schematic diagram of example syngas generation system 100. As shown, syngas generation system 100 includes reducing gas source 102, oxidant source 106, and reactor system 114. Also shown in FIG. 1 are flow regulation unit 104, flow regulation unit 108, input stream oxygen (O) monitor 110, and output stream oxygen (O) monitor 118. Other embodiments can include more or fewer components.

Reactor system 114 includes one or more reactors operating under similar conditions and receiving the same input stream 112. Typically, when reactor system 114 includes more than one reactor, each reactor operates in parallel. Output stream 116 from reactor system 114 includes syngas generated in reactor system 114. Each reactor in reactor system 114 also includes metal oxide. In some implementations, the reactors are in fixed bed configurations.

Input stream 112 is provided to reactor system 114, and the input stream includes reducing gas and oxidant provided from reducing gas source 102 and oxidant source 106, respectively. In some instances, reducing gas from reducing gas source 102 is pre-heated before entering reactor system 114. Heat for increasing the temperature of the reducing gas can be provided in various ways, such as with heat exchangers, waste heat streams, solar energy, gas energy, and electrical energy. The net reactions occurring in reactor system 114 are endothermic.

One or more components can be used to adjust a mole ratio of reducing gas to oxidant in the input stream 112. For instance, reducing gas source 102 can include flow regulation unit 104 and oxidant source 106 can include flow regulation unit 108. Flow regulation units 104 and 106 operate to adjust the flow rate of reducing gas and oxidant, respectively. An example flow regulation unit is, without limitation, a valve.

As another example not shown in FIG. 1, input stream 112 can receive flow from a first reducing gas/oxidant source having a first mole ratio of reducing gas to oxidant and from a second reducing gas/oxidant source having a second mole ratio of reducing gas to oxidant. Each of these combined sources can include flow regulation devices usable to adjust the mole ratio of reducing gas and oxidant in input stream 112.

Broadly, during operation, oxygen monitor 110 measures an oxygen (O) content of input stream 112, and oxygen monitor 118 measures an oxygen (O) content of output stream 116. The oxygen content refers to oxygen present in any gas stream in molecular form (eg. CO₂, H₂O, CO etc.). Oxygen content can be measured using one or more devices known in the art. Typically, oxygen monitor 110 and oxygen monitor 118 are in electrical communication with one or more controllers (not shown in FIG. 1), where the one or more controllers can adjust the mole ratio of reducing gas to oxidant in the input stream 112.

B. Exemplary Configurations with Two or More Reactor Systems

FIG. 2 shows a schematic diagram of example syngas generation system 200. As shown, syngas generation system 200 includes reducing gas and oxidant source 202, reducing gas and oxidant source 204, reactor system 222, and reactor system 224. Also shown in FIG. 2 are flow regulation units 206, 208, 210, and 212, input stream oxygen (O) monitor 214, input stream oxygen (O) monitor 216, output stream oxygen (O) monitor 230, and output stream oxygen (O) monitor 232. Other embodiments can include more or fewer components.

Syngas generation system 200 includes two reactor systems: reactor system 222 and reactor system 224. Reactor system 222 and reactor system 224 operate at different mole ratios of reducing gas to oxidant. Each reactor system 222 and 224 can include multiple reactors operating in parallel. Each reactor in reactor system 222 and reactor system 224 also includes metal oxide. In some implementations, the reactors are in fixed bed configurations.

Reducing gas and oxidant source 202 provides a first mole ratio of reducing gas to oxidant and reducing gas and oxidant source 204 provides a second mole ratio of reducing gas to oxidant, where the first mole ratio and the second mole ratios are different during typical operation.

Reactor system 222 receives input stream 218 that includes reducing gas and oxidant. Flow regulation unit 206 adjusts a flow rate from reducing gas and oxidant source 202 into input stream 218. Flow regulation unit 208 adjusts a flow rate from reducing gas and oxidant source 204 into input stream 218. Oxygen monitor 214 measures the oxygen (O) content of input stream 218 provided to reactor system 222.

Reactor system 224 receives input stream 220 that includes reducing gas and oxidant. Flow regulation unit 210 adjusts a flow rate from reducing gas and oxidant source 202 into input stream 220. Flow regulation unit 212 adjusts a flow rate from reducing gas and oxidant source 204 into input stream 220. Oxygen monitor 216 measures the oxygen (O) content of input stream 220 provided to reactor system 224.

Reactor system 222 provides output stream 226 that includes syngas generated in reactor system 222. Oxygen monitor 230 measures the oxygen (O) content of output stream 226 provided by reactor system 222.

Reactor system 224 provides output stream 228 that includes syngas generated in reactor system 224. Oxygen monitor 232 measures the oxygen (O) content of output stream 228 provided by reactor system 224.

Typically, oxygen monitor 214, oxygen monitor 216, oxygen monitor 230, and oxygen monitor 232 are in electrical communication with one or more controllers (not shown in FIG. 2). The one or more controllers can adjust the mole ratio of reducing gas to oxidant in input stream 218 and input stream 220.

In implementations with three or more reactor systems, not shown in the figures, the system can be arranged similarly to system 200. That is, the third (and other) reactor systems can be provided with input streams including an adjustable reducing gas to oxidant mole ratio. Oxygen content monitors are disposed upstream and downstream of each reactor system.

C. Exemplary Operating Conditions

Example systems disclosed herein can operate at various conditions. For instance, reactors/reactor systems disclosed herein typically operate at temperatures of 700° C. to 1100° C. In various implementations, reactors/reactor systems can operate at 700° C. to 1000° C.; 800° C. to 1100° C.; 700° C. to 900° C.; 800° C. to 1000° C.; 900° C. to 1100° C.; 850° C. to 1050° C.; 700° C. to 800° C.; 800° C. to 900° C.; 900° C. to 1000° C.; or 1000° C. to 1100° C. In various implementations, reactors/reactor systems can operate at no less than 700° C.; no less than 800° C.; no less than 900° C.; or no less than 1000° C. In various implementations, reactors/reactor systems can operate at no more than 1100° C.; no more than 1000° C.; no more than 900° C.; or no more than 800° C.

Reactors/reactor systems disclosed herein typically operate at pressures of 0.1 atm to 80 atm. In various implementations, reactors/reactor systems can operate at 0.1 atm to 60 atm; 0.5 atm to 50 atm; 0.5 atm to 5 atm; 1 atm to 40 atm; 2 atm to 30 atm; 5 atm to 20 atm; 10 atm to 15 atm; 1 atm to 20 atm; 20 atm to 40 atm; or 40 atm to 60 atm. In various implementations, reactors/reactor systems can operate at no less than 0.1 atm; no less than 0.5 atm; no less than 1 atm; no less than 5 atm; no less than 10 atm; no less than 20 atm; no less than 30 atm; no less than 40 atm; or no less than 50 atm. In various implementations, reactors/reactor systems can operate at no more than 60 atm; no more than 50 atm; no more than 40 atm; no more than 30 atm; no more than 20 atm; no more than 10 atm; no more than 5 atm; no more than 2 atm; no more than 1 atm; or no more than 0.5 atm.

In one reactor system configurations, such as that shown schematically in FIG. 1, each reactor in the system has constant or near constant mole ratios of reducing gas to oxidant, defined as x₁. At typical steady state operation, x₁ is less than 10⁶ and greater than 10⁻⁶.

In two reactor system configurations, such as that shown schematically in FIG. 2, each reactor in a first reactor system has constant or near constant mole ratios of reducing gas to oxidant, defined as x₁, and each reactor in a second reactor system has constant or near constant mole ratios of reducing gas to oxidant, defined as x₂. At typical steady state operation, x₂ is less than x₁, and x₁ and x₂ are less than 10⁶ and greater than 10⁻⁶. The mole ratios will be such that x₁ represents a net reducing gas based on the metal oxide phase present in the first reaction system. This can be determined based on the phase diagram of the metal oxide similar to the example mentioned in FIG. 8 and FIG. 9. Similarly, x₂ represents a net oxidizing gas to the metal oxide phase present in the second reaction system.

In implementations with more than two reactor system configurations, each reactor in each reactor system has constant or near constant mole ratios of reducing gas to oxidant, defined as x₁, x₂, x₃ . . . ‘x_n’ a first reactor system has constant or near constant mole ratios of reducing gas to oxidant, defined as x₁, and the second reactor system has constant or near constant mole ratios of reducing gas to oxidant, defined as x₂ and so on till the n^th reactor system that has constant or near constant mole ratios of reducing gas to oxidant, defined as x_n. At typical steady state operation, there are m number of streams, such that m<n, where x₁ to x_m streams are net reducing in nature and x_m+1 to x_n are net oxidizing in nature with respect to the solid phase present in the reaction system. The nature of the stream (reducing or oxidizing) can be determined based on the phase diagram of the metal oxide similar to the example mentioned in FIG. 8 and FIG. 9, where x₁ to x_n are less than 10⁶ and greater than 10⁻⁶ in all these reaction systems.

The various mole ratios mentioned above can be procured from natural sources or combined on-site or off-site to produce the desired compositions for the reaction systems. Some examples of natural sources for such gases include natural gas with x=0.9-0.99, biogas with x=0.3-0.7 etc.

D. Exemplary Reducing Gases and Oxidant

Various reducing gases and oxidizing gases can be used in exemplary systems and methods disclosed herein. For instance, reducing gases can include: natural gas, which can include methane (CH₄), H₂, CO, and mixtures thereof. Example oxidant includes CO₂, steam (H₂O), and mixtures thereof.

E. Exemplary Metal Oxides

Reactors in example systems disclosed herein include metal oxides/metal alloys. These metal oxides/metal alloys act as oxygen carriers that can undergo reduction/oxidation reactions with gaseous reducing agents, such as methane, and oxidizing agents, such as CO₂ or H₂O. In some instances, the metal oxides are provided in powder form. In some instances, the powder form has an average particle size between 150 μm and 250 μm. The metal oxides can also be in pellet form of various shapes with largest dimensions up to 3 mm.

Certain design considerations for metal oxides include reactivity, recyclability and mechanical strength, along with the oxygen carrying capacity. Transition metal oxides such as iron oxide, nickel oxide, copper oxide can be used as active oxygen carriers and have high oxygen carrying capacity, good reactivity and low cost among all the transition metal oxide candidates.

The recyclability of active metal oxide oxygen carriers can be promoted by adding supportive oxides which affect lattice oxygen ion diffusivity. The support material can be any support material known and used in the art. Non-limiting examples of support materials include, but are not limited to, silica, alumina, ceria, titania, zirconia, or a combination comprising two or more of the aforementioned supports, such as MgAl₂O₄. The amount of support material can vary from 20%, 30% 40%, 50%, 60%, 70%, 80% or any value in between.

Metal oxide reactivity can be enhanced by low concentration dopant modification. 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. It is thought that these transition metal dopants play three roles in reactivity enhancement of cyclic chemical looping redox reactions: (1) providing extra reaction sites during CO₂ and CH₄ conversion in addition to the host transition metal oxides such as iron oxides, cobalt oxides, nickel oxides, copper oxides and manganese oxides; (2) the nature of aliovalent dopants, such as Cu²⁺, Co²⁺, Ni²⁺ vs Fe³⁺, results in an increase of oxygen vacancies which promotes oxygen ion transport in methane partial oxidation; and (3) these catalytic dopants can lower reaction energy barriers of CO₂ and CH₄ activation with the host transition metal oxide materials such as FeO, FeTiO₃, FeAl₂O₄, CoTiO₃, etc.

III. Example Methods of Operation

Broadly, example methods disclosed and contemplated herein involve operating systems described above.

A. Example Methods of Operating Configurations with One Reactor System

FIG. 3 shows example method 400 for operating a reactor system. Method 400 involves operation of a single reactor or a group of reactors operating under the same or similar conditions. Other embodiments can include more or fewer operations.

Prior to steady-state operation, one or more start-up operations may take place. For instance, reactors in the system may be heated to desired temperatures and operating pressures. Typically, the reactors in the system are heated to a temperature between 700° C. and 1100° C. In some instances, the reactors in the system are heated to a temperature between 800° C. and 1050° C. Typically, the reactors in the system are operated at a pressure between 0.1 atm and 80 atm. In some instances, the reactors in the system are operated at a pressure between 0.5 atm and 5 atm

As another example, a value or range of values for a target mole ratio of reducing gas to oxidant may be determined (operation 402). Metal oxide oxygen content is also measured (operation 404) before steady-state operation. The oxygen content of the metal oxide can be monitored in-situ by keeping track of the oxygen in the inlet and the outlet stream of the reactor system. Through an oxygen balance, any accumulation or removal of oxygen from the metal oxide can be estimated. Alternatively and additionally, if a provision for solid sampling is present in the reaction system, the oxygen content can be measured by using one or more devices known in the art.

In some instances, metal oxide is in a powder form. The average particle size of the metal oxide powder can be between 150 μm and 250 μm. Typically, metal oxide is of the form Fe_xM_yO_z. In some instances, M is titanium (Ti) or nickel (Ni). In some instances, M is nickel (Ni) and cobalt (Co). The metal oxide can be supported on MgAl₂O₄.

An input stream is also provided to the reactor system (operation 406). The input stream receives a reducing gas stream including reducing gas and an oxidant stream including oxidant. An example reducing gas is natural gas, which can include methane (CH₄). An example oxidant includes CO₂ and/or steam (H₂O). A set of mass flow controllers may be used to adjust the mole ratio in the input stream to the desired mole ratio value or range of mole ratio values.

The oxygen content of the reactor system output stream is also measured (operation 408). Measuring the oxygen content can be performed at one or more locations downstream of the reactor system. Measurements can be obtained continuously or at periodic intervals, such as, for instance, every 1 second, every 2 seconds, every 5 seconds, every 10 seconds, every 20 seconds, every 30 seconds, every 1 minute, every 2 minutes, every 5 minutes, every 10 minutes, every 15 minutes, every 20 minutes, every 30 minutes, or every 60 minutes.

The oxygen content of the input stream is also measured (operation 410). Measuring the oxygen content can be performed at one or more locations upstream of the reactor system. Measurements can be obtained continuously or at periodic intervals, such as, for instance, every 1 second, every 2 seconds, every 5 seconds, every 10 seconds, every 20 seconds, every 30 seconds, every 1 minute, every 2 minutes, every 5 minutes, every 10 minutes, every 15 minutes, every 20 minutes, every 30 minutes, or every 60 minutes.

Next, a percent oxygen depletion is calculated (operation 412) for the reactor system. The percent oxygen depletion can be calculated by dividing the difference of the oxygen (O) in the outlet stream and the input stream by the oxygen (O) content in the metal oxide before startup. This calculation can be expressed as the following formula:

$\mathrm{Percent}O\mathrm{depletion}=\frac{\begin{array}{c}O\mathrm{content}\mathrm{in}\mathrm{outlet}\mathrm{stream}-\\ O\mathrm{content}\mathrm{in}\mathrm{input}\mathrm{stream}\end{array}}{\mathrm{inital}O\mathrm{content}\mathrm{of}\mathrm{metal}\mathrm{oxide}}\times 100\%$

Based on the oxygen depletion calculated in operation 412, a determination is made whether the percent oxygen depletion is above a threshold (operation 414). The threshold can be predetermined. Example thresholds include, but are not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%.

When it is determined that the percent oxygen depletion is not above the threshold, then method 400 can return to monitor the oxygen content of the output stream (operation 408) and input stream (operation 410).

When it is determined that the percent oxygen depletion is above the threshold, the reducing gas to oxidant mole ratio is adjusted (operation 416). Adjusting the reducing gas to oxidant mole ratio can include actuating one or more flow controllers for a reducing gas stream and for an oxidant stream. In some implementations, two mixed streams are available, where each stream has a different mole ratio of reducing gas to oxidant, and one or more flow controllers actuate the relative amounts of each stream as the input stream.

For instance, the threshold for O depletion will be estimated based on pre-determined information of the metal oxide system. This information is related to the kinetics of the gas-solid reactions based on the phases that are generated during O depletion of the metal oxide. For instance, if the O depletion threshold is defined at 10%, upon reaching this threshold, the gas composition will be adjusted to ensure the O content of the metal oxide and thus the desired solid phases are maintained in the reaction system. This adjustment can be achieved by adjusting the reducing gas to oxidizing gas ratio based on the reducing and oxidizing kinetics of the gas-solid system. The adjustment will vary with metal oxide system, gas composition, pressure, temperature gas flow rate, gas hourly space velocity of the reaction system, etc.

After adjusting the mole ratio of reducing gas to oxidant, method 400 can return to monitor the oxygen content of the output stream (operation 408) and input stream (operation 410).

The mole ratio of the input stream may also have to be adjusted if there is an indication of carbon deposition on the metal oxide surface. Carbon deposition can be monitored by measuring the carbon accumulation in the reactor system by looking at the compositions of the input and the out streams. These compositions can be measured using one or more devices known in the art.

B. Example Methods of Operating Configurations with Two or More Reactor Systems

FIG. 4 shows example method 500 for operating a reactor system. Method 500 involves operation of a two or more reactor systems, where each reactor system can include one or more reactors operating under the same or similar conditions. Other embodiments can include more or fewer operations.

Prior to steady-state operation, one or more start-up operations may take place. Ranges of operating temperatures and pressures are the same as those described above with reference to method 400, and will not be repeated here for purposes of brevity.

Method 500 also includes determining a first mole ratio and a second mole ratio (operation 502). The first mole ratio of reducing gas to oxidant, x₁, is for the first reactor system. The second mole ratio of reducing gas to oxidant, x₂, is for the second reactor system. In implementations with more than two reactor systems, mole ratios for each reactor system are also determined.

Metal oxide content is also measured (operation 504) before startup. Typically, the same metal oxide is used in each reactor system. The oxygen content of the metal oxide can be monitored in-situ by keeping track of the oxygen in the inlet and the outlet stream of the reactor system. Through an oxygen balance, any accumulation or removal of oxygen from the metal oxide can be estimated. Alternatively and additionally, if a provision for solid sampling is present in the reaction system, the oxygen content can be measured by using one or more devices known in the art. Exemplary metal oxides are described above with reference to method 400, and will not be repeated here for purposes of brevity.

Input streams are also provided to each reactor system (operation 506). Exemplary aspects of the input stream are described above with reference to method 400 and system 200, and will not be repeated here for purposes of brevity.

The oxygen content of each reactor system output stream is measured (operation 508), and the oxygen content of each reactor system input stream is measured (operation 510). Exemplary aspects of oxygen content measuring are described above with reference to method 400 and system 200, and will not be repeated here for purposes of brevity.

Next, a percent oxygen depletion is calculated (operation 512) for each reactor system. As described in greater detail above, calculating percent oxygen depletion for each reactor system can be expressed as the following formula:

$\mathrm{Percent}O\mathrm{depletion}=\frac{\begin{array}{c}O\mathrm{content}\mathrm{in}\mathrm{outlet}\mathrm{stream}-\\ O\mathrm{content}\mathrm{in}\mathrm{input}\mathrm{stream}\end{array}}{\mathrm{inital}O\mathrm{content}\mathrm{of}\mathrm{metal}\mathrm{oxide}}\times 100\%$

Based on the oxygen depletion calculated in operation 512, a determination is made whether the percent oxygen depletion in a given reactor system is above a threshold (operation 514). The threshold can be predetermined. Example thresholds include, but are not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%.

When it is determined that the percent oxygen depletion is not above the threshold, then method 400 can return to monitor the oxygen content of the output stream (operation 408) and input stream (operation 410).

When it is determined that the percent oxygen depletion is above the threshold, the reducing gas to oxidant mole ratio is adjusted (operation 416). Adjusting the reducing gas to oxidant mole ratio can include actuating one or more flow controllers for a reducing gas stream and for an oxidant stream. In some implementations, two mixed streams are available, where each stream has a different mole ratio of reducing gas to oxidant, and one or more flow controllers actuate the relative amounts of each stream as the input stream.

As an example, when the operating conditions have a high ratio of reducing gas to oxidant, reaction kinetics may lead to a higher degree of carbon formation through the reactor system. This is typically characterized by a breakthrough curve, wherein after a given amount of time, the amount of unconverted reducing gas in the output stream will start to increase. In such a kinetically controlled operating regime, it can be useful to switch over to a lower mole ratio of oxidant to the reducing gas to mitigate the carbon formation before switching back to the original input feed condition.

An example representation of this variation in operation condition could involve periodic swinging for all reactors in the reactor system. Specifically, in one type of swing, reactors in both systems could be simultaneously alternated between two different mole ratios. As one example, each reactor system could operate at a different mass ratio simultaneously, which could then be switched depending on the degree of kinetic control desired. As another example, a first reactor system is operated at the relatively highest mole ratio and a second reactor system is operated at a lower mole ratio. For systems with more than two reactor systems, one reactor system can operate at the highest mole ratio, one reactor system at the lowest mole ratio, and the other reactor systems operate at stepped down values between the high and low mole ratios.

After adjusting the mole ratio of reducing gas to oxidant, method 400 can return to monitor the oxygen content of the output stream (operation 408) and input stream (operation 410).

IV. Experimental Examples

Various aspects of the systems and methods were experimentally evaluated. Without limitation, those experiments and the results are discussed below.

A. Thermodynamic Calculations for Example Systems

This section discusses thermodynamic calculation results of example systems obtained using ASPENPLUS v10 (Aspen Technology, Inc., Bedford, Mass.) and compares the syngas production performance of the example systems to conventional steam methane reforming process. The simulation results obtained in this section are based on the principle of Gibbs free energy minimization. The example system has been investigated under different temperatures, pressures, and using various metal oxide materials. Two operating modes, namely constant feedstock mode and alternating feedstock mode, have been investigated.

The first set of thermodynamic calculations were conducted using the constant feedstock operating mode under 1000° C., 10 atm. FeTiO₃ was used as the metal oxide material in the fixed bed. CH₄, CO₂ and H₂O were co-injected into the fixed bed reactor to react with FeTiO₃. While CH₄ continuously extracted oxygen from FeTiO₃, the oxygen vacancy was immediately filled by H₂O and CO₂. High purity syngas is generated without overall change in FeTiO₃ oxidation state. The system performance of case 1 is summarized in Table 1, below.

TABLE 1
Performance of the SP system using FeTiO3 at 1000° C., 10 atm.
Operation mode    Constant feedstock
Temperature, ° C. 1000
Pressure, atm     10
Feedstock         CH4, H2O, CO2
                  (H2O/CH4 = 1.15, CO2/CH4 = 0.45)
CH4 conversion, % 97
Syngas yield,     3.89
(H2 + CO) out/CH4 in
Syngas purity, %  95

Definitions of CH₄ conversion, syngas yield and syngas purity are given below:

${\mathrm{CH}}_4\mathrm{conversion}=\left(1-\frac{\mathrm{unreacted}{\mathrm{CH}}_4\mathrm{in}\mathrm{syngas}\mathrm{product}}{\mathrm{total}{\mathrm{CH}}_4\mathrm{feedstock}}\right)\times 100\%$ $\mathrm{syngas}\mathrm{yield}=\frac{H_2+\mathrm{CO}}{\mathrm{total}{\mathrm{CH}}_4\mathrm{feedstock}}$ $\mathrm{syngas}\mathrm{purity}=\left(\frac{H_2+\mathrm{CO}}{\mathrm{total}\mathrm{syngas}\mathrm{excluding}{H}_{2}O}\right)\times 100\%$

The second set of thermodynamic calculations were conducted using alternating feedstock under 1000° C., 30 atm. FeO and Fe₂SiO₄ were used as the metal oxide material in the fixed bed simulation. As previously mentioned, the gaseous feedstock was switched between a reducing gas mixture mainly composed of CH₄ (stage I), and an oxidizing gas mixture containing mostly H₂O (stage II). During stage I, CH₄ was partially oxidized into syngas while the metal oxide material was reduced to a lower oxidation state. In stage II, the reduced metal oxide was oxidized by H₂O or CO₂ back to its original oxidation state while producing H₂ or CO.

By separating the operation into two distinct phases, the system thermodynamics of the alternating feedstock operating mode can be fundamentally different from the gaseous phase reactions of conventional steam methane reforming. One difference can be shown in the following case studies.

Two case studies were conducted under 1000° C. and 950° C., respectively, under 30 atm. In each case study, three different systems were simulated and compared. The first system was an FeO—Fe based system. The second system was an Fe₂SiO₄—Fe based SP system. The third system was the conventional SMR system serving as a basis for comparison. The parameters compared between the three systems include CH₄ conversion, syngas yield, and syngas purity, as defined in the equations given above.

FIG. 5 and FIG. 6 show the comparison of methane conversion of the two example systems and the steam methane reforming (SMR) system under 30 atm, 1000° C. and 950° C., respectively. The x-axis of each graph is the H₂O/CH₄ ratio fed into the reactor. For the example systems, the H₂O injection is a sum of the total H₂O injection of the two operating stages. CH₄ conversion for the example systems was calculated based on the total syngas produced from the two stages.

As illustrated in FIG. 5 and FIG. 6, as H₂O/CH₄ ratio increases, the CH₄ conversion keeps increasing for all the three systems. However, the trends of the three systems follow different profiles. For a certain H₂O/CH₄ range, the example systems show a higher CH₄ conversion than the conventional SMR system, as indicated by the shaded areas in the graphs. If the example system is operated in the shaded area, the CH₄ conversion of the overall example process will be higher than the conventional SMR process.

A comparison between the example system using FeO as the metal oxide material with the SMR system operating using the same amount of feedstock (CH₄ and H₂O) was also conducted. The operating point is indicated by a black dot on FIG. 6. The results are shown in table 2, below.

TABLE 2
Comparison between SP system using FeO and conventional SMR
		Example system,	Conventional
	Case	FeO	SMR system
	CH4 input, kmol/hr	1	1
	H2O input, kmol/hr	3.33	3.33
	H2 product, kmol/hr	3.20	3.11
	CO product, kmol/hr	0.67	0.65
	CH4 conversion, %	95.7	93.9
	Syngas yield, %	3.87	3.75
	Syngas purity, %	92.2	91.4

As shown in the table, by using equal amount of feedstock, the example system is able to achieve higher CH₄ conversion, syngas yield, and syngas purity than the SMR process.

B. Kinetic Aspects of Example Systems

This section discusses kinetic aspects of example metal oxide interaction with CH₄ as the reducing gas and CO₂ as the oxidizing gas over Fe/FeTiO₃ as an example metal oxide.

FIG. 7 shows the solid conversion profile under CH₄ reduction of FeTiO₃ with 0% depicting FeTiO₃ and 100% depicting Fe+TiO₂ solid phase. FIG. 7 also highlights differences in reactivities as the reduction proceeds, indicating a change in reaction kinetics with phase change of the metal oxide. These phase change characteristics are absent in conventional catalytic systems, thus providing additional degrees of freedom for the proposed process. These rates also help define the operating conditions for the system and can be considered for the bed preparation step, which may be necessary to attain a suitable starting composition.

Performance of exemplary metal oxide was tested in a U-tube fixed bed reactor. Methane/carbon dioxide (CH₄/CO₂) ratios ranging from 0.8 to 9 were tested as feed to the reactor with a total gas flow of 20 ml/min. The reactant gas conversion and product purity were calculated based on gas analysis in a mass spectrometer. The solids were initially reduced under a gas mixture with a mole ratio of CH₄ to CO₂ of 9 for 15-20 min, to achieve a suitable starting composition. Table 3 shows the gas analysis for Fe—Ti oxide of particle size 150-250 microns at 1000° C.

TABLE 3
Experimental results for Fe-Ti system in a U-tube fixed bed reactor
CH4/CO2	CH4	CO2	Dry syngas	H2/CO
in feed	conversion	conversion	purity	ratio
1.5	>95%	>99.5%	>98%	1.47

The gas analysis for a Ni-doped Fe oxide supported on MgAl₂O₄ is shown in Table 4. The powder size was between 150-250 microns and the reaction temperature was 1000° C.

TABLE 4
Experimental results for Ni doped Fe oxide-
MgAl2O4 system in a U-tube fixed bed reactor
CH4/CO2	CH4	CO2	Dry syngas	H2/CO
in feed	conversion	conversion	purity	ratio
0.8	>99.5%	>92%	>97%	0.86

These reactant conversion and syngas purity values for the two metal oxides tested were steady for a period of over 2 hours, depicting negligible drop-in activity throughout that time.

C. Stratification Analysis of Example Systems

This section discusses stratification for exemplary systems. More specifically, the stratification analysis was for a nickel (Ni)-doped Fe oxide supported on MgAl₂O₄ in a U-tube reactor, and the results are shown in Table 5.

TABLE 5
Oxygen content of an exemplary metal oxide across
the bed in a U-tube fixed bed reactor
Layer number (1:inlet and 4:outlet) Percent (%) oxygen content
1                                44.78
2                                35.06
3                                35.64
4                                33.11

This metal oxide of powder size between 150-250 microns was reacted with a CH₄/CO₂ mixture at temperature of 1000° C. and 1 atm pressure. Experimental results are summarized in Table 6.

TABLE 6
Gas phase product results for Ni doped Fe oxide
supported on MgAl2O4 in a U-tube reactor
CH4/CO2	CH4	CO2	Dry syngas	H2/CO	(H2 + CO)/
in feed	conversion	conversion	purity	ratio	CH4
0.67	>99.5%	>86.5%	>93.5%	0.66	3.07

The metal oxide bed was segregated into 4 layers to investigate the change in oxidation state across the bed. The oxygen content represents the amount of active lattice oxygen that the metal oxide contains. This oxygen content value was estimated by oxidation studies on a thermogravimetric analyzer. Evidently, the oxygen content decreases from the inlet of the bed to the outlet of the bed. These data appear to be evidence of bed stratification and thus of a different reaction mechanism than the traditional catalytic process.

D. Example Metal Oxide Pre-Treatment

Pre-treatment of exemplary metal oxide was also investigated. Pre-treatment of the metal oxide appears to influence the desired oxidation state of the metal oxide. The kinetic equilibrium between the output stream (including product gas) and the stratified solid metal oxide appears directed related to the solid phase present in the reactor. FIG. 7 depicts the different reduction kinetics of FeTiO₃, indicating regions of high and low CH₄ conversion. The pre-treatment drives the equilibrium towards the high conversion region, thus improving the per pass syngas yield.

Table 7 shows the difference in the performance parameters for the syngen process with and without pre-treatment.

TABLE 7
Experimental results showing effect of pre-treatment on syngas generation.
Pre-	CH4/CO2	CH4	CO2	Dry syngas	H2/CO	(H2 + CO)/
treatment?	in feed	conversion	conversion	purity	ratio	CH4
No	0.74	25.63%	44.1%	35.09%	0.31	0.63
Yes	0.74	79.3%	99.5	92.29%	1.1	2.5

For the data in Table 7, the pre-treatment was carried out in a reducing environment to achieve a metallic iron rich solid phase. These results have been shown to be stable for up to 60 hours of operation, which is evidence of the stability of the kinetic equilibrium and the solid metal oxide phase.

E. Parametric Studies of Exemplary Processes

Effects of gas hourly space velocity (GHSV) and operating pressure were evaluated for an experimental, fixed bed U-tube reactor. Results are discussed below.

Experiments were conducted evaluating the effect of gas hourly space velocity (GHSV) for an Ni-doped Fe oxide supported on MgAl₂O₄. The CO₂:CH₄ ratio was constant at 1.5 with the reaction conducted at 1000° C. and 1 atm. Table 8 shows the change in product composition with the increase in GHSV.

TABLE 8
Effects of GHSV on an Ni doped Fe oxide at CO2:CH4 = 1.5
GHSV	CH4	CO2	Dry syngas	H2/CO	(H2 + CO)/
(min−1)	conversion	conversion	purity	ratio	CH4
12.74	99.93	80.92	93.49	0.91	4.12
25.48	99.96	82.49	93.72	0.83	3.93
63.69	98.86	82.56	93.36	0.81	4.08

The example system does not show a strong correlation with GHSV, thus indicating the flexibility and improved turndown ratio for the example system.

To evaluate the effect of operating pressure, dual doped material was synthesized to attain higher CO₂ conversions at higher pressures. This metal oxide included Co and Ni doped in a Fe based oxide with MgAl₂O₄ support. This metal oxide was investigated at a temperature of 1000° C. and pressures of 1 and 5 atm at CO₂ to CH₄ ratio of 1.5. Between 1 and 5 atm, the GHSV at reaction conditions was kept the same by increasing the standard volumetric flow rate proportional to the increase in pressure. The experimental data for these runs has been depicted in Table 9. The efficiency of the example dual doped material is highlighted from a high syngas yield of 3.94 per mole of CH₄ at 5 atm.

TABLE 9
Effects of operating pressures on
an example system at CO2:CH4 = 1.5
Pressure	CH4	CO2	Dry syngas	H2/CO	(H2 + CO)/
(atm)	conversion	conversion	purity	ratio	CH4
1	99.84	83.89	93.99	0.78	3.8
5	95.68	80.90	92.28	0.77	3.94

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. Example 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. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

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.

The modifier “about” used in connection with a quantity is 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 particular quantity). The modifier “about” 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.

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, 75^th Ed., inside cover, and specific functional groups are generally defined as described therein.

For the recitation of numeric ranges herein, each intervening number there between with the same degree of precision is explicitly 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 number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly contemplated. For example, when a pressure range is described as being between ambient pressure and another pressure, a pressure that is ambient pressure is expressly contemplated.

Claims

1. A method for operating a reactor system, the method comprising: providing an input stream to the reactor system, the input stream including a reducing gas stream and an oxidant stream;determining an initial oxygen content of a metal oxide in the reactor system;measuring an oxygen content of the input stream;measuring an oxygen content of an output stream from the reactor system;calculating a percent oxygen depletion of the metal oxide using the initial oxygen content of the metal oxide, the oxygen content of the input stream, and the oxygen content of the output stream; andwhen the percent oxygen depletion of the metal oxide is above a predetermined threshold between 5% and 15%, adjusting a mole ratio of reducing gas to oxidant in the input stream.

2. The method according to claim 1, wherein the reducing gas stream includes natural gas.

3. The method according to claim 1, wherein the oxidant stream includes H2O.

4. The method according to claim 3, wherein the oxidant stream includes CO2.

5. The method according to claim 1, further comprising operating the reactor system at a steady state mole ratio of reducing gas to oxidant that is less than 106 and more than 10−6.

6. The method according to claim 1, further comprising operating the reactor at a temperature 700° C. and 1100° C.

7. The method according to claim 6, wherein the temperature is between 800° C. and 1050° C.

8. The method according to claim 1, further comprising operating the reactor at a pressure between 0.1 atm and 80 atm.

9. The method according to claim 8, wherein the pressure is between 0.5 atm and 5 atm.

10. The method according to claim 1, wherein the metal oxide is of the form FexMyOz.

11. The method according to claim 10, wherein M is titanium (Ti) or nickel (Ni).

12. The method according to claim 10, wherein Mis nickel (Ni) and cobalt (Co).

13. The method according to claim 10, wherein the metal oxide is supported on MgAl2O4.

14. The method according to claim 1, wherein the metal oxide is in powder form.

15. The method according to claim 14, wherein the powder form has an average particle size between 150 μm and 250 μm.

16. The method according to claim 1, wherein the output stream includes CO and H2.

17. A method for operating a reactor system, the method comprising: providing a first input stream to a first reactor assembly in the reactor system, the first input stream including reducing gas and oxidant;determining an initial oxygen content of a first metal oxide in the first reactor assembly;measuring a first input stream oxygen content;measuring an oxygen content of an output of the first reactor assembly;calculating a percent oxygen depletion of the first metal oxide using the initial oxygen content of the first metal oxide, the first input stream oxygen content, and the oxygen content of the output of the first reactor assembly;when the percent oxygen depletion of the first metal oxide is above a first predetermined threshold between 5% and 15%, adjusting a mole ratio of reducing gas to oxidant in the first input stream;providing a second input stream to a second reactor assembly in the reactor system, the second input stream including reducing gas and oxidant;determining an initial oxygen content of a second metal oxide in the second reactor assembly;measuring a second input stream oxygen content;measuring an oxygen content of an output of the second reactor assembly;calculating a percent oxygen depletion of the second metal oxide using the initial oxygen content of the second metal oxide, the second input stream oxygen content, and the oxygen content of the output stream; and

18. The method according to claim 17, wherein the first reactor assembly includes at least two reactors, wherein the second reactor assembly includes at least two reactors, and further comprising: operating each reactor in the first reactor assembly to have a first target mole ratio of reducing gas to oxidant between 106 and 10−6; andoperating each reactor in the second reactor assembly to have a second target mole ratio of reducing gas to oxidant between 106 and 10−6, wherein the first target mole ratio of reducing gas to oxidant is different from the second target mole ratio of reducing gas to oxidant.

19. The method according to claim 17, wherein the first input stream is in communication with a reducing gas source and an oxidant source; and wherein the first input stream includes at least one flow regulation device arranged to modify a ratio of flow from the reducing gas source and the oxidant source.

20. The method according to claim 17, wherein the first input stream is in communication with a first supply source and a second supply source, the first supply source having a first predetermined ratio of reducing gas to oxidant between 0.9 and 0.99; and the second supply source having a second predetermined ratio of reducing gas to oxidant between 0.9 and 0.99.

21. The method according to claim 17, further comprising: providing a third input stream to a third reactor assembly in the reactor system, the third input stream including reducing gas and oxidant;determining an initial oxygen content of a third metal oxide in the third reactor assembly;measuring a third input stream oxygen content;measuring an oxygen content of an output of the third reactor assembly;calculating a percent oxygen depletion of the third metal oxide using the initial oxygen content of the third metal oxide, the third input stream oxygen content, and the oxygen content of the output stream; andwhen the percent oxygen depletion of the third metal oxide is above a third predetermined threshold between 5% and 15%, adjusting a mole ratio of reducing gas to oxidant in the third input stream.

22. The method according to claim 21, wherein the third reactor assembly includes at least two reactors, and further comprising: operating each reactor in the third reactor assembly to have a third target mole ratio between 106 and 10−6 of reducing gas to oxidant,