Carbon formation chemical looping using oxygen

Abstract

A process of integrating heat in a reaction includes performing an exothermic reaction, generating heat and products in response to performing the exothermic reaction, transferring the heat to an endothermic reaction, and performing the endothermic reaction in response to the heat from the exothermic reaction. In addition, a reaction system includes an exothermic reactor configured to perform an exothermic reaction, an endothermic reactor configured to perform an endothermic reaction, and a heat exchange surface configured to transfer heat from the exothermic reaction to the endothermic reaction.

Description

CARBON FORMATION CHEMICAL LOOPING USING OXYGENCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 509,720 filed on June 22, 2023 and entitled “CARBON FORMATION CHEMICAL LOOPING USING OXYGEN,” the entire disclosure of which is incorporated herein by reference.STATEMENT REGARDING GOVERNMENTALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] None.BACKGROUND

[0003] Industrial hydrogen can be produced primarily by reacting hydrocarbon feedstocks (e.g. CH4, naphtha, biomass, coal, etc) with oxy gen-containing species (e.g. O2, H2O, CO2) to produce a desired mixture of H2, CO2, and H2O. Overall the carbon input to the system exits as CO2, which is typically released to the environment or, in future scenarios, geologically sequestered. This results in significant additional costs resulting from CO2 handling and sequestration process costs, a carbon tax, or a negative externality on society (e.g., climate change).SUMMARY

[0004] In some embodiments, a process of integrating heat in a reaction comprises performing an exothermic reaction, generating heat and products in response to performing the exothermic reaction, transferring the heat to an endothermic reaction, and performing the endothermic reaction in response to the heat from the exothermic reaction.

[0005] In some embodiments, a reaction system comprises: an exothermic reactor configured to perform an exothermic reaction, an endothermic reactor configured to perform an endothermic reaction, and a heat exchange surface configured to transfer heat from the exothermic reaction to the endothermic reaction.

[0006] In some embodiments, a process of integrating heat in a carbon formation reaction comprises: reacting a feed stream comprising a hydrocarbon and at least one carbon oxide to form solid carbon, generating heat and gaseous products in response to forming the solid carbon, transferring the heat to an endothermic reaction, and performing the endothermic reaction in response to the heat from forming the solid carbon.

[0007] These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings and claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] For a more complete understanding of the present disclosure, reference is now made to the following brief description, taken in connection with the accompanying drawings and detailed description:

[0009] FIG. 1 schematically illustrates a carbon formation system according to some embodiments.

[0010] FIG. 2 schematically illustrates another carbon formation system according to some embodiments.

[0011] FIG. 3 schematically illustrates still another carbon formation system according to some embodiments.

[0012] FIG. 4 schematically illustrates an integrated carbon formation reactor according to some embodiments.

[0013] FIG. 5 schematically illustrates a carbon formation system according to some embodiments.

[0014] FIG. 6 schematically illustrates another carbon formation system according to some embodiments.

[0015] FIGS. 7A and 7B illustrate heat exchanger reactors using direct heat exchange according to some embodiments.DETAILED DESCRIPTION

[0016] Industrial hydrogen can be produced primarily by reacting hydrocarbon feedstocks (e.g. CH4, naphtha, biomass, coal, etc) with oxy gen-containing species (e.g. O2, H2O, CO2) to produce a desired mixture of H2, CO2, and H2O. Overall the carbon input to the system exits as CO2, which is typically released to the environment or, in future scenarios, geologically sequestered. This results in significant additional costs resulting from CO2 handling and sequestration process costs, a carbon tax, or a negative externality on society (e.g., climate change).

[0017] In order to address the issues with hydrogen production and the concurrent production of carbon dioxide, various forms of hydrocarbon reactions can be carried out to shift the carbonaceous product to solid carbon. This can be accomplished via several different reaction pathways including:CH4 ^ C + 2 H2 AH0= 76 kJ / mol CH4 (pyrolysis)2 CO C + CO2 AH0= -86 kJ / mol CO (Boudouard reaction)CO + H2^ C + H2O AH0= -175 kJ / mol CO (CO reduction)

[0018] When C, H, and O are present, other reactions including water gas shift (WGS), reverse water gas shift (rWGS), methanation, and hydrocarbon reforming will be occurring to shift the composition towards thermodynamic equilibrium. The carbon forming reactions tend to be either strongly endothermic or strongly exothermic, requiring continuous heat addition or removal from the reactor. This can be problematic as solid surfaces have a propensity to accumulate carbon when carbon formation reactions are occurring. Additionally, the large heat of reaction can reduce the overall thermal efficiency of the process by requiring large heat flows between streams. It is advantageous to have the net reaction within the carbon formation reactor be autothermal or exothermic to eliminate the need for heat addition / removal and increase thermal efficiency. The coupling of carbon formation reactions and / or the coupling of carbon formation reactions with other complementary reactions (e.g. reforming, rWGS, etc.) can be used to achieve this goal.

[0019] As disclosed herein, a system that uses hydrocarbons (e.g., light alkanes such as CH4, naphtha, biomass, ethanol, plant oils, crude oil, etc.) and oxygen containing compounds (e.g., O2, CO, and / or CO2) as feedstocks and produces predominantly C, H2O, and H2 can be designed to utilize a carbon formation reactor. The carbon formation reactor can generally operate as an exothermic reactor. Within the carbon formation reactor, solid carbon can be formed starting with CO as the carbonaceous species which is fed into the carbon formation reactor along with predominantly hydrocarbons (e.g., CH4, naphtha, biomass, ethanol, plant oils, crude oil. etc), oxygen, and / or carbon dioxide.

[0020] The exothermic carbon formation reaction can be coupled with an endothermic reaction during the process. The thermal coupling can allow for improved process efficiency as well as temperature control for the reactions occurring during the process. Within the overall process, various endothermic processes can be carried out. This can include reforming reactions such as steam methane reforming (SMR), dry methane reforming (DMR), reverse water gas shift (rWGS) reactions, and the like. It should be noted that the present systems and methods can be used with any endothermic reaction and is not limited to those described herein.

[0021] The thermal coupling of an exothermic reaction with an endothermic reaction can be carried out through direct or indirect heat exchange, and when indirect heat exchange is used, the heat exchange can be carried out in one or more heat exchangers. In some aspects, the heat available from a product stream of an exothermic reaction can be adjusted prior to supplying the heat to an endothermic reaction. As an example, a partial oxidation reactor can be used with the introduction of oxygen to carry out an exothermic oxidation reaction to add available heat fortransfer to a stream used in an endothermic reaction. These various configurations are described in more detail herein.

[0022] FIG. 1 illustrates a process flow diagram of a process for converting a hydrocarbon to hydrogen and solid carbon using the heat from a carbon formation reactor product stream to heat an adiabatic reformer feed stream. As shown, a process 100 can comprise a carbon formation reactor 132 having an outlet gas heat exchanger 121 that can provide heat to a reformer 122 feed gas. The heated reformer feed gas can then react in the reformer 122 to produce products such as a hydrocarbon and CO that can be passed to and react in the carbon formation reactor 132.

[0023] Within the system 100, a stream 102 comprising a hydrocarbon can be passed to a preheater 103 to heat the hydrocarbon. The hydrocarbon in the hydrocarbon stream 102 can comprise any suitable hydrocarbon such as one or more light alkanes such as methane, ethane, natural gas, as well as other gaseous, liquid, and solid hydrocarbons (e.g. ethanol, crude oil, biomass, naphtha, etc.). In some aspects, a gasification reactor can be used to convert one or more hydrocarbon containing species into a gaseous stream. In some aspects, the hydrocarbon can be provided as a fluidized solid or other form.

[0024] Steam can be introduced in stream 104 and combined with the hydrocarbon before passing to a secondary preheater 105. The preheater 105 can be heated using any suitable source, and in some aspects, can be a fired heater. As an example, preheater 105 can be heated using hydrogen for stream 106 and oxygen 107 with the resulting flue gas stream comprising water and some amount of nitrogen. The use of hydrogen in stream 106 may help to avoid the production of CO2 in the flue gas stream. While shown as hydrogen in stream 106, in some aspects, a hydrocarbon source can also be used as fuel.

[0025] In some aspects, stream 107 can comprise an oxygen enriched stream. An oxygen enriched stream refers to any stream having an oxygen concentration greater than the atmospheric concentration of oxygen. The oxygen stream 107 can be obtained at a desired purity from an oxygen storage tank, or via an oxygen enrichment process, for example, the separation of air into nitrogen and oxygen, such as pressure swing adsorption (PSA), vacuum swing adsorption (V SA), or cryogenic separation techniques. The oxygen in the oxygen stream 107 may have at least about 70 vol%. at least 80 vol%, or at least 90 vol % oxygen (e.g., 90, 91, 92, 93, 94. 95. 96. 97. 98, 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9, or 100 vol % oxygen). The use of hydrogen and an oxygen enriched stream can result in the production of predominantly water in the flue gas stream.

[0026] The individual feed streams 102, 104 may be at any suitable pressure and temperature, and one or more heat exchangers (e.g., preheater 103, preheater 105, etc.) can be used to adjustthe temperature of the corresponding stream. The combined stream leaving the second preheater 105 may have a pressure between about 1 bar to about 50 bar, or between about 5 bar and about 20 bar, and a temperature between about 200°C to about 700°C, or betw een about 250°C to about 400.

[0027] A first portion 108 of the heated stream can be passed to a reformer 111. Some amount of oxygen in oxygen stream 110 can be combined with the heater hydrocarbon and steam in stream 108 before passing to the reformer 111. As with stream 107, the oxygen in stream 110 can be an oxygen enriched stream in some aspects.

[0028] V arious reforming reactions can be used in the reformer 111 to form carbon oxides such as CO and / or CO2 from the hydrocarbon, oxygen, and / or water so that the carbon oxides can be used within the carbon formation reactor 132. Any suitable reforming reactions can be used, and in some aspects, the reformer 111 may be used to carry out a steam methane reforming (SMR) reaction or a dry reforming of methane (DRM) reaction, each of which is an endothermic process.

[0029] In some aspects, the reformer 111 can be used to cany' out an SMR reaction. An SMR reaction can convert water and a hydrocarbon feed, with or without oxygen, to CO and H2. An exemplary SMR reaction using methane as an example can proceed according to the following:CH + H2O CO + 3H2When CO2 is introduced along with the hydrocarbon and water, some amount of dry reforming can also occur according to the following:CH4+ CO2 2CO + 2H2

[0030] As shown in FIG. 1, the SMR reaction can occur within the reformer 111, which can contain a catalyst to improve the reforming reaction rates. In some embodiments, the reformer section of the reactor 100 can comprise any suitable reactor, such as for example a tubular reactor, a multitubular reactor, fixed bed reactor, or the like, or combinations thereof. In some embodiment, the SMR reaction can take place in the presence of a catalyst such as a nickel-based catalyst (e.g., sulfur sensitive nickel-based catalyst) and / or a sulfur passivated nickel-based catalyst (to avoid carbon depositions). The reforming reaction for hydrocarbons such as methane can be endothermic, and a reaction rate depends on the temperature, pressure and catalyst type. The hydrocarbon can undergo the reforming reaction at high temperatures, however, in the presence of a catalyst (e g., nickel-based catalyst), the temperature at which the hydrocarbon can be reformed can be lowered. In some aspects, the SMR reaction can be carried out at a temperature between about 700 °C to about 1100 °C, or from about 800 °C to about 900 °C. Inan embodiment, the reformer can be characterized by a reforming pressure of from about 1 bar to about 30 bars.

[0031] In some aspects, the reformer can be used to carry out other types of reforming to form carbon oxides. In some aspects, the reforming reaction can function using the dry reforming of methane (DRM). Dry reforming of a hydrocarbon is an endothermic reaction that occurs according to the reaction:CH4+ CO2 2CO + 2H2, with a AH (at 1,000 °C of -265 kJ / mol)

[0032] The DRM reaction can be carried out in the reformer 111, which can contain a catalyst to improve the reforming reaction rates. When the DRM reaction is used, stream 110 may comprise CO2 with or without oxygen, and the feed to the reformer 111 may be free of water or substantially free of water. Exemplary catalysts can include supported or bulk catalyst containing Group VIII (Columns 8-10) metals that are catalytically active towards reforming reactions. By way of example, nickel, rhodium, ruthenium, or platinum or any combination thereof based catalysts can be used in dry methane reforming.

[0033] When a DRM reaction is carried out, the reaction conditions within the reformer 111 may include a pressure of between about 1 bar to about 50 bar, or between about 1 bar to about 20 bar, a temperature of about 750°C to about 1100°C, or between about 800°C to about 950°C, and a GHSV of about 500 h1to about 100,000 h '. In some embodiments, the hydrocarbon (e.g., methane, etc.) conversion in the reaction can be about 60% to about 80%. The hydrogen gas to carbon monoxide ratio (H2 / CO) in the product stream leaving the reformer 11 1 can range from about 0.5 to about 1. In addition, some amount of unreacted hydrocarbon gas and carbon dioxide can also be present depending on the overall conversion.

[0034] In some aspects, the reformer 111 can be operated as an adiabatic reformer without any heat input beyond that of the inlet streams, or the reformer 111 may be heated. The reformer 111 can also be operated as an autothermal reformer through the introduction of the oxygen in stream110. The reaction of the oxygen with the hydrocarbon can then generate heat within the reformer111. When any portion of the heat is supplied other than through the introduction of O2 into the reformer 111 or as part of the feed stream, the heat source may be generated using CO2 free sources such as through the combustion of hydrogen and / or using electrical sources. In some aspects when electrical heating is used, the electricity can be generated using green sources such as wind or solar generation.

[0035] The outlet stream 112 from the reformer 111 can be at the operating temperature of the reformer 111 of betw een about 700°C to about 1100°C. The outlet stream can pass through theexchanger 114 to cool the outlet stream 112. Exchanger 114 can serve, in some aspects, as a steam generator that can accept a feed water in stream 113 and generate steam in outlet stream 115. The outlet stream leaving the exchanger 114 can be cooled between about 200°C to about 400°C. The outlet stream can be further cooled in a second exchanger 116 to cool the outlet stream to condense at least a portion of any water in the stream. The stream can then be cooled to between 0°C to 50°C, or to less than 30°C in the condenser 116 to condense at least a portion of the water in the outlet stream. The condensed water can be removed as water stream 117. When higher levels of water removal are needed, additional or alternative units can be used such as glycol dehydrators and the like. The remaining stream can then comprise CO, CO2, H2, unreacted hydrocarbons, and trace amounts of water.

[0036] The remaining portions of stream can pass to a separator 118 where hydrogen can be separated to pass out of the system as outlet hydrogen stream 120. In some aspects, the separator 118 can comprise a PSA unit that can be used to separate at least a portion of the hydrogen from the product stream from condenser 116. While shown as a PSA unit, other suitable separation units such as temperature swing adsorption, membrane units, and the like can also be used to separate at least a portion of the hydrogen. In some aspects, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of the hydrogen (by volume) in the product stream from the condenser 116 can be separated in the separator 118 to form the outlet hydrogen stream 120 and a carbon formation stream having a reduced hydrogen concentration.

[0037] Returning to the second portion 109 of the heated stream, the second portion 109 can pass a heat exchanger 121 to be preheated prior to passing to a secondary reformer 122. The heat exchanger 121 can provide indirect heat exchange betw een the carbon formation reactor 132 outlet stream and the second portion 109 being passed into the secondary reformer 122. The second portion 109 of the heated stream passing through the second exchanger 121 may have a pressure between about 1 bar to about 50 bar, or between about 5 bar and about 20 bar, and a temperature between about 200 °C to about 700 °C. In some aspects, a lower pressure can favor a higher conversion, including a higher conversion at a lower temperature. As a result, in some aspects, the pressure within the secondary reformer 122 may have a pressure between about 1 to about 5 bar. In addition, when the reformer is operated as an SMR reactor, the ratio of water to carbon can be between about 2: 1 to about 4: 1, or about 3:1.

[0038] The second portion 109 of the heated stream can then pass to the secondary reformer 122. In some aspects, the secondary reformer 122 can operate as an adiabatic reformer without the addition of heat within the reformer 122 itself. The secondary reformer 122 can operate as asingle adiabatic reformer or as a series of adiabatic reformers with heat exchange to further heat the reacting stream between adjacent adiabatic reformers. For example, the heat exchanger 121 can be integrated with the secondary reformer 122 so that the secondary reformer 122 comprises a series of reforming reactors with the heat from the outlet of the carbon formation reactor 132 exchanged with the reforming stream upstream of each reforming reactor in the series.

[0039] In the embodiment shown in FIG. 1, the secondary reformer 122 may be used to perform and SMR reaction with an input of a hydrocarbon and steam. The SMR reaction can be the same as that described with respect to the reformer 111, including any of the catalysts, reactor types, and reaction conditions. In some aspects, other endothermic reforming reactions such a DRM can also be carried out with the appropriate feed stream composition. In some aspects, no additional oxygen may be added into the second portion 109 of the heated stream prior to entering the secondary reformer 122.

[0040] As with the outlet stream 112 of the reformer 111, the outlet stream of the secondary reformer 122 can pass through a heat exchanger 123, which can operate as a steam generator to generate steam from a cooling water stream, and then through a condenser 124 to condense and remove an outlet water stream. The resulting dried stream 125 can comprise CO, CO2, H2, unreacted hydrocarbons, and trace amounts of water.

[0041] The dried stream 125 can then be combined with the outlet of the separator 118 to form a combined stream 126, which can be compressed in compressor 127. An optional CO2 stream 128 comprising predominantly CO2 can be combined with the combined stream 126 to adjust the amount of CO2 passing to the carbon formation reactor 132 and to form stream 129. An addition stream within the recycle loop of the carbon formation reactor 132 can also be optionally combined with the stream 129 prior to the carbon formation reactor feed stream passing to a heat exchanger 130. The heat exchanger 130 can serve to adjust the temperature of the carbon formation feed stream using the outlet stream from the carbon formation reactor 132 after is has passed through heat exchanger 121 used to preheat the secondary reformer 122 feed stream. The entire stream can then comprise CO, CO2, H2, hydrocarbons, and trace amounts of water, which can be passed into the carbon formation reactor 132.

[0042] Within the carbon formation reactor 132, carbon can be formed along with H2 and H2O. Various reactions can occur that can result in the formation of solid carbon and other reaction products comprising hydrogen, w aler. CO, and CO2 according to the following reactions:2CO — C + CO2CO2 + CH4 2CO + 2H2H2O+ CH4 CO + 3H202+ 2CH42C0 + 4H2CO + H2— C + H20CO + H2O CO2 + H2

[0043] The carbon formation reaction is generally exothermic overall, though some additional reactions can occur that are endothermic. The reaction conditions within the carbon formation reactor 132 may include a pressure of between about 1 bar to about 50 bar, or between about 1 bar to about 20 bar, a temperature of about 400 °C to about 1000 °C, or between about 500 °C to about 750 °C. The temperature within the carbon formation reactor 132 may be maintained by providing an adiabatic reactor vessel and / or providing the reactants at the desired temperature into the reactor to maintain the temperature within the desired temperature range. The carbon formation reactor 132 can take a variety of forms such as a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, or the like.

[0044] The carbon formation reactor 132 can use a catalyst to promote the reactions and the formation of solid carbon. The catalyst material can include any material suitable for catalyzing the formation of the solid carbon material from the carbon oxide and the gaseous reducing material. As an example, the catalyst material may be an element of Group VI, Group VII, or Group VIII of the Periodic Table of Elements (e.g., iron, nickel, molybdenum, platinum, chromium, cobalt, tungsten, etc.), an actinide, a lanthanide, oxides thereof, alloys thereof, or combinations thereof. Any metal known to be subject to metal coking may also be suitable for use as the catalyst material.

[0045] The catalyst material may be provided within the carbon formation reactor 132 (e.g., within the reaction chamber) as one or more solid structures (e.g., a particle, a wafer, cylinder, plate, sheet, sphere, pellet, mesh, fiber, etc.), and / or as at least a partial coating on another structure (e.g., particles of the at least one material deposited on a structure, such as a wafer, cylinder, plate, sheet, sphere, mesh, pellet, etc.) within the reactor vessel. In some embodiments, the catalyst material may be provided within the reactor as a plurality of particles or particulates. The catalyst material may be stationary (e.g. , as a catalyst bed) or mobile (e.g., as a fluidized bed) within the reactor. In some embodiments, a portion of the catalyst material may be mobile within the reactor and another portion of the catalyst material may be stationary within the reactor.

[0046] As an example, the catalyst for the carbon formation reaction can include an iron-based catalyst. While not intending to be limited by theory', a dissociated carbon (e.g., a methane dissociated in contact with the iron, and / or one or more carbon oxides within the reactor) cancontact the iron (e.g., a ferrite) within the catalyst to form an iron carbide. The iron carbide can then dissociate to reform the ferrite along with a layer of carbon (e.g. , graphite, etc.) on the ferrite. The process can continue and result in the build up of carbon layers on the ferrite, where the reaction rate can decrease as the thickness of the carbon layer on the iron builds due to increased diffusion resistance to the reactive iron core. The catalyst may then deactivate upon the build up of a sufficient carbon layer.

[0047] The formation of the solid carbon then occurs on or around the catalyst such that the removal of solid carbon from the reactor vessel (e.g., using a separator such as a cyclone, settling chamber, etc.) can also result in the removal of the catalyst from the reactor. As a result, a small amount of catalyst may be introduced into the carbon formation reactor 132 along with the reactants while a corresponding amount of catalyst may be removed with the solid carbon. In some aspects, the amount of catalyst added into the reactor may have a mass ratio of catalyst to reactants of between about 0.0001 : 1 to about 1 : 1 , or between about 0.001 : 1 to about 0.1 :1.

[0048] The cataly st may comprise an oxide, and the resulting oxy gen in the oxide as well as the oxygen in the CO may form some amount of water in the gaseous product stream from the carbon formation reactor 132. The products from the carbon formation reactor can then include the gaseous product stream comprising CO, H2O, H2, and CO2, while the solid product stream can comprise solid carbon along with the catalyst or a portion of the catalyst. The solid product stream can be removed from the carbon formation reactor 132 as a separate product stream from the gaseous product stream and removed from the system 100. In some aspects, the solid carbon product can be removed with the gaseous product stream and removed in a solids separator 133. The solids separator 133 can comprise any suitable gas-solid separator such as a cyclone, settling chamber, bag house, filter, and the like. The resulting separated solids stream can leave the system as solids stream 134.

[0049] The reaction can result in an outlet temperature of the gaseous stream in the range of 400 °C-750 °C. The gaseous products leaving the carbon formation reactor 132 can pass to the heat exchanger 121 to heat the second portion 109 of the heated stream as an inlet to the secondary’ reformer 122 as described herein. The cooled gas stream can further pass to exchanger 130 to adjust the temperature of the carbon formation reactor feed stream 129. The resulting gaseous product stream can then pass to a cooler 135 to cool the gaseous product stream, which can then pass to a separator 136. Within the separator 136, any condensed water can be separated as a w ater stream, and the remaining gaseous products can pass to a compressor 137 before being combined with the carbon formation reactor feed stream 129. In some aspects, an optional slipstream can be taken out of the gaseous product stream for processing to avoid the build up of impurities or unreacted components within the carbon formation reactor 132.

[0050] Within the system 100, the gaseous product stream from the carbon formation reactor 132 can be used to exchange heat with the feed stream to the secondary reformer 122. The heated feed stream can then react in the secondary reformer 122 to form an inlet stream to the carbon formation reactor 132. This process can integrate the heat from the exothermic carbon formation reaction as a heat source for the feed stream to the endothermic reforming reactions. The resulting heat integration between the exothermic and endothermic reactions can improve the efficiency of the carbon and hydrogen production process.

[0051] Some embodiments can use a heat exchange reformer (HER) to more closely integrate the exchange of heat from the exothermic reaction with the heat input into an endothermic reaction. As an example, the gaseous product stream from the carbon formation reactor can be pass through a HER to provide input directly into the heat exchanger or reactor in which the endothermic reforming reaction is occurring. This arrangement is similar to a theoretically infinite number of stages of reforming reaction with upstream heat exchangers. Overall, this process can more closely integrate the heat exchange to improve the efficiency of the reforming reactor.

[0052] A configuration showing the use of the HER 221 is illustrated in FIG. 2. The system 200 illustrated in FIG. 2 is similar to the system as shown in FIG. 1, and the like components can be the same or similar to those described with respect to FIG. 1. As a result, like components will not be re-described.

[0053] The main difference between the system of FIG. 1 and the system 200 of FIG. 2, is the use of the HER 221 to exchange heat betw een the gaseous products from the carbon formation reactor 132 and the second portion 109 of the heat stream. Rather than heat the feed stream to the secondary reformer upstream of the secondary reformer, the HER 221 serves to exchange heat between the gaseous products from the carbon formation reactor 132 and the reformer feed stream and catalyst during the reforming reaction.

[0054] The HER 221 can be formed as a heat exchanger having the reformer reaction occurring within the heat exchanger itself. For example, the HER can comprise a shell and tube exchanger with the gaseous products passing through the shell side and the reforming catalyst and reactants disposed within the tubes, or vice versa. The exchanger can be a counter-current exchanger, a bayonet tube exchanger, a co-current exchanger, or any other type of shell and tube exchanger. Other types of heat exchangers can also be used with the gaseous products from the carbon formation reactor 132 exchanging heat with the reforming feed and catalyst during the formationreaction. The HER can be designed to provide a desired heat exchange profile to maintain the reforming reaction reactants and catalyst at the desired reaction temperature. The reforming reaction within the HER can occur a temperature between about 200 °C to about 700 °C. In some aspects, a lower pressure can favor a higher conversion, including a higher conversion at a lower temperature. As a result, in some aspects, the pressure within the HER 221 may have a pressure between about 1 to about 5 bar.

[0055] The feed stream composition, the catalyst, and the outlet products from the HER 221 can be the same as those described with respect to the secondary reformer 122. In some aspects, the outlet from the HER 221 can be passed to one or more additional reforming processes, which can allow for a desired level of products to be formed wile also allowing the HER 221 to operate at a higher pressure. For example, an additional downstream reformer such as an autothermal reformer, SMR reformer, or the like can be used when a higher pressure within the HER results in a lower product conversion.

[0056] The configuration using the HER can allow for heat integration betw een the exothermic carbon formation reaction and the endothermic reforming reactions using indirect heat exchange between the gaseous products from the carbon formation reactor and the reforming reaction. This can allow for a more efficient carbon and hydrogen formation process.

[0057] Some embodiments can use an embedded reformer design that places the reforming reaction within the exothermic carbon formation reactor to more closely integrate the exchange of heat from the exothermic reaction with the heat input into an endothermic reaction. In this configuration, the carbon formation reactor can be designed to contain a carbon formation reaction volume and a reforming reaction volume within a single reactor vessel. The release of heat from the exothermic carbon formation reaction can then be transferred to the reforming reaction volume through heat exchange surfaces to provide the heat to the drive the endothermic reforming reactions.

[0058] A configuration showing the use of embedded reformer design is illustrated in FIG. 3. The system 300 illustrated in FIG. 3 is similar to the systems as shown in FIGS. 1 and 2, and the like components can be the same or similar to those described with respect to FIGS. 1 and 2. As a result, like components will not be re-described.

[0059] The main difference betw een the system of FIGS. 1 and 2 and the system 300 of FIG. 3, is the integration of the secondary reformer 321 into the carbon formation reactor to form an integrated carbon formation reactor 332. This configuration can allow- for exchange heat between products of the carbon formation reactor as the products form and the reforming feed stream. Rather than heat the feed stream to the secondary reformer upstream of the secondary reformer,the integrated carbon formation reactor 332 serves to exchange heat between the carbon formation reaction and the reformer feed stream and catalyst during the reforming reaction.

[0060] The integrated carbon formation reactor 332 can be designed using any suitable heat exchange surfaces that separate the carbon formation reaction and the reforming reaction while allowing for heat exchange during the reaction process. Any suitable configurations that allow for both reactions can be used. In some aspects, the integrated carbon formation reactor 332 can be formed as a shell and tube exchanger, a HER. or the like.

[0061] An exemplary embodiment of the integrated carbon formation reactor 332 is shown in FIG. 4. In this embodiment, a reforming reaction volume can be defined within the tubes 304 disposed within the outer reactor vessel. The volume between the inner walls of the reactor and the tubes 304 can define the carbon formation reaction volume. This configuration is similar to a shell and tube exchanger with the reforming reaction volume being defined within the tubes, and the carbon formation reaction volume being defined in the shell space. The reforming reaction can take place within the tubes 304, which can have the reforming catalyst 306 disposed therein. The carbon formation volume can comprise a carbon formation catalyst 310 disposed about the tubes 304. In some aspects, the carbon formation catalyst 310 can be used to cover the tubes 304 to allow the exothermic carbon formation reaction to occur over the length of the tubes 304, which can serve as the heat exchange surface between the exothermic carbon formation reaction and the endothermic reforming reaction.

[0062] The carbon formation reaction volume can carry out the carbon formation reaction using any of the conditions and catalysts as described herein. In some aspects, the carbon formation catalyst 310 can form a fluidized bed around the tubes 304. The reactants in stream 129 can be introduced into a lower portion of the integrated carbon formation reactor 332 and react over the catalyst 310. The heat integration can allow the temperature of the carbon formation to be regulated within the integrated carbon formation reactor 332, and any of the conditions described with respect to the carbon formation reaction can be used in the carbon formation reaction volume.

[0063] Similarly, the reforming reaction feed stream 109 can be introduced into the tubes 304. The temperature of the reactants can be maintained along the length of the tubes 304 to allow the reforming reaction to be carried out. The reforming reaction outlet stream 314 can then comprise the reforming reaction products. Any of the reaction conditions described with respect to the reforming reaction can be used in the reforming reaction volume. In an embodiment, the reforming reaction volume can be characterized by a reforming pressure of from about 1 bar to about 30 bars. In some aspects, the reforming reaction can be carried out at a pressure that islower than that of the carbon formation reaction. As a result, the pressure within the tubes 304 can be lower than the pressure within the carbon formation reaction volume. In some aspects, a ratio of the pressure within the carbon formation reaction volume to the pressure within the reforming reaction volume can be between about 1.1 : 1 to about 10: 1.

[0064] The tubes 304 within the integrated carbon formation reactor 332 can have one or more heat exchange structures such as plates, fins, corrugated structures, or other heat transfer surfaces. In some aspects, the heat transfer surfaces can comprise a carbon formation catalyst to allow heat to be exchanged with the tubes while also promoting the carbon formation reaction. The tubes an also provide for some advantages within the reactor. For example, the tubes can serve to control the carbon formation catalyst during the reaction. This can be beneficial when the carbon formation catalyst is operated as a fluidized bed, and the tubes can serve as bubble breakers to reduce slugging within the fluidized bed.

[0065] In still another embodiment, the carbon formation reaction can be integrated with an endothermic reaction such as a reforming reaction using a partial oxidation reach on of the carbon formation reaction gaseous products to further increase the temperature of the gaseous carbon formation reaction products prior to exchanging heat with the reformer feed stream. An embodiment of this system is shown in FIG. 5. The system 400 illustrated in FIG. 5 is similar to the systems as shown in FIGS. 1-3, and the like components can be the same or similar to those described with respect to FIGS. 1-3. As a result, like components will not be re-described.

[0066] In the embodiment as shown in FIG. 5, the heated stream 409 from the inlet of the system 400 can be passed to a HER 421 . The HER 421 can be the same or similar to the HER 221 described with respect to FIG. 2. The HER 421 can be configured to carry out a reforming reaction to produce reforming products that can pass to the heat exchanger 123, which can be used as a steam generator. The cooled reformer products from the heat exchanger 123 can then pass to a condenser 124 to remove at least a portion of the water in the cooled stream, which can produce a dried reformer product stream. The heat exchanger 123 and the condenser 124 can be the same as or similar to the same elements described with respect to FIGS. 1-3.

[0067] The dried reformer product stream can then be compressed in compressor 426 before passing to separator 418. The separator 418 can separate at least a portion of the hydrogen in the dried reformer product stream. The separator 418 can be the same as or similar to the separator 118 described with respect to FIGS. 1-3. The hydrogen in the hydrogen stream 420 can pass out of the system 400. The remaining components comprising CO, CO2, unreacted hydrocarbons, and trace amounts of water and H2 can be compressed in compressor 427.

[0068] An optional CO2 stream comprising predominantly CO2 can be combined with the compressed stream from the compressor 427 to adjust the amount of CO2 passing to the carbon formation reactor 132. An addition stream within the recycle loop of the carbon formation reactor 132 can also be optionally combined with the compressed stream prior to the carbon formation reactor feed stream passing to a heat exchanger 130. The heat exchanger 130 can serve to adjust the temperature of the carbon formation feed stream using the outlet stream from the carbon formation reactor 132 after it has passed through the HER 421. The entire stream can then comprise CO, CO2, hydrocarbons, minor amounts of H2, and trace amounts of water, which can be passed into the carbon formation reactor 132.

[0069] Within the carbon formation reactor 132, the exothermic carbon formation reaction can convert at least a portion of the carbon oxides, hydrocarbons, and hydrogen into solid carbon. The carbon formation reaction can be the same as described with respect to FIG. 1, and the resulting product stream can be passed through a separator 133 to remove the solids to produce a solid carbon product stream.

[0070] The embodiment of FIG. 5 differs from the previous embodiments through the use of a partial oxidation reaction (POX) carried out with the gaseous products from the carbon formation reactor 132. The POX reaction can result in the partial or incomplete oxidation of the hydrocarbons and / or hydrogen in the gaseous product stream with an oxygen containing species. As shown in FIG. 5, the oxygen containing species can be oxygen or air. and the oxygen in stream 406 can be an oxygen enriched stream. Upon introduction of oxygen into the gaseous product stream from the carbon formation reactor, the stream can be combusted as a homogenous reaction. Alternatively, a fired POX reactor can be used. The resulting combustion can heat the gaseous product stream due to the exothermic combustion. Some amount of unreacted hydrocarbons can remain in the stream in addition to the other carbon oxides, hydrogen, and water. The entire stream can then pass to the HER 421.

[0071] In some aspects, the HER 421 can provide indirect contact between the heated carbon formation reactor products passing from the POX reactor. The HER 421 can be used to carry out a reforming reaction in the presence of a catalyst. In some embodiments, the heated gaseous product stream can have a temperature between about 400 °C to about 1100 °C. or between about 600 °C to about 1000 °C. The higher temperatures can be used to provide a greater throughput in the reformer, which may eliminate the need for a second or supplemental reformer. The higher gaseous product stream temperatures can also allow the reforming reaction to be carried out at a higher temperature and pressure, which may help with reducing the compression energy usagewithin the system. The remainder of the system can be the same or similar to that described herein.

[0072] While the HER 421 can be used to carry out the reforming reaction, other configurations such as the use of an exchanger to heat a reforming feed stream followed by a downstream dedicated reformer, or a series of reforming reactors using the heated gaseous products stream in a plurality’ of exchangers upstream of each reactor can also be used.

[0073] The introduction of oxygen in the POX reactor can also have anumber of benefits within the system. For example, the HER 421 can be operated at a higher temperature, which can allow for a higher conversion within the reforming reaction. The temperature reached within the HER 421 can be controlled by the amount of oxygen introduced for combustion in the POX reactor, and the amount can be selected to provide a desired temperature and conversion in the reforming reaction. In addition, the addition of oxygen reduces the likelihood of metal dusting occurring within the downstream components including the HER 421 or any other reforming steps. Metal dusting is a process whereby metals react to form carbides that can then wear resulting in attrition that can remove a portion of the metal surface. As oxygen is added, the reactivity of the metals with carbon tends to decrease, thereby low ering the likelihood of metal wear or dusting due to the contact with the low oxygen gases at high temperatures.

[0074] The configuration of FIG. 5 results in the indirect contact of the heated gaseous reaction products from the carbon formation reactor w ith the reforming feed stream to the HER. In some aspects, the two streams can be directly mixed to exchange heat and provide a feed stream to the reforming reaction. An embodiment showing a direct mixing of the POX reactor product with the reformer feed or product stream is illustrated in FIG. 6. The system 500 illustrated in FIG. 6 is similar to the system as shown in FIG. 5, and the like components can be the same or similar to those described with respect to FIG. 5. As a result, like components will not be re-described.

[0075] As shown in FIG. 6, the embodiment of FIG. 6 uses a POX reaction carried out with the gaseous products from the carbon formation reactor 132. The POX reaction can result in the partial or incomplete oxidation of the hydrocarbons and / or hydrogen in the gaseous product stream with an oxygen containing species. As shown in FIG. 6. the oxygen containing species can be oxygen or air, and the oxygen in stream 406 can be an oxygen ennched stream. Upon introduction of oxygen into the gaseous product stream from the carbon formation reactor, the stream can be combusted as a homogenous reaction. Alternatively, a fired POX reactor can be used. The resulting combustion can heat the gaseous product stream due to the exothermic combustion. Some amount of unreacted hydrocarbons can remain in the stream in addition to the other carbon oxides, hydrogen, and w ater. The entire stream can then pass to the HER 521.

[0076] In some aspects, the HER 521 can provide direct contact between the heated carbon formation reactor products 505 passing from the POX reactor with the reforming feed stream 409 and / or the reforming reaction products. The heated carbon formation reaction products 505 from the POX reactor can be mixed with the reforming feed gas in stream 409 and / or mixed with the reforming reaction product gases after the reforming reaction has occurred. Whether or not the heated carbon formation reactor products 505 are mixed with the reformer feed stream 409 or the reforming reaction product stream, the HER 521 can be used to carry out a reforming reaction in the presence of a catalyst. In some embodiments, the heated gaseous product stream 505 can have a temperature between about 400 °C to about 1100 °C, or between about 600 °C to about 1000 °C. The higher temperatures can be used to provide a greater throughput in the reformer, which may eliminate the need for a second or supplemental reformer. The higher gaseous product stream temperatures can also allow the reforming reaction to be carried out at a higher temperature and pressure, which may help with reducing the compression energy usage within the system. The remainder of the system can be the same or similar to that described herein.

[0077] While the HER 521 can be used to carry out the reforming reaction, other configurations such as the use of an exchanger to heat a reforming feed stream followed by a downstream dedicated reformer, or a series of reforming reactors using the heated gaseous products stream in a plurality' of exchangers upstream of each reactor can also be used.

[0078] Specific embodiments of the HER 521 are shown in FIGS. 7A and 7B. As shown in FIG. 7A, the heated carbon formation reaction products 505 can be combined with the reforming reaction product stream prior to heat exchange with the reformer feed stream. In this embodiment, the reforming reaction feed stream 409 can pass downward through a reforming reaction catalyst bed and react to form the reforming reaction products. The reforming reaction products can then directly mix with the heated carbon formation reaction products 505 before passing back through one or more channels that serve as heat exchange surfaces with the reforming catalyst beds. The combined stream can then passing out of the HER 521 as the HER product stream 507.

[0079] FIG. 7B illustrates an embodiment of the HER 521 in which the heated carbon formation reaction products 505 are combined with the reforming reaction product stream after heat exchange with the reforming reaction feed stream 409. As illustrated in FIG. 7B, the reforming reaction feed stream 409 can pass down ward through a reforming reaction catalyst bed and react to form the reforming reaction products. The reforming reaction can be carried out in the tubes containing the reforming catalyst, which can pass downwards and back upwards into a mixing chamber. The heated carbon formation reaction products 505 can pass over the tubescontaining the reforming catalyst and heat exchange with the reforming reaction catalyst along the length of the reformation reaction pathway. The reforming reaction products can then directly mix with the heated carbon formation reaction products 505 at the outlet of the tubes. The combined stream can then pass out of the HER 521 as the HER product stream 507.

[0080] Returning to FIG. 6, The HER product stream 507 from the HER 521 can be split, with a first portion passing to the heat exchanger 123, which can be used as a steam generator. A second portion can pass to the heat exchanger 130 used to preheat the carbon formation reactor 132 feed stream. The cooled reformer products in stream 502 and the cooled second portion 506 from the heat exchanger 130 can be combined to form stream 504 and passed to a condenser 124 to remove at least a portion of the water in the cooled stream, which can produce a dried reformer product stream. The heat exchanger 123 and the condenser 124 can be the same as or similar to the same elements described with respect to FIGS. 1-3.

[0081] The dried reformer product stream can then be compressed in compressor 426 before passing to separator 418. The separator 418 can separate at least a portion of the hydrogen in the dried reformer product stream. The separator 418 can be the same as or similar to the separator 118 described with respect to FIGS. 1-3. The hydrogen in the hydrogen stream 420 can pass out of the system 400. The remaining components comprising CO, CO2, unreacted hydrocarbons, and trace amounts of water and H2 can be compressed in compressor 427.

[0082] An optional CO2 stream 128 comprising predominantly CO2 can be combined with the compressed stream from the compressor 427 to adjust the amount of CO2 passing to the carbon formation reactor 132. An addition stream within the recycle loop of the carbon formation reactor 132 can also be optionally combined with the compressed stream prior to the carbon formation reactor feed stream passing to a heat exchanger 130. The heat exchanger 130 can serve to adjust the temperature of the carbon formation reactor feed stream using the outlet stream from the carbon formation reactor 132 after it has passed through the HER 521. The entire stream can then comprise CO, CO2, hydrocarbons, minor amounts of H2, and trace amounts of water, which can be passed into the carbon formation reactor 132.

[0083] While the HER 521 can be used to carry out the reforming reaction, other configurations such as the use of an exchanger to heat a reforming feed stream followed by a downstream dedicated reformer, or a series of reforming reactors using the heated gaseous products stream in a plurality^ of exchangers upstream of each reactor can also be used.

[0084] The introduction of oxygen in the POX reactor can also have a number of benefits within the system. For example, the HER 521 can be operated at a higher temperature, which can allow for a higher conversion within the reforming reaction. The temperature reached within the HER521 can be controlled by the amount of oxygen introduced for combustion in the POX reactor, and the amount can be selected to provide a desired temperature and conversion in the reforming reaction. In addition, the addition of oxygen reduces the likelihood of metal dusting occurring within the downstream components including the HER 521 or any other reforming steps.

[0085] Having described various systems, processes, catalyst, and reactors, certain aspects can include, but are not limited to:

[0086] In a first aspect, a process of integrating heat in a reaction comprises: performing an exothermic reaction; generating heat and products in response to performing the exothermic reaction; transferring the heat to an endothermic reaction; and performing the endothermic reaction in response to the heat from the exothermic reaction.

[0087] A second aspect can include the process of the first aspect, wherein the exothermic reaction comprises a carbon formation reaction.

[0088] A third aspect can include the process of the second aspect, wherein the carbon formation reaction comprises: contacting a stream comprising a hydrocarbon and a carbon oxide with a catalyst; forming solid carbon in response to the contacting; and generating the heat in response to the contacting.

[0089] A fourth aspect can include the process of any one of the first to third aspects, wherein the endothermic reaction comprises at least one of a steam methane reforming reaction, a dry reforming of methane reaction, or a reverse water gas shift reaction.

[0090] A fifth aspect can include the process of any one of the first to fourth aspects, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to a feed stream; and introducing the feed stream into the endothermic reaction.

[0091] A sixth aspect can include the process of any one of the first to fifth aspects, wherein transferring the heat to an endothermic reaction comprises: transferring the heat to a reactor, wherein the endothermic reaction occurs in the reactor.

[0092] A seventh aspect can include the process of any one of the first to sixth aspects, wherein the endothermic reaction produces endothermic reaction products, and where the process further comprises: mixing the products and the endothermic reaction products downstream of the endothermic reaction.

[0093] In an eighth aspect, a reaction system comprises: an exothermic reactor configured to perform an exothermic reaction; an endothermic reactor configured to perform an endothermic reaction; and a heat exchange surface configured to transfer heat from the exothermic reach on to the endothermic reaction.

[0094] A ninth aspect can include the reaction system of the eighth aspect, wherein the heat exchange surface comprises a heat exchanger in fluid communication with the exothermic reactor and the endothermic reactor, wherein the heat exchanger is configured to transfer the heat from the exothermic reaction to a feed stream to the endothermic reaction.

[0095] A tenth aspect can include the reaction system of the eighth aspect, wherein the heat exchange surface is part of the endothermic reactor, and wherein the endothermic reactor is configured to receive the heat to drive the endothermic reaction.

[0096] An eleventh aspect can include the reaction system of the eighth aspect, wherein the heat exchange surface is disposed wi thin the exothermic reactor, wherein the endothermic reactor is disposed within the heat exchange surface within the exothermic reactor, and wherein the endothermic reactor is configured to receive the heat from the exothermic reaction within the exothermic reactor.

[0097] A twelfth aspect can include the reaction system of any one of the eighth to eleventh aspects, further comprising: a partial oxidation reactor, wherein the partial oxidation reactor is configured to receive a product stream from the exothermic reactor, heat the product stream, and pass the product stream to the heat exchange surface.

[0098] A thirteenth aspect can include the reaction system of any one of the eighth to twelfth aspects, wherein the exothermic reaction comprises a carbon formation reaction, and wherein the endothermic reaction comprises a reforming reaction.

[0099] In a fourteenth aspect, a process of integrating heat in a carbon formation reaction comprises: reacting a feed stream comprising a hydrocarbon and at least one carbon oxide to form solid carbon; generating heat and gaseous products in response to forming the solid carbon; transferring the heat to an endothermic reaction; and performing the endothermic reaction in response to the heat from forming the solid carbon.

[0100] A fifteenth aspect can include the process of the fourteenth aspect, wherein the endothermic reaction comprises at least one of a steam methane reforming reaction, a dry reforming of methane reaction, or a reverse w ater gas shift reaction.

[0101] A sixteenth aspect can include the process of the fourteenth or fifteenth aspect, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to an endothermic reaction feed stream; and introducing the endothermic reaction feed stream into the endothermic reaction.

[0102] A seventeenth aspect can include the process of the sixteenth aspect, wherein transferring the heat to the endothermic reaction feed stream comprises passing the gaseousproducts through one or more heat exchangers, and heating the endothermic reaction feed stream in the one or more heat exchangers.

[0103] An eighteenth aspect can include the process of the sixteenth or seventeenth aspect, wherein the endothermic reaction is performed in one or more adiabatic reactors.

[0104] A nineteenth aspect can include the process of the fourteenth or fifteenth aspect, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to a reactor, wherein the endothermic reaction occurs in the reactor.

[0105] A twentieth aspect can include the process of the nineteenth aspect, wherein the reactor comprises a heat exchange reformer.

[0106] A twenty first aspect can include the process of the nineteenth or twentieth aspect, wherein transferring the heat to the endothermic reaction comprises transferring the heat to an endothermic reaction feed stream in the reactor.

[0107] A twenty second aspect can include the process of the fourteenth or fifteenth aspect, wherein the reacting of the feed stream occurs in an exothermic reaction volume within a reactor, wherein the endothermic reaction occurs in an endothermic reaction volume within the reactor, wherein the exothermic reaction volume is separated from the endothermic reaction volume by a heat exchange surface within the reactor, and wherein transferring the heat to the endothermic reaction comprises: transferring the heat to the endothermic reaction volume through the heat exchange surface.

[0108] A twenty third aspect can include the process of the twenty second aspect, wherein the heat exchange surface comprises one or more tubes disposed within the reactor.

[0109] A twenty fourth aspect can include the process of the twenty third aspect, wherein a reforming catalyst is disposed within the tubes, and wherein the endothermic reaction comprises a reforming reaction occurring in contact with the catalyst.

[0110] A twenty fifth aspect can include the process of the twenty third to twenty fourth aspect, wherein a pressure within the one or more tubes is lower than a pressure in the exothermic reaction volume.

[0111] A twenty sixth aspect can include the process of the fourteenth or fifteenth aspect, further comprising: introducing oxygen into the gaseous products; combusting the oxygen in the gaseous products; and heating the gaseous products based on the combusting prior to transferring the heat to the endothermic reaction.

[0112] A twenty seventh aspect can include the process of the tw enty sixth aspect, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to anendothermic reaction feed stream; and introducing the endothermic reaction feed stream into the endothermic reaction.

[0113] A twenty eighth aspect can include the process of the twenty sixth or twenty seventh aspect, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to a reactor, wherein the endothermic reaction occurs in the reactor.

[0114] A twenty ninth aspect can include the process of any one of the twenty sixth to twenty eighth aspects, further comprising: producing endothermic reaction products from the endothermic reaction; and mixing the gaseous products and the endothermic reaction products downstream of the endothermic reaction.

[0115] A thirtieth aspect can include the process of the twenty ninth aspect, wherein mixing the gaseous products and the endothermic reaction products occurs prior to transferring the heat to the endothermic reaction.

[0116] A thirty first aspect can include the process of the twenty ninth aspect, wherein mixing the gaseous products and the endothermic reaction products occurs after to transferring the heat to the endothermic reaction.

[0117] It is to be further understood that the present descnption is not limited to the particular methodology, compounds, materials, manufacturing techniques, uses, and applications, described herein, as these may vary. It is also to be understood that the terminology7used herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present systems and methods. It must be noted that as used herein and in the appended claims (in this application, or any derived applications thereof), the singular forms "a," "an," and "the" include the plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to "an element" is a reference to one or more elements and includes equivalents thereof known to those skilled in the art. All conjunctions used are to be understood in the most inclusive sense possible. Thus, the word "or" should be understood as having the definition of a logical "or" rather than that of a logical "exclusive or" unless the context clearly necessitates otherwise. Structures described herein are to be understood also to refer to functional equivalents of such structures. Language that may be construed to express approximation should be so understood unless the context clearly dictates otherwise.

[0118] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary' skill in the art to which this description belongs. Preferred methods, techniques, devices, and materials are described, although any methods, techniques, devices, or materials similar or equivalent to those described herein may be used in the practice or testing of the present systems and methods. Structures described hereinare to be understood also to refer to functional equivalents of such structures. The present systems and methods will now be described in detail with reference to embodiments thereof as illustrated in the accompanying drawings.

[0119] From reading the present disclosure, other variations and modifications will be apparent to persons skilled in the art. Such variations and modifications may involve equivalent and other features which are already known in the art, and which may be used instead of or in addition to features already described herein.

[0120] Although claims may be formulated in this Application or of any further Application derived therefrom, to particular combinations of features, it should be understood that the scope of the disclosure also includes any novel feature or any novel combination of features disclosed herein either explicitly or implicitly or any generalization thereof, whether or not it relates to the same systems or methods as presently claimed in any Claim and whether or not it mitigates any or all of the same technical problems as do the present systems and methods.

[0121] Features which are described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination. The Applicants hereby give notice that new claims may be formulated to such features and / or combinations of such features during the prosecution of the present Application or of any further Application derived therefrom.

Claims

CLAIMS1. A process of integrating heat in a reaction, the process comprising: performing an exothermic reaction; generating heat and products in response to performing the exothermic reaction; transferring the heat to an endothermic reaction; and performing the endothermic reaction in response to the heat from the exothermic reaction.

2. The process of claim 1, wherein the exothermic reaction comprises a carbon formation reaction.

3. The process of claim 2, wherein the carbon formation reaction comprises: contacting a stream comprising a hydrocarbon and a carbon oxide with a catalyst; forming solid carbon in response to the contacting; and generating the heat in response to the contacting.

4. The process of claim 1, wherein the endothermic reaction comprises at least one of a steam methane reforming reaction, a dry reforming of methane reaction, or a reverse water gas shift reaction.

5. The process of claim 1, wherein transferring the heat to the endothermic reaction compnses: transferring the heat to a feed stream; and introducing the feed stream into the endothermic reaction.

6. The process of claim 1, wherein transferring the heat to an endothermic reaction comprises: transferring the heat to a reactor, wherein the endothermic reaction occurs in the reactor.

7. The process of claim 1, wherein the endothermic reaction produces endothermic reaction products, and where the process further comprises: mixing the products and the endothermic reaction products downstream of the endothermic reaction.

8. A reaction system comprising: an exothermic reactor configured to perform an exothermic reaction; an endothermic reactor configured to perform an endothermic reaction; and a heat exchange surface configured to transfer heat from the exothermic reaction to the endothermic reaction.

9. The reaction system of claim 8, wherein the heat exchange surface comprises a heat exchanger in fluid communication with the exothermic reactor and the endothermicreactor, wherein the heat exchanger is configured to transfer the heat from the exothermic reaction to a feed stream to the endothermic reaction.

10. The reaction system of claim 8, wherein the heat exchange surface is part of the endothermic reactor, and wherein the endothermic reactor is configured to receive the heat to drive the endothermic reaction.

11. The reaction system of claim B81 , wherein the heat exchange surface is disposed within the exothermic reactor, wherein the endothermic reactor is disposed within the heat exchange surface within the exothermic reactor, and wherein the endothermic reactor is configured to receive the heat from the exothermic reaction within the exothermic reactor.

12. The reaction system of claim 8. further comprising: a partial oxidation reactor, wherein the partial oxidation reactor is configured to receive a product stream from the exothermic reactor, heat the product stream, and pass the product stream to the heat exchange surface.

13. The reaction system of claim 8, wherein the exothermic reaction comprises a carbon formation reaction, and wherein the endothermic reaction comprises a reforming reaction.

14. A process of integrating heat in a carbon formation reaction, the process comprising: reacting a feed stream comprising a hydrocarbon and at least one carbon oxide to form solid carbon; generating heat and gaseous products in response to forming the solid carbon; transferring the heat to an endothermic reaction; and performing the endothermic reaction in response to the heat from forming the solid carbon.

15. The process of claim 14, wherein the endothermic reaction comprises at least one of a steam methane reforming reaction, a dry reforming of methane reaction, or a reverse water gas shift reaction.

16. The process of claim 14, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to an endothermic reaction feed stream; and introducing the endothermic reaction feed stream into the endothermic reaction.

17. The process of claim 16, wherein transferring the heat to the endothermic reaction feed stream comprises passing the gaseous products through one or more heat exchangers, and heating the endothermic reaction feed stream in the one or more heat exchangers.

18. The process of claim 16, wherein the endothermic reaction is performed in one or more adiabatic reactors.

19. The process of claim 14, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to a reactor, wherein the endothermic reaction occurs in the reactor.

20. The process of claim 19, wherein the reactor comprises a heat exchange reformer.

21. The process of claim 19, wherein transferring the heat to the endothermic reaction comprises transferring the heat to an endothermic reaction feed stream in the reactor.

22. The process of claim 14, wherein the reacting of the feed stream occurs in an exothermic reaction volume within a reactor, wherein the endothermic reaction occurs in an endothermic reaction volume within the reactor, wherein the exothermic reaction volume is separated from the endothermic reaction volume by a heat exchange surface within the reactor, and wherein transferring the heat to the endothermic reaction comprises: transferring the heat to the endothermic reaction volume through the heat exchange surface.

23. The process of claim 22, wherein the heat exchange surface comprises one or more tubes disposed within the reactor.

24. The process of claim 23, wherein a reforming catalyst is disposed within the tubes, and wherein the endothermic reaction comprises a reforming reaction occurring in contact with the catalyst.

25. The process of claim 23, wherein a pressure within the one or more tubes is lower than a pressure in the exothermic reaction volume.

26. The process of claim 14, further comprising: introducing oxygen into the gaseous products; combusting the oxygen in the gaseous products; and heating the gaseous products based on the combusting prior to transferring the heat to the endothermic reaction.

27. The process of claim 26, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to an endothermic reaction feed stream; and introducing the endothermic reaction feed stream into the endothermic reaction.

28. The process of claim 26, wherein transferring the heat to the endothermic reaction comprises: transferring the heat to a reactor, wherein the endothermic reaction occurs in the reactor.

29. The process of claim 26, further comprising: producing endothermic reaction products from the endothermic reaction; and mixing the gaseous products and the endothermic reaction products downstream of the endothermic reaction.

30. The process of claim 29, wherein mixing the gaseous products and the endothermic reaction products occurs prior to transferring the heat to the endothermic reaction.

31. The process of claim 29, wherein mixing the gaseous products and the endothermic reaction products occurs after to transferring the heat to the endothermic reaction.

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