Corrosion resistant materials and structures for chemical processing

Abstract

A chemical processing unit includes a vessel having at least one vessel inlet and at least one vessel outlet; and a structure, the structure at least partially positioned within the vessel, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, the matrix material including one or more of copper and nickel, wherein at least one of copper and nickel has a weight percentage greater than 10 wt.% based on a total weight of the structure.

Description

CORROSION RESISTANT MATERIALS AND STRUCTURES FOR CHEMICAL PROCESSINGCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application 63 / 693,779, titled “CORROSION RESISTANT MATERIALS FOR CHEMICAL PROCESSING”, filed September 12, 2024, the contents of which are incorporated by reference herein.TECHNICAL FIELD

[0002] The subject matter disclosed herein relates broadly to the fields of chemical processing and energy conversion, and more particularly to corrosion resistant materials and structures for chemical processing applications.BACKGROUND

[0003] Chemical processing facilities can convert one or more reactants to one or more products, such as by utilizing reaction and / or separation units. Often, these facilities utilize, produce, or separate a chemical that can be highly corrosive to common materials that interact with the chemical during the process. Example reactions performed in a chemical processing facility include the reverse-water gas shift reaction, the steam methane reforming reaction, and the Fischer-Tropsch process. The reverse-water gas shift (RWGS) reaction is an endothermic reaction producing syngas and water vapor from carbon dioxide and hydrogen. The steam methane reforming reaction (SMR) is capable of producing hydrogen and carbon monoxide by a catalytic reaction of hydrocarbons with water. As these reactions are endothermic, reactants are typically heated to high temperatures to perform the reaction. The Fischer-Tropsch process is a catalytic chemical reaction for converting carbon monoxide and hydrogen into hydrocarbons of various molecular weights. Typically, the input hydrogen and carbon monoxide must be compressed to high pressures before entering the reactor.

[0004] Reactors, heat exchangers, and other structures (such as tubular structures) subjected to carbon-containing gases, such as carbon monoxide, and / or hydrogen gas can suffer from coking and from the highly corrosive environment and metal dusting, a type of corrosivedegradation of the material forming the reactor, heat exchanger, or other structure. Accordingly, these high operating temperatures and pressures have conventionally required expensive reactor materials, inefficient heating units, and frequent service intervals due to metal fatigue. Therefore, it is desirable to provide materials and structures for improved corrosion resistance and thermal conductivity.SUMMARY

[0005] According to one aspect, a chemical processing unit includes a vessel having at least one vessel inlet and at least one vessel outlet; and a structure, the structure at least partially positioned within the vessel, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, the matrix material including one or more of copper and nickel, wherein at least one of copper and nickel has a weight percentage greater than 10 wt.% based on a total weight of the structure.

[0006] According to another aspect, a tubular assembly for use in chemical processing includes a first component including a metal-containing matrix material and a metal-oxide dispersed in the metal-containing matrix material; and a second component including at least one of a metal-containing material and a ceramic-containing material.

[0007] According to another aspect, a method for improving corrosion resistance in chemical processing includes utilizing a structure in a chemical processing unit to improve corrosion resistance to at least one of hydrogen gas, water vapor, and carbon monoxide gas, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, wherein the matrix material includes at least one of copper and nickel.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1A illustrates an exploded view of chemical processing unit 100, according to some embodiments.

[0009] FIG. IB illustrates chemical processing unit 100, according to some embodiments.

[0010] FIG. 1C illustrates a side view of chemical processing unit 150, according to some embodiments.

[0011] FIG. ID illustrates chemical processing unit 150, according to some embodiments.

[0012] FIG. 2A illustrates fluid transfer structure 200, according to some embodiments.

[0013] FIG. 2B illustrates an end view of fluid transfer structure 200, according to some embodiments.

[0014] FIG. 2C illustrates an end view of fluid transfer structure 200, according to some embodiments.

[0015] FIG. 2D illustrates a view of detail C from FIG. 2B, according to some embodiments.

[0016] FIG. 2E illustrates a view of detail D from FIG. 2C, according to some embodiments.

[0017] FIG. 3 illustrates method 300 for improving corrosion resistance in a chemical processing unit, according to some embodiments.

[0018] FIG. 4 illustrates method 400 for improving corrosion resistance in a chemical processing unit, according to some embodiments.DETAILED DESCRIPTION

[0019] Embodiments of the present disclosure provide materials for improving corrosion resistance and / or thermal conductivity in chemical processing and energy conversion applications. Conventionally, iron and nickel alloys have been used in petrochemical applications, such as for chemical reactor vessels. Reactors, heat exchangers, and other structures (such as tubular structures) subjected to carbon-containing gases, such as carbon monoxide, and / or hydrogen gas can suffer from the highly corrosive environment and / or, at least in the case of syngas applications - metal dusting. For example, nickel and ferrous alloys suffer from corrosion in the presence of carbon monoxide in certain temperature ranges. Materials of the present disclosure can be used within, or coated as a barrier layer on, various structures that are subjected to corrosive gases under non-ideal temperature conditions in chemical processing applications - improving the corrosion resistance.

[0020] Structures and chemical processing units of the present disclosure can include a first material. First materials of the present disclosure generally include a matrix material and a metal- oxide component. The metal-oxide component is generally dispersed in the matrix material. The matrix material is capable of at least partially surrounding or encapsulating other components of the present disclosure, such as the metal-oxide component. In one example, the metal-oxide component is substantially homogeneously dispersed in the matrix material.

[0021] The matrix material includes a metal (e.g., a transition metal) or alloy thereof. In one example, the matrix material includes copper or alloys thereof. Accordingly, the matrix material can include substantially pure copper. Alternatively, the matrix material can include a copper alloy, including copper and one or more additional elemental species. The one or more additional elemental species can include at least one transition metal and / or post-transition metal. Examples of the at least one transition metal for use in the matrix material can include chromium, nickel, silver, zinc, zirconium, titanium, tungsten, molybdenum, and iron. In one nonlimiting example, the matrix material includes a copper chromium alloy. In another non-limiting example, the matrix material includes a copper zirconium alloy.

[0022] The weight percentage of copper in the matrix material can be greater than about 60 wt.%. The weight percentage of copper in the matrix material can be greater than about 70 wt.%. The weight percentage of copper in the matrix material can be greater than about 90 wt.%. In one example, the weight percentage of copper in the matrix material ranges from about 60 wt.% to 100 wt.%. In another example, the weight percentage of copper in the matrix material ranges from about 75 wt.% to 99.9 wt.%. In another example, the weight percentage of copper in the matrix material ranges from about 80 wt.% to 100 wt.%. The weight percentage of copper in the first material can be greater than about 10 wt.%, based on a total weight of the first material. The weight percentage of copper in the first material can be greater than about 20 wt.%. In one example, the weight percentage of copper in the first material can be greater than about 50 wt.%. In another example, the weight percentage of copper in the first material ranges from about 80 wt.% to 99.95 wt.%.

[0023] In one example, the matrix material includes nickel or alloys thereof. Accordingly, the matrix material can include substantially pure nickel. Alternatively, the matrix material can include a nickel alloy, including nickel and one or more additional elemental species. The one or more additional elemental species can include at least one transition metal and / or post-transition metal. Examples of the at least one transition metal for use in the matrix material can include chromium, copper, zirconium, titanium, tungsten, molybdenum, tungsten, manganese, niobium, cobalt, and iron. The matrix material can include silicon.

[0024] The weight percentage of nickel in the matrix material can be greater than about 60 wt.%. The weight percentage of nickel in the matrix material can be greater than about 70 wt.%. The weight percentage of nickel in the matrix material can be greater than about 90 wt.%. In oneexample, the weight percentage of nickel in the matrix material ranges from about 60 wt.% to 100 wt.%. In another example, the weight percentage of nickel in the matrix material ranges from about 75 wt.% to 99.9 wt.%. The weight percentage of nickel in the first material can be greater than about 10 wt.%. The weight percentage of nickel in the first material can be greater than about 20 wt.%. In one example, the weight percentage of nickel in the first material can be greater than about 50 wt.%. In another example, the weight percentage of nickel in the first material ranges from about 80 wt.% to 99.95 wt.%.[00251 In one example, the matrix material includes chromium or alloys thereof. Accordingly, the matrix material can include substantially pure chromium. Alternatively, the matrix material can include a chromium alloy, including chromium and one or more additional elemental species. The one or more additional elemental species can include at least one transition metal and / or post-transition metal. Examples of the at least one transition metal for use in the matrix material can include chromium, copper, zirconium, titanium, tungsten, molybdenum, tungsten, manganese, niobium, cobalt, and iron. The matrix material can include silicon.

[0026] The weight percentage of the matrix material in the first material can be greater than about 80 wt.%. In one example, the weight percentage of the matrix material in the first material is greater than about 85 wt.%. In another example, the weight percentage of the matrix material in the first material is greater than about 90 wt.%. In another example, the weight percentage of the matrix material in the first material is greater than about 95 wt.%. In another example, the weight percentage of the matrix material in the first material is greater than about 98 wt.%. In another example, the weight percentage of the matrix material in the first material is greater than about 94 wt.%, greater than about 96 wt.%, greater than about 97 wt.%, greater than about 98 wt.%, greater than about 99 wt.%, or values therebetween. In one example, the weight percentage of the matrix material in the first material ranges from about 75 wt.% to about 99.99 wt.%. In another example, the weight percentage of the matrix material in the first material ranges from about 90 wt.% to about 99.97 wt.%.

[0027] The density of the matrix material can be greater than about 4 g / cm3. The density of the matrix material can be greater than about 6 g / cm3. The density of the matrix material can be less than about 10 g / cm3. The density of the matrix material can be less than about 9 g / cm3. The density of the matrix material can range from about 7 g / cm3to about 9 g / cm3. The native thermalconductivity of the matrix material can be greater than about 100 W / m*K. The native thermal conductivity of the matrix material can be the average thermal conductivity of the material(s) forming the matrix material if isolated and in the substantially pure form, typically distinct from the overall thermal conductivity of the first material. For example, if the matrix material is copper, the native thermal conductivity of the matrix material is about 400 W / m*K.

[0028] In one example, the native thermal conductivity of the matrix material is greater than about 200 W / m*K. In another example, the native thermal conductivity of the matrix material is greater than about 250 W / m*K. In another example, the native thermal conductivity of the matrix material is greater than about 300 W / m*K. The native thermal conductivity of the matrix material can range from about 100 W / m*K to about 500 W / m*K. The native thermal conductivity of the matrix material can range from about 200 W / m*K to about 500 W / m*K.

[0029] A metal-oxide component can be dispersed in the matrix material. Additionally, the metal-oxide component can be dispersed on the surface of the matrix material. The metal-oxide component can stabilize the grain structure of the matrix material. In one example, while pure copper has excellent thermal and electrical conductivity, pure copper tends to soften well below its melting point of about 1084 °C. In one embodiment, the metal-oxide component and the matrix material form an oxide dispersion strengthened metal alloy. By utilizing the metal-oxide component in combination with the matrix material, the first material can be used long-term at temperatures closer to its melting point. Further, compared to ferrous and nickel-based alloys, the first material exhibits improved corrosion resistance in various applications, such as applications utilizing or producing hydrogen gas, water vapor, and / or carbon monoxide gas. These gases and vapors are conventionally capable of initiating and promoting corrosion to materials at various temperatures.

[0030] The metal-oxide component can include one or more metal-oxides. In one example, the metal-oxide component can include at least one oxide of aluminum, yttrium, and magnesium. For example, the metal-oxide component can include at least one of aluminum oxide, yttrium oxide, and magnesium oxide. The inclusion of the metal-oxide component in and / or on the matrix material can stabilize the grain structure and boundaries of the matrix material up to very high temperatures. Accordingly, the inclusion of the metal-oxide component in and / or on the matrix material can improve the thermal stability of the matrix material at high temperatures(such as temperatures up to 1000 °C). Additionally, the first material can improve thermal conductivity compared to nickel-containing alloys.

[0031] The weight percentage of the metal-oxide component in the first material can be greater than 0.001 wt.%. In one example, the weight percentage of the metal-oxide component in the first material can be greater than 0.01 wt.%. In another example, the weight percentage of the metal-oxide component in the first material can be greater than 0.1 wt.%. The weight percentage of the metal-oxide component in the first material can range from about 0.03 wt.% to about 5 wt.%. In one example, the weight percentage of the metal-oxide component in the first material ranges from about 0.1 wt.% to about 3 wt.%. The weight percentage of the metal-oxide component in the first material can be less than 10 wt.%. The weight percentage of the metal- oxide component in the first material can be less than 5 wt.%. The weight percentage of the metal-oxide component in the first material can be less than 2 wt.%. The inclusion of the metal- oxide component, with weight percentages of the present disclosure, can be used to tune the thermal stability and mechanical properties (such as ductility) of the first material.

[0032] The metal-oxide component can be in the form of particles dispersed in the matrix material. In one example, the metal-oxide component includes particles having a mean particle size of less than about 1 pm. In another example, the metal-oxide component includes particles having a mean particle size of less than about 100 nm. In another example, the metal-oxide component includes particles having a mean particle size of less than about 50 nm. In another example, the metal-oxide component includes particles having a mean particle size of less than about 10 nm. Accordingly, the metal-oxide component can include a plurality of nanoparticles dispersed in the matrix material. In one example, the metal-oxide component includes particles having a mean particle size of greater than about 5 nm. In another example, the metal-oxide component includes particles having a mean particle size of greater than about 20 nm. For the purposes hereof, the term “mean particle size” refers to a cumulative weight average value (dso) in which 50% of the particles are larger than the value, and 50% of the particles arc smaller than the value.

[0033] The density of the first material can be greater than about 4 g / cm3. The density of the first material can be greater than about 6 g / cm3. The density of the first material can be less than about 10 g / cm3. The density of the first material can be less than about 9 g / cm3. In one example, the density of the first material can range from about 7 g / cm3to about 9 g / cm3. Theoverall thermal conductivity of the first material can be greater than about 100 W / m*K. In one example, the overall thermal conductivity of the first material is greater than about 200 W / m*K. In another example, the overall thermal conductivity of the first material is greater than about 250 W / m*K. In another example, the overall thermal conductivity of the first material is greater than about 300 W / m*K. The overall thermal conductivity of the first material can range from about 100 W / m*K to about 500 W / m*K. The overall thermal conductivity of the first material can range from about 200 W / m*K to about 500 W / m*K.[00341 The electrical conductivity of the first material can be greater than 20 MS / m at about 20 °C. The electrical conductivity of the first material can be greater than 40 MS / m at about 20 °C. The electrical conductivity of the first material can be greater than 50 MS / m at about 20 °C. In one example, the electrical conductivity of the first material ranges from about10 MS / m at about 20 °C to about 60 MS / m at about 20 °C. In another example, the electrical conductivity of the first material ranges from about 30 MS / m at about 20 °C to about 60 MS / m at about 20 °C.

[0035] In one embodiment, the first material can be formed by melting an elemental species into / with a metal-containing material, such as a copper-containing material, to form a mixture. For example, the elemental species can include at least one of aluminum, yttrium, and magnesium. This mixture may be formed into a powder. Subsequently, the elemental species, such as at least one of aluminum, yttrium, and magnesium, can be selectively oxidized. Therefore, by oxidizing the elemental species, a metal-oxide can be formed (metal-oxide component of the present disclosure) and at least partially dispersed within the matrix material. In another embodiments, the first material can be formed by mechanically mixing alloycontaining powder(s) with an oxide component, such as metal oxide. In another embodiment, the first material is formed with a billet, including melting and mixing to form a grain boundary mixture of the oxide component in the alloy. In one non-limiting example, the first materials of the present disclosure include an oxide dispersion strengthened copper or copper alloy material. The first material can be extruded, drawn, bent, and / or cut to form desired structures.

[0036] Structures useful in chemical processing applications can be formed from and include at least the first material. In one example, the structure includes a channel capable of permitting fluid flow therethrough. In another example, the structure includes at least one of tubes, baffles, and fin structures. Examples of fin structures include a straight fin and a helicalfin. The helical fin can include a single helix or spiral configuration. Alternatively, or additionally, the helical fin may include a multi-helix fin structure, such as a double helix or triple helix or more configuration. In some embodiments, the helical fin can include the same, or various, helices along the length of a tubular structure. For example, a first portion of the helical fin along a first portion of a tubular structure can include a single helix, while a second portion of the helical fin along a second portion of the tubular structure can include a double helix or triple helix or more configuration.[00371 Since the first material exhibits a high thermal conductivity value, heat can be efficiently transferred through the structure to one or more fluids. The tubular structure can exhibit an annular cross- section. For example, the first material can be drawn to form these tubular structures. Tubular structures including the first material can be fluidically connected to other tubular structures formed from distinct materials using a suitable connection technique, such as brazing techniques, where the brazed joint forms a liquid and / or gas-tight seal.Additional connection techniques can include tube rolling (e.g., for heat exchanger).

[0038] Embodiments of the present disclosure include utilizing the structure including the first material in a chemical processing unit. Chemical processing units of the present disclosure include chemical reactors, heat exchangers, tubular structures for fluid transfer, and the like. In one example, the chemical processing unit includes a chemical reactor vessel. A chemical reactor is an engineered system or vessel in which chemical reaction(s) can occur under controlled conditions of temperature, pressure, flow, and / or concentration. In another example, the chemical processing unit includes at least a portion of a heat exchanger. A heat exchanger is an apparatus designed to efficiently transfer or exchange heat from one fluid to another fluid, without mixing them.

[0039] At least one structure within the chemical processing unit can include the first material of the present disclosure. Various structures, such as tubes, fins, baffles, and / or helical structures can include / be formed from the first material. In another example, the first material can be used to form a vessel, such as a conduit, chemical reactor vessel, or heat exchange vessel. The conduit can be used as transfer piping between vessels. The first material can be utilized in at least a portion of the chemical processing unit subjected to, and in fluid communication with, one or more corrosion-promoting gases (such as at least one of hydrogen gas, water vapor, and carbon monoxide gas at high temperatures). Importantly, the first material can be utilized in atleast a portion of the chemical processing unit to improve at least one of corrosion resistance and thermal conductivity.

[0040] The first material can also be formed as a coating composition. In one example, the coating composition can be cold-spray coated. The coating composition can be applied as coating using various thermal spray methods. For example, the coating composition can be coldspray coated to form an environmental barrier layer. In another example, the coating composition can be cold-spray coated to connect two or more structures together, such as fins or baffles to tubes. In another example, the coating composition can be used as a gas sealant for joints between two structures. The first material can be in the form of a solid powder, such as a solid powder having a mean particle size of less than about 100 pm, or between about 1 pm and about 50 pm. This solid powder can be accelerated using a gas jet to deposit and adhere the first material on a second material, such as a substrate (e.g., pipe, reactor, and / or heat exchanger). In another example, the first material can be utilized as a liner (e.g., cladding) inside of / on a second material. For example, if the second material is in the form of a pipe, the combination can be manufactured by hydraulic expansion of an oxide dispersion strengthened alloy tube liner into the pipe.

[0041] Embodiments of the present disclosure include utilizing the first material as an environmental barrier coating (e.g., in the form of cladding) on one or more surfaces of a chemical processing unit, where the one or more surfaces can include a second material distinct from the first material. The environmental barrier coating can reduce or prevent corrosion caused by one or more gases that can otherwise occur to the second material without an environmental barrier layer. In one example, corrosion includes deterioration of a material as a result of a chemical reaction / interaction with its environment. Extreme corrosion can include metal dusting. For example, metal dusting is a severe form of corrosive degradation of metals at various temperatures (such as 100-500 °C) in carbon-containing gaseous environments, often causing pitting and degradation (e.g., of the second material) into small particles. In one example, coking can occur at temperatures ranging from about 500-800 °C. Utilizing the environmental barrier layer reduces or prevents corrosion to materials that can otherwise suffer from corrosive deterioration by reducing interaction of the material with corrosion-causing gases or vapors.

[0042] The environmental barrier coating can include a layer sufficient to reduce or prevent corrosion from at least one of hydrogen gas, water vapor, and carbon monoxide gas atvarious temperatures. The second material can include a metal-containing material. The metalcontaining material can include one or more of iron and nickel. For example, the metalcontaining material can include an iron alloy or a nickel alloy. The metal-containing material can include an iron nickel alloy. In one example, the metal-containing material includes one or more of iron, carbon, chromium, nickel, manganese, molybdenum, zinc, cobalt, copper, titanium, niobium, and tungsten. Various structures of the present disclosure can include the second material, such as vessels, heat exchangers or tubes. The second material can form a tubular structure. In one example, the first material can be cold-spray coated on the second material to form the environmental barrier layer.

[0043] FIG. 1A illustrates an exploded view of at least a portion of chemical processing unit 100. Chemical processing unit 100 includes a chemical reactor. Chemical processing unit 100 includes internal reaction volume 104, inlet 106, outlet 108, return conduit 110, distal portion 122, and proximal portion 124. FIG. IB illustrates chemical processing unit 100, according to some embodiments. FIG. IB shows only some of the major components of chemical processing unit 100 to better illustrate the bayonet design reactor flow paths. One of skill in the art will readily appreciate that the components of the reactors that are not shown in FIG. IB but are described elsewhere herein are equally applicable to the embodiment of chemical processing unit 100. While chemical processing unit 100 is shown as a chemical reactor in the non-limiting illustration of FIG. IB, alternatively, the chemical processing unit can include a heat exchanger or portions thereof, such as a heat exchanger tube and / or a heat exchanger liner.

[0044] Chemical processing unit 100 includes vessel 102, inlet 106, and outlet 108. Vessel 102 is shown as partially translucent in FIG. IB to better illustrate the internal structure of chemical processing unit 100. Vessel 102 is generally tubular in shape with its internal walls defining internal reaction volume 104. While vessel 102 is generally tubular in shape, in other embodiments the vessels of the present disclosure take other shapes, such as prismatic, hexagonal, or other geometries. Vessel 102 also includes distal portion 122 and proximal portion 124 opposite distal portion 122. Vessel 102 can be formed from the second material including at least one of iron, nickel, and alloys thereof. In other embodiments, vessel 102 is formed from at least a second material including a ceramic material. For example, the ceramic material can include silicon carbide. Vessel 102 can include an interior coating or liner. Accordingly, vessel102 can be made from silicon carbide or alumina. Vessel 102 can be formed from oxide or nonoxide ceramics, where the oxide or non-oxide ceramics are a pressure vessel.

[0045] Internal reaction volume 104 is the portion or area of chemical processing unit 100 in which catalytic reactions occur to convert reactant(s) to product(s) (catalyst materials are not illustrated in FIG. IB). Internal reaction volume 104 is also defined by the outer walls of return conduit 110. Return conduit 110 is arranged within and can span most of the length of vessel 102. A proximal end of return conduit 110 is attached to or otherwise secured against outlet 108 at or near the proximal end of vessel 102, while a distal end of return conduit 110 is positioned at or near the distal end of vessel 102. Collectively, the inner walls of return conduit 110 and outlet 108 define a return flow channel. While only one return conduit 110 is shown in FIG. IB, more than one return conduit 110 can be utilized. In one example, the return conduit 110 includes a tubular structure. In other embodiments, chemical processing unitlOO can function as a reactor without return conduit 110. Accordingly, chemical processing unit 100 can include vessel 102, inlet 106, and outlet 108, without return conduit 110. For example, chemical processing unit 100 can include a fixed bed reactor, with various bed and vessel configurations possible.

[0046] With regard to the fluidic flow path of chemical processing unit 100, during use one or more fluidic reactants are directed into a proximal portion of chemical processing unit 100 through inlet 106 along direction 112. While only one inlet 106 is shown in FIG. IB, more than one inlet 106 can be utilized. The reactants then travel generally along direction 114 through internal reaction volume 104 along the length, and towards a distal portion, of chemical processing unit 100. While traveling through internal reaction volume 104, the reactants contact catalyst materials (e.g. heterogeneous catalyst materials) and undergo catalytic reactions to produce one or more products (e.g., one or more fluidic products). In some embodiments, chemical processing units of the present disclosure can use slurry-bed catalysts. Once in the distal portion of chemical processing unit 100, the reactant(s) and / or formed reaction product(s) enter the return flow channel by generally following direction 116 and pass into the distal end of return conduit 110. In one example, return conduit 110 and the return flow channel are devoid of catalyst materials, thus the catalytic conversion of reactant(s) to product(s) decreases or stops once the reactant(s) and / or reaction product(s) enter return conduit 110. In other embodiments, catalyst materials can be positioned in at least a portion of return conduit 110. The reactant(s) and / or reaction product(s) then flow back up along the return flow channel towards the proximalend of chemical processing unit 100 through return conduit 110 along direction 118 and out of chemical processing unit 100 via outlet 108 along direction 120.

[0047] The first material of the present disclosure can be used within various portions of chemical processing unit 100. For example, at least a portion of return conduit 110 can include the first material of the present disclosure. In one example, return conduit 110 is formed from the first material. In another example, the first material is in contact with at least a portion of return conduit 110, where the first material acts as a barrier layer to reduce or prevent corrosion to return conduit 110. In some examples, the first material is coated on at least a portion of return conduit 110. Additionally, or alternatively, the first material may be provided on at least a portion of an interior or exterior surface of vessel 102 to act as a barrier layer to reduce or prevent corrosion to vessel 102. During operation, since at least a portion of chemical processing unit 100 can interact with at least one of hydrogen gas, water vapor, and carbon monoxide gas, and at least a portion of chemical processing unit 100 can be operated at (conventionally) corrosion promoting temperatures of between 400 °C and 1000 °C, the utilization of the first material is important for reducing or preventing corrosion at these temperatures.

[0048] In one embodiment, chemical processing unit 100 includes a plug-flow reactor (PFR). Plug flow reactors are tubular reactors in which each reactant molecule enters and travels through the reactor as a plug. Plug-flow reactors generally include a tubular reaction vessel having at least one inlet and at least one outlet. The tubular reaction vessel can include a volume including one or more catalytic materials, where the reactants can be consumed as the reactants flow from the inlet to the outlet. Alternatively, or additionally, the catalytic material can be in contact with at least one surface of the tubular reaction vessel.

[0049] FIG. 1C illustrates a side view of at least a portion of chemical processing unit 150. FIG. ID illustrates chemical processing unit 150, according to some embodiments. Chemical processing unit 150 includes a heat exchanger (e.g., shell and tube heat exchanger). Various front end head types, shell types, and rear end head types may be utilized. Chemical processing unit 150 can include additional structures not shown, such as inlets, outlets, fins, baffles, and multiple tubes. For example, chemical processing unit 150 can utilize a plurality of tubes for heat transfer.

[0050] Chemical processing unit 150 includes first conduit 170 and shell 180. First conduit 170 includes conduit inlet 172 and conduit outlet 174. Shell 180 includes shell inlet 182and shell outlet 184. Heat is transferred from first fluid(s) flowing along example flow path 176 to second fluid(s) flowing along example flow path 186, or from second fluid(s) flowing along example flow path 186 to first fluid(s) flowing along example flow path 176. While the example flow paths in FIG. ID are shown as one example, the flow paths can exhibit concurrent flows, cross-flow orientations, or countercurrent flow orientations.

[0051] Chemical processing unit 150 can be formed from materials of the present disclosure, such as metal alloys and ceramics. The first material of the present disclosure can be used within various portions of chemical processing unit 150. For example, at least a portion of conduit 170 can include the first material of the present disclosure. In one example, conduit 170 is formed from the first material. In another example, the first material is in contact with at least a portion of conduit 170, where the first material acts as a barrier layer to reduce or prevent corrosion to conduit 170. First material can also be applied as a barrier coating to alternative surfaces of chemical processing unit 150, such as a surface of shell 180. In one example, the first material can be utilized for additional structures not shown, such as inlets, outlets, fins, baffles, and multiple tubes.

[0052] While chemical processing unit 150 is shown as an example shell and tube heat exchanger in FIG. ID, and first conduit 170 is shown as a tubular structure extending through shell 180, alternative heat exchanger designs can be useful for the present disclosure. Chemical processing unit 150 can include an indirect heat exchanger. For example, chemical processing unit 150 can include a plate heat exchanger. Additional examples of heat exchangers include double-pipe, non-tubular heat exchangers, boilers, evaporators, and condensers. In some embodiments, the heat exchanger can include an inlet and outlet for one or more gases and a heating element (e.g., electrical heating element) for transferring heat to the one or more gases.

[0053] FIG. 2A illustrates fluid transfer structure 200, according to some embodiments. In one example, fluid transfer structure 200 is a chemical processing unit. In another example, fluid transfer structure is utilized in at least a portion of a chemical processing unit, such as chemical processing unit 100 or chemical processing unit 150. In one embodiment, fluid transfer structure 200 is an assembly, such as a tubular assembly. Fluid transfer structure 200 includes inlet 210 on a first end and outlet 220 on a second end. Fluid transfer structure 200 generally includes a structure capable of holding or transporting fluid(s). For example, at least a portion of fluid transfer structure 200 generally includes a tubular structure. In some embodiments, the tubularstructure can be shaped as a hollow cylinder, hollow square tube, hollow rectangular tube, or other shapes of hollow tubing having an inner channel. The tubular- structure can include an inner channel configured for holding or transporting fluids. In one example, at least a portion of fluid transfer structure 200 can include an annular- cross section. For example, at least a portion of fluid transfer structure 200 can be shaped as a hollow cylinder, with the inner channel having a circular cross-sectional shape. The inner channel can exhibit alternative cross-sectional shapes, such as the shape of a triangle, square, rectangle, oval, or hexagon.[00541 FIG. 2B illustrates an end view of fluid transfer structure 200, according to some embodiments. Fluid transfer structure 200 includes first component 250 and second component 260. As shown in FIG. 2B, second component 260 is arranged surrounding first component 250, sufficient for second component 260 to be an environmental barrier cladding for first component 250. Therefore, at least a portion of an exterior surface of fluid transfer structure 200 is formed of second component 260. Second component 260 can be utilized to prevent or reduce corrosion to first component 250 by chemicals, such as gases and / or vapors, external to fluid transfer structure 200.

[0055] First component 250 can include a metal-containing material. The metal -containing material can include a metal alloy. The metal-containing material can include one or more of iron, carbon, chromium, nickel, manganese, molybdenum, zinc, cobalt, copper, titanium, niobium, tungsten, and alloys thereof. In one example, the metal-containing material includes two or more of iron, carbon, chromium, molybdenum, titanium, niobium, tungsten, and nickel. In another example, the metal-containing material can include stainless steel having at least iron, chromium, and nickel. In another example, the metal-containing material can include stainless steel having at least chromium, nickel, and molybdenum.

[0056] The metal-containing material can include at least 5 wt.% nickel. In one example, the metal-containing material includes between about 5 wt.% and about 15 wt.% nickel. The metal-containing material can include at least 15 wt.% chromium. In one example, the metalcontaining material includes between about 16 wt.% and about 20 wt.% chromium. The metalcontaining material can include at least 2 wt.% molybdenum. In one example, the metalcontaining material includes between 2 wt.% and 4 wt.% molybdenum. The metal-containing material can include at least 60 wt.% iron. The metal-containing material can include at least 80 wt.% copper.

[0057] First component 250 can include a ceramic-containing material. In one example, the ceramic-containing material can include one or more non-oxide ceramics. Examples of nonoxide ceramics include carbides and nitrides of boron, aluminum, silicon, titanium, and zirconium. In another example, the ceramic-containing material includes one or more oxide ceramics. Examples of oxide ceramics include oxides of aluminum, silicon, magnesium, zirconium, yttrium, and mixtures thereof. In one example, the ceramic-containing material includes at least one of carbon, silicon, nitrogen, and aluminum. In another example, the ceramic-containing material includes at least one of silicon carbide, silicon nitride, and aluminum nitride. For example, the first component 250 may include silicon carbide. Silicon carbide can be selected due to the excellent high temperature properties and chemical resistance of silicon carbide.

[0058] Second component 260 includes a matrix material and a metal-oxide component of the present disclosure. The matrix material is capable of at least partially surrounding or encapsulating other components of the present disclosure, such as the metal-oxide component. Since the overall thermal conductivity of second component 260 can be greater than about 200 W / m*K, second component 260 can be utilized to improve corrosion resistance without sacrificing heat transfer to first component 250. Accordingly, the combination of first component 250 and second component 260 improves corrosion resistance without sacrificing overall thermal conductivity.

[0059] In one example, the matrix material includes copper or alloys thereof. Accordingly, the matrix material can include substantially pure copper. Alternatively, the matrix material can include a copper alloy, including copper and one or more additional elemental species. The one or more additional elemental species can include at least one transition metal and / or posttransition metal. Examples of the at least one transition metal for use in the matrix material can include chromium, nickel, silver, zinc, and zirconium. In one non-limiting example, the matrix material includes a copper chromium alloy. In another non-limiting example, the matrix material includes a copper zirconium alloy.

[0060] The metal-oxide component can include one or more metal-oxides. In one example, metal in the metal-oxide component can include at least one of aluminum, yttrium, and magnesium. For example, the metal-oxide component can include at least one of aluminum oxide, yttrium oxide, and magnesium oxide. The inclusion of the metal-oxide component inand / or on the matrix material can stabilize the grain structure and boundaries of the matrix material up to very high temperatures. Accordingly, the inclusion of the metal-oxide component in and / or on the matrix material can improve the thermal stability of the matrix material at high temperatures (such as temperatures up to 1000 °C).

[0061] FIG. 2C illustrates an end view of fluid transfer structure 200, according to some embodiments. FIG. 2C illustrates an alternative embodiment from FIG. 2B, where second component 260 is utilized as a liner on an interior surface of first component 250. Therefore, at least a portion of an interior surface of fluid transfer structure 200 is formed of second component 260. Second component 260 can be utilized to prevent or reduce corrosion to first component 250 by chemicals, such as gases and / or vapors, being transferred by, or contained within, fluid transfer structure 200.

[0062] FIG. 2D illustrates a view of detail C from FIG. 2B, according to some embodiments. FIG. 2E illustrates a view of detail D from FIG. 2C, according to some embodiments. FIG. 2D and FIG. 2E illustrate that additional layer 262 can be utilized between first component 250 and second component 260. Additional layer 262 can be used as an interface between first component 250 and second component 260 for added mechanical and / or chemical protection. Additional layer 262 can include one or more metals or alloys thereof. In one example, additional layer 262 includes a chromium-containing material. For example, the chromium-containing material can be applied to at least one of the first component 250 and the second component 260 using electroplating. The additional layer 262 can enhance mechanical abrasion resistance and / or chemical protection from leaching or copper diffusion into the first component 250.

[0063] FIG. 3 illustrates method 300 for improving corrosion resistance in a chemical processing unit, according to some embodiments. Method 300 includes at least Step 310. Referring to Step 310, a structure is provided, where the structure includes a matrix material and a metal-oxide dispersed in the matrix material. The metal-oxide includes metal-oxide components of the present disclosure, and the matrix material includes matrix materials of the present disclosure. The structure can be utilized in a chemical processing unit, such as in a chemical reactor vessel or in a heat exchanger vessel. In one example, at least a portion of the structure includes a tubular structure. In another example, at least a portion of the structure has an annular cross section. In another example, at least a portion of the structure includes a finstructure. Examples of fin structures include a straight fin and a helical fin. The structure can include at least one of a tube, return conduit, exhaust tube, baffle, and a fin structure, optionally utilized in a chemical reactor and / or heat exchanger. The structure can exhibit a high thermal conductivity and can be stable at a wide range of temperatures while exhibiting excellent corrosion resistance.

[0064] FIG. 4 illustrates method 400 for improving corrosion resistance in a chemical processing unit, according to some embodiments. Method 400 includes at least Step 410. Referring to Step 410, a first material is applied to a second material sufficient for at least a portion of the first material to be in contact with at least a portion of the second material. The first material and the second material include first materials and second materials of the present disclosure, respectively. For example, the first material can be coated on the second material sufficient to form a barrier layer to improve corrosion resistance of a surface or structure of the chemical processing unit. Various application methods can be utilized, such as cold-spray coating. In one non-limiting example, the first material is applied to a second material, where the second material forms a chemical reactor vessel having an inner surface. Method 400 can include utilizing the structure in a chemical processing unit operated at a temperature ranging from 300 °C to 1000 °C. Method 400 can include utilizing the structure in a chemical processing unit operated at a temperature ranging from 500 °C to 800 °C.Discussion of Possible Embodiments

[0065] Clause 1. A chemical processing unit, including: a vessel having at least one vessel inlet and at least one vessel outlet; and a structure, the structure at least partially positioned within the vessel, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, the matrix material including one or more of copper and nickel, wherein at least one of copper and nickel has a weight percentage greater than 10 wt.% based on a total weight of the structure.

[0066] The clause of the preceding paragraph can optionally include, additionally and / or alternatively any one or more of the following features, configurations and / or additional components.

[0067] Clause 2. The chemical processing unit of clause 1, wherein at least a portion of the structure includes a tubular structure.

[0068] Clause 3. The chemical processing unit of clause 1, wherein at least a portion of the structure has an annular cross section.

[0069] Clause 4. The chemical processing unit of clause 1, wherein at least a portion of the structure includes a fin structure.

[0070] Clause 5. The chemical processing unit of clause 4, wherein the fin structure includes a straight fin.

[0071] Clause 6. The chemical processing unit of clause 4, wherein the fin structure includes a helical fin.

[0072] Clause 7. The chemical processing unit of clause 1, wherein the metal-oxide includes at least one of aluminum oxide, yttrium oxide, and magnesium oxide.

[0073] Clause 8. The chemical processing unit of clause 1, wherein a weight percentage of the metal-oxide in the structure ranges from about 0.03 wt.% to about 5 wt.%.

[0074] Clause 9. The chemical processing unit of clause 1, wherein a weight percentage of copper in the structure ranges from about 80 wt.% to about 99.95 wt.%.

[0075] Clause 10. The chemical processing unit of clause 1, wherein the matrix material further includes at least one of chromium and zirconium.

[0076] Clause 11. The chemical processing unit of any one of clauses 1-10, wherein the vessel includes a ceramic material.

[0077] Clause 12. The chemical processing unit of clause 11, wherein the ceramic material includes silicon carbide.

[0078] Clause 13. The chemical processing unit of any one of clauses 1-10, wherein the vessel includes an alloy having at least one of nickel and iron.

[0079] Clause 14. The chemical processing unit of any one of clauses 1-10, wherein the vessel is a chemical reactor vessel.

[0080] Clause 15. The chemical processing unit of any one of clauses 1-10, wherein the vessel is a heat exchanger vessel.

[0081] Clause 16. A tubular assembly for use in chemical processing, including: a first component including a metal-containing matrix material and a metal-oxide dispersed in the metal-containing matrix material; and a second component including at least one of a metalcontaining material and a ceramic-containing material.

[0082] The clause of the preceding paragraph can optionally include, additionally and / or alternatively any one or more of the following features, configurations and / or additional components.

[0083] Clause 17. The tubular assembly of clause 16, wherein the metal-containing matrix material includes at least one of nickel and copper.

[0084] Clause 18. The tubular assembly of clause 16, wherein the metal-containing matrix material includes at least 10 wt.% copper based on a total weight of the first component.

[0085] Clause 19. The tubular assembly of clause 16, wherein the metal-containing matrix material includes at least 10 wt.% nickel based on a total weight of the first component.

[0086] Clause 20. The tubular assembly of clause 16, wherein the metal-oxide includes at least one of aluminum oxide, yttrium oxide, and magnesium oxide.

[0087] Clause 21. The tubular assembly of clause 16, wherein the second component includes the metal-containing material, and the metal-containing material includes one or more of iron, carbon, chromium, nickel, manganese, molybdenum, zinc, cobalt, copper, titanium, niobium, and tungsten.

[0088] Clause 22. The tubular assembly of any one of clauses 16-21, wherein at least a portion of the tubular assembly has an annular cross section.

[0089] Clause 23. The tubular assembly of any one of clauses 16-21, wherein at least a portion of the first component is in contact with at least a portion of the second component.

[0090] Clause 24. The tubular assembly of clause 16, further including an additional layer arranged between the first component and the second component.

[0091] Clause 25. The tubular assembly of clause 24, wherein the additional layer includes a chromium-containing material.

[0092] Clause 26. The tubular assembly of any one of clauses 16-21, wherein the first component is arranged substantially surrounding the second component sufficient for the first component to be an environmental barrier cladding.

[0093] Clause 27. The tubular assembly of any one of clauses 16-21, wherein the first component is positioned in the form of a liner and in contact with an interior surface of the second component.

[0094] Clause 28. A method for improving corrosion resistance in chemical processing, including: utilizing a structure in a chemical processing unit to improve corrosion resistance to atleast one of hydrogen gas, water vapor, and carbon monoxide gas, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, wherein the matrix material includes at least one of copper and nickel.

[0095] The clause of the preceding paragraph can optionally include, additionally and / or alternatively any one or more of the following features, configurations and / or additional components.

[0096] Clause 29. The method of clause 28, including utilizing the structure in a chemical reactor vessel.

[0097] Clause 30. The method of clause 28, including utilizing the structure in a heat exchanger vessel.

[0098] Clause 31. The method of clause 28, wherein the metal-oxide includes at least one of aluminum oxide, yttrium oxide, and magnesium oxide.

[0099] Clause 32. The method of clause 28, wherein a weight percentage of the metal- oxide in the structure ranges from about 0.03 wt.% to about 5 wt.%.

[0100] Clause 33. The method of clause 28, wherein a weight percentage of copper in the structure ranges from about 80 wt.% to about 99.95 wt.%.

[0101] Clause 34. The method of clause 28, including utilizing the structure in a chemical processing unit operated at a temperature ranging from 300 °C to 1000 °C.

[0102] While the invention has been described with reference to an exemplary embodiment(s), it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment(s) disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims

CLAIMS:

1. A chemical processing unit, comprising: a vessel having at least one vessel inlet and at least one vessel outlet; and a structure, the structure at least partially positioned within the vessel, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, the matrix material including one or more of copper and nickel, wherein at least one of copper and nickel has a weight percentage greater than 10 wt.% based on a total weight of the structure.

2. The chemical processing unit of claim 1, wherein at least a portion of the structure includes a tubular structure.

3. The chemical processing unit of claim 1, wherein at least a portion of the structure has an annular cross section.

4. The chemical processing unit of claim 1, wherein at least a portion of the structure includes a fin structure.

5. The chemical processing unit of claim 4, wherein the fin structure includes a straight fin.

6. The chemical processing unit of claim 4, wherein the fin structure includes a helical fin.

7. The chemical processing unit of claim 1, wherein the metal-oxide includes at least one of aluminum oxide, yttrium oxide, and magnesium oxide.

8. The chemical processing unit of claim 1, wherein a weight percentage of the metal-oxide in the structure ranges from about 0.03 wt.% to about 5 wt.%.

9. The chemical processing unit of claim 1, wherein a weight percentage of copper in the structure ranges from about 80 wt.% to about 99.95 wt.%.

10. The chemical processing unit of claim 1, wherein the matrix material further includes at least one of chromium and zirconium.

11. The chemical processing unit of any one of claims 1-10, wherein the vessel includes a ceramic material.

12. The chemical processing unit of claim 11, wherein the ceramic material includes silicon carbide.

13. The chemical processing unit of any one of claims 1-10, wherein the vessel includes an alloy having at least one of nickel and iron.

14. The chemical processing unit of any one of claims 1-10, wherein the vessel is a chemical reactor vessel.

15. The chemical processing unit of any one of claims 1-10, wherein the vessel is a heat exchanger vessel.

16. A tubular assembly for use in chemical processing, comprising: a first component including a metal-containing matrix material and a metal-oxide dispersed in the metal-containing matrix material; and a second component including at least one of a metal-containing material and a ceramiccontaining material.

17. The tubular assembly of claim 16, wherein the metal-containing matrix material includes at least one of nickel and copper.

18. The tubular assembly of claim 16, wherein the metal-containing matrix material includes at least 10 wt.% copper based on a total weight of the first component.

19. The tubular assembly of claim 16, wherein the metal-containing matrix material includes at least 10 wt.% nickel based on a total weight of the first component.

20. The tubular assembly of claim 16, wherein the metal-oxide includes at least one of aluminum oxide, yttrium oxide, and magnesium oxide.

21. The tubular assembly of claim 16, wherein the second component includes the metalcontaining material, and the metal-containing material includes one or more of iron, carbon, chromium, nickel, manganese, molybdenum, zinc, cobalt, copper, titanium, niobium, and tungsten.

22. The tubular assembly of any one of claims 16-21, wherein at least a portion of the tubular assembly has an annular cross section.

23. The tubular assembly of any one of claims 16-21, wherein at least a portion of the first component is in contact with at least a portion of the second component.

24. The tubular assembly of claim 16, further including an additional layer arranged between the first component and the second component.

25. The tubular assembly of claim 24, wherein the additional layer includes a chromium- containing material.

26. The tubular assembly of any one of claims 16-21, wherein the first component is arranged substantially surrounding the second component sufficient for the first component to be an environmental barrier cladding.

27. The tubular assembly of any one of claims 16-21, wherein the first component is positioned in the form of a liner and in contact with an interior surface of the second component.

28. A method for improving corrosion resistance in chemical processing, comprising:utilizing a structure in a chemical processing unit to improve corrosion resistance to at least one of hydrogen gas, water vapor, and carbon monoxide gas, wherein the structure includes a matrix material and a metal-oxide dispersed in the matrix material, wherein the matrix material includes at least one of copper and nickel.

29. The method of claim 28, including utilizing the structure in a chemical reactor vessel.

30. The method of claim 28, including utilizing the structure in a heat exchanger vessel.

31. The method of claim 28, wherein the metal-oxide includes at least one of aluminum oxide, yttrium oxide, and magnesium oxide.

32. The method of claim 28, wherein a weight percentage of the metal-oxide in the structure ranges from about 0.03 wt.% to about 5 wt.%.

33. The method of claim 28, wherein a weight percentage of copper in the structure ranges from about 80 wt.% to about 99.95 wt.%.

34. The method of claim 28, including utilizing the structure in a chemical processing unit operated at a temperature ranging from 300 °C to 1000 °C.

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