Integrated oxidative reforming and electrolysis system and method for hydrogen production - Patents.com

Abstract

Methods and systems for producing hydrogen gas are described in which water is electrolyzed to produce hydrogen and oxygen, and a feedstock containing oxygenates and / or hydrocarbons is non-autothermal catalytic oxidatively reformed with oxygen to produce hydrogen. In certain implementations, the hydrogen production system includes an electrolyzer configured to receive water and produce hydrogen and oxygen from the water, and a non-autothermal segmented adiabatic reactor including a non-autothermal oxidative reforming catalyst configured to receive the feedstock, water, and oxygen produced in the electrolyzer for a non-autothermal catalytic oxidative reforming reaction to produce hydrogen. The hydrogen production method and system are particularly advantageous for using bioethanol to produce green hydrogen.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. §120 to U.S. patent application Ser. No. 17 / 727,720, filed April 23, 2022 in the names of Jeffrey Baker Harrison, Timothy Griffith Fogarty, Devendra Pakhare, Timothy David Appleberry, and Joshua Aaron Gubitz for OXIDATIVE REFORMING AND ELECTROLYSIS SYSTEM AND PROCESS FOR HYDROGEN GENERATION, which application and U.S. patent application Ser. No. 17 / 727,720 each claim priority under 35 U.S.C. §119 to Jeffrey Baker Harrison, Timothy Griffith Fogarty, Devendra Pakhare, Timothy David Appleberry, and Joshua Aaron Gubitz for OXIDATIVE REFORMING AND ELECTROLYSIS SYSTEM AND PROCESS FOR HYDROGEN GENERATION. This application claims the benefit of U.S. Provisional Patent Application No. 63 / 278,164, filed November 11, 2021 in the name of Gubitz. Each of U.S. Provisional Patent Application No. 63 / 278,164 and U.S. Patent Application No. 17 / 727,720 is incorporated herein by reference in its entirety for all purposes.

[0002] Field of the Disclosure

[0002] The present disclosure relates to hydrogen production, and more specifically, to an integrated oxidative reforming and electrolysis system and method for producing hydrogen in an efficient and cost-effective manner. The disclosed system and method can use a variety of feedstocks and are particularly advantageous in applications using renewable energy and renewable feedstock materials. The integrated oxidative reforming and electrolysis system and method can also be further integrated with (i) an ethanol refinery and / or (ii) a CO2 processing or carbon capture plant in various specific implementations and embodiments. [Background technology]

[0003] Description of Background and Related Art

[0003] Approximately 75 million metric tons / year of pure hydrogen are produced worldwide for use in petroleum refining, steel production, food processing, and industrial production of ammonia, methanol, and other chemical products.

[0004]

[0004] In recent years, more and more efforts and resources are being directed to realizing efficient, cost-effective and renewable hydrogen production, thereby accelerating the acceptance and use of hydrogen as an energy source. Hydrogen is attractive for use in fuel cells to generate electricity in a highly efficient and environmentally favorable manner, with water as the only by-product. It is expected that hydrogen will be increasingly used as an energy carrier to generate electricity for mobile and small to medium-scale stationary applications using fuel cells. This development will correspondingly encourage the development of technologies to use hydrogen as a clean fuel for vehicles and transportation power systems.

[0005]

[0005] A fundamental problem associated with current hydrogen production relates to the fact that the majority of hydrogen is currently produced by steam methane reforming ("SMR"). SMR is a highly energy intensive process due to the correspondingly high endothermic nature of the reforming reaction, and the hydrogen product of SMR is referred to as grey hydrogen because it releases significant amounts of greenhouse gases into the environment. As a result of these shortcomings, increasing attention and investment is being directed towards the development of green hydrogen, i.e. hydrogen produced using renewable energy sources. In the United States, significant efforts are being put into achieving green hydrogen production at a cost of US$1 per kilogram of H2 by 2030.

[0006]

[0006] Steam reforming of hydrocarbons other than methane can be carried out, but the reaction chemistry involved requires specialized equipment, metallurgy, and catalysts, as well as significant heating. As a result, high capital and operating costs make such steam reforming processes uneconomical for small-scale hydrogen production.

[0007]

[0007] Water electrolysis is a process for hydrogen production, but as a result of its high cost and high energy requirements, as water hydrolysis requires significant power to split water to obtain hydrogen and oxygen, less than 0.1% of the world's dedicated hydrogen production is obtained from water electrolysis. The thermal efficiency of industrial electrolyzers ranges from 60% to 70%, but the overall energy efficiency of water electrolysis ranges from only about 25% to 40% when considering transmission line losses and other power conversion losses. The energy requirements of current electrolysis systems range from 53.4 to 70.1 kWh per kilogram of hydrogen produced, and therefore the cost of electricity for the energy-intensive water electrolysis process is a major factor in the high production cost of hydrogen produced by such systems. This is true whether non-renewable or renewable power is used.

[0008]

[0008] In the face of the above challenges, the art continues to seek new approaches to producing hydrogen in an economical, efficient, and environmentally friendly manner. Summary of the Invention [Means for solving the problem]

[0009] overview The present disclosure relates to systems and methods for hydrogen production.

[0010]

[0010] In one aspect, the present disclosure relates to a method for producing hydrogen that includes electrolyzing water to produce hydrogen and oxygen, and using such oxygen to catalytically oxidatively reform a hydrocarbon feedstock to produce additional hydrogen.

[0011]

[0011] In another aspect, the present disclosure relates to a hydrogen generation system that includes an electrolyzer configured to receive water and produce hydrogen and oxygen therefrom, and a reactor including an oxidative reforming catalyst configured to receive a hydrocarbon feedstock, water, and oxygen produced in the electrolyzer for a catalytic oxidative reforming reaction of the hydrocarbon feedstock, water, and oxygen to produce hydrogen.

[0012]

[0012] In a further aspect, the present disclosure relates to a combined hydrogen production system including a water electrolyzer and a catalytic oxidative reforming reactor configured to receive oxygen from the water electrolyzer.

[0013]

[0013] Another aspect of the present disclosure relates to a method for producing hydrogen, the method including: (i) electrolyzing water to produce hydrogen and oxygen; and (ii) conducting an oxidative reforming reaction using the oxygen from the electrolysis.

[0014]

[0014] In another aspect, the disclosure relates to a method for producing hydrogen comprising electrolyzing water to produce hydrogen and oxygen, and non-autothermal catalytic oxidative reforming a feedstock fuel using the oxygen and water to produce hydrogen, wherein the feedstock fuel comprises a fuel selected from the group consisting of oxygenated additives, hydrocarbons, and mixtures thereof, and the feedstock fuel has a bio-derived content in the range of 5% by volume to 100% by volume based on the total volume of the feedstock fuel, and the reforming is carried out in a single adiabatic reactor into which the hydrocarbon feedstock fuel, oxygen, and water are introduced and into which produced hydrogen is discharged, the single adiabatic reactor comprising successive catalyst beds that are contacted sequentially in a flow through the reactor, the catalyst beds comprising (i) a first catalyst bed comprising a partial oxidation catalyst, (ii) a second catalyst bed comprising a steam reforming catalyst, (iii) a third catalyst bed comprising a high temperature water gas shift catalyst, and optionally (iv) a fourth catalyst bed comprising a low temperature water gas shift catalyst.

[0015]

[0015] Such a hydrogen production method can be carried out in an alternative embodiment in which the optional fourth catalyst bed is not present in the single adiabatic reactor, but is present in a low temperature water gas shift reactor external to the single adiabatic reactor.

[0016]

[0016] A further aspect of the present disclosure is a hydrogen production system including an electrolyzer configured to receive water and produce hydrogen and oxygen from the water, and a non-autothermal oxidative reforming system including a single adiabatic reactor configured to receive oxygen from the electrolyzer, a feed fuel from a feed fuel source, and water from a water source, the reactor including successive catalyst beds contacted sequentially in a flow through the reactor, the catalyst beds including: (i) a first catalyst bed including a partial oxidation catalyst; (ii) a second catalyst bed including a steam reforming catalyst; and (iii) a third catalyst bed including a high temperature water gas shift catalyst. and (iv) a fourth catalyst bed comprising a low temperature water gas shift catalyst, whereby a feed fuel from a feed fuel source, together with oxygen and water from the electrolyzer, is catalytically oxidatively reformed in the reactor to produce hydrogen, the reactor being configured to discharge the produced hydrogen, the feed fuel source being configured to provide a feed fuel comprising a fuel selected from the group consisting of an oxygenate, a hydrocarbon, and mixtures thereof, the feed fuel having a bio-derived content in the range of 5% by volume to 100% by volume, based on the total volume of the feed fuel.

[0017]

[0017] In another embodiment, such a hydrogen production system may be configured in an arrangement in which the optional fourth catalyst bed is not present in the single adiabatic reactor, but is present in a low temperature water gas shift reactor external to the single adiabatic reactor in the hydrogen production system.

[0018]

[0018] In another aspect, the disclosure is a thermally integrated hydrogen production system, the non-autothermal oxidative reforming system including: (A) an electrolyzer configured to receive water and produce hydrogen gas and oxygen gas therefrom; (B) an oxygen storage tank configured to receive oxygen gas from the electrolyzer; and (C) a single adiabatic reactor configured to receive oxygen gas from the oxygen storage tank, a feed fuel from a feed fuel source containing the feed fuel, and water from a water source, the single adiabatic reactor including successive catalyst beds that are contacted sequentially in a flow through the single adiabatic reactor, (i) a first catalyst bed comprising a partial oxidation catalyst, (ii) a second catalyst bed comprising a steam reforming catalyst, and (iii) a third catalyst bed comprising a high temperature water gas shift catalyst, whereby a feed fuel from a feed fuel supply source, together with oxygen from an oxygen storage tank and water from a water supply source, is catalytically oxidatively reformed in the single adiabatic reactor to produce an oxidatively reformed gas, which is primarily hydrogen, and the single adiabatic reactor is configured to exhaust the produced oxidatively reformed gas; and (D) a catalytically oxidatively reformed gas produced from the single adiabatic reactor. (E) a low temperature water-gas shift reactor configured to receive the reduced temperature oxidatively reformed gas from the first heat exchanger and convert at least a portion of the carbon monoxide in the reduced temperature oxidatively reformed gas to carbon dioxide to produce a low temperature water-gas shift reacted gas having a reduced carbon monoxide content, the low temperature water-gas shift reactor comprising a fourth catalyst bed comprising a low temperature water-gas shift catalyst; and (F) a low temperature water-gas shift reactor configured to receive the reduced temperature oxidatively reformed gas from the first heat exchanger and convert at least a portion of the carbon monoxide in the reduced temperature oxidatively reformed gas to carbon dioxide to produce a low temperature water-gas shift reacted gas having a reduced carbon monoxide content. (G) a hydrogen gas purifier configured to receive the low temperature water-gas shift reaction gas having a reduced carbon monoxide content from the water-gas shift reactor and produce separated hydrogen gas, and a carbon dioxide-containing exhaust gas; (H) a hydrogen gas storage configured to receive the hydrogen gas from the electrolyzer and the separated hydrogen gas from the hydrogen gas purifier; (I) a burner configured to combust the carbon dioxide-containing exhaust gas produced by the hydrogen gas purifier to obtain a flue gas; and (II) oxygen gas from an oxygen storage tank, a feed fuel from a feed fuel source, andand a second heat exchanger configured to receive flue gas from the burner for heating water from the water source; and (J) a process controller configured and arranged to coordinate operation of the electrolyzer and the non-autothermal oxidative reforming system in the thermally integrated hydrogen production system and to adjust the throughput of each of the electrolyzer and the non-autothermal oxidative reforming system to control the temperature in the single adiabatic reactor, wherein the feed fuel included in the feed fuel source comprises a fuel selected from the group consisting of oxygenates, hydrocarbons, and mixtures thereof, and the feed fuel has a bio-derived content in the range of 5% to 100% by volume, based on the total volume of the feed fuel.

[0019]

[0019] A further aspect of the present disclosure relates to a hydrogen production method comprising operating the thermally integrated hydrogen production system described immediately above to perform a hydrogen production method comprising electrolyzing water to produce hydrogen gas and oxygen gas therefrom; and non-autothermal catalytic oxidative reforming of a feedstock fuel together with the oxygen gas and water from a water source to produce hydrogen.

[0020]

[0020] Other aspects, features and embodiments of the present disclosure will become more fully apparent from the following description and the appended claims. [Brief description of the drawings]

[0021] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] 1 is a schematic flow diagram of a hydrogen production system according to one embodiment of the present disclosure that integrates an oxidative reforming process system with a low temperature electrolysis system. [Diagram 2]

[0022] 1 is a schematic flow diagram of a hydrogen production system according to another embodiment of the present disclosure, which integrates an oxidative reforming process system with a high temperature electrolysis system. [Diagram 3]

[0023] FIG. 1 is a schematic diagram of a segmented adiabatic reactor of a type useful for the hydrogen production systems and methods of the present disclosure, in one embodiment of the present disclosure. [Figure 4]

[0024] FIG. 1 is a schematic diagram of the reactor interior showing an exemplary arrangement for minimizing pressure drop and / or enhancing heat transfer from one catalyst bed to the next in a segmented adiabatic reactor according to another embodiment of the present disclosure. [Diagram 5]

[0025] FIG. 1 is a schematic diagram of a hydrogen production system including an integrated oxidative reforming and electrolysis plant, which is further integrated with an ethanol refiner and a CO2 processing or carbon capture system, according to another embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Detailed Description

[0026] The present disclosure relates to systems and methods for producing hydrogen in a cost-effective, efficient and environmentally beneficial manner.

[0023]

[0027] As used in this specification and the appended claims, the singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise.

[0024]

[0028] As used herein and in the appended claims, the term "about" in connection with a numerical value means a range of the corresponding value that may vary by ±10% in relation to the numerical value.

[0025]

[0029] As used herein and in the appended claims, the terms "biologically produced" and "bio-derived" in reference to fuel feedstocks exclude fossil fuel hydrocarbon feedstocks and fossil fuel hydrocarbon feedstock components.

[0026]

[0030] As used herein and in the appended claims, the term "high purity oxygen" refers to a gas containing at least 98 mol% oxygen (O2), and the term "high purity hydrogen" refers to a gas containing at least 98 mol% hydrogen.

[0027]

[0031] As used herein and in the appended claims, the term "predominantly" in reference to a component of a gas means that such component makes up more than 50 mol % of the gas.

[0028]

[0032] As used herein and in the appended claims, the term "oxygenate" refers to a chemical compound that contains oxygen as part of its chemical structure, which can be non-autothermally oxidatively reformed to produce hydrogen. Non-limiting examples of oxygenates include alcohols, such as methanol, ethanol, isopropyl alcohol, n-butanol, and tert-butanol, and ethers, such as methyl tert-butyl ether, tert-amyl methyl ether, tert-hexyl methyl ether, ethyl tert-butyl ether, tert-amyl ethyl ether, diisopropyl ether, glycols, such as ethylene glycol, propylene glycol, butanediol, aldehydes, such as formaldehyde, acetaldehyde, and acids, such as formic acid, acetic acid, lactic acid, and citric acid.

[0029]

[0033] As used in this specification and the appended claims, the term "autothermal reforming" means a conversion process carried out with partial combustion of a feedstock fuel in the presence of an oxidizer using a burner prior to contact with an oxidation catalyst, and the term "non-autothermal oxidative reforming" means oxidative reforming carried out without such combustion, where the conversion process is fully catalytic.

[0030]

[0034] The present disclosure may be configured to include, consist of, or consist essentially of, in certain implementations, any or all of such features, aspects, and embodiments, as well as elements and components thereof that may be combined to form various further implementations of the present disclosure, as variously described herein with respect to its features, aspects, and embodiments. The present disclosure is described in various embodiments herein with respect to various features and aspects of the present disclosure. The present disclosure contemplates such features, aspects, and embodiments in various permutations and combinations as being within the scope of the present invention. Thus, the present disclosure may be defined as including, consisting of, or consisting essentially of any of these specific features, aspects, and embodiments, or selected one or more such combinations and permutations thereof.

[0031]

[0035] The present disclosure provides hydrogen production systems and methods that avoid and / or overcome various problems present in prior conventional approaches to hydrogen production, as described in the Background and Related Art Description sections herein. The hydrogen production systems and methods of the present disclosure integrate water electrolysis with non-autothermal oxidative reforming, where oxygen produced as a by-product of the water electrolysis reaction is advantageously used in the non-autothermal oxidative reforming ("OR") reaction.

[0032]

[0036] The oxidative reforming carried out in the integrated electrolysis and oxidative reforming system of the present disclosure is non-autothermal oxidative reforming, and such non-autothermal oxidative reforming is advantageously carried out in an adiabatic reactor system such that no external heat, other than pre-heating of the reactants, is required to sustain the conversion process.

[0033]

[0037] The basic object of the present disclosure is an integrated combination of an electrolysis system and a non-autothermal oxidative reforming system for converting oxygenates and / or mixtures of oxygenates and hydrocarbons to produce primarily hydrogen. In this integrated system, the primary oxygen source is the electrolysis system, but the oxygen requirements of the integrated system can be supplemented by additional high purity oxygen sources and suppliers, including, but not limited to, cryogenic air separation plants, adsorbent-based air separation systems, such as pressure swing adsorption (PSA) plants, temperature swing adsorption (TSA) plants, pressure swing adsorption / temperature swing adsorption (PSA / TSA) plants, high purity oxygen pipelines, tanks, tube trailers, and other systems, equipment, and reservoirs effective to deliver high purity oxygen for use in the integrated electrolysis and non-autothermal oxidative reforming system.

[0034]

[0038] Non-autothermal oxidative reforming in the disclosed hydrogen production systems and methods can be carried out using any suitable type or types of feedstock fuel, where the bio-derived content of the feedstock fuel ranges from 5% to 100% by volume, based on the total volume of the feedstock fuel.

[0035]

[0039] The feedstock fuels used in the integrated electrolysis and oxidative reforming system of the present disclosure can be bio-derived, oxygenates, landfill gas, hydrocarbons, and combinations of the above. Although fossil fuel hydrocarbons can be used in combination with bio-derived fuels, it is a distinguishing feature of the hydrogen production technology of the present disclosure that the bio-derived content of the feedstock fuel ranges from 5% to 100% by volume, based on the total volume of the feedstock fuel.

[0036]

[0040] In various embodiments, the bio-derived content of the feedstock fuel can be within a range where the lower endpoint is 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%, and the upper endpoint is one of the above numbers above the lower endpoint.

[0037]

[0041] The feedstock fuel may include, for example, gaseous and / or liquid hydrocarbons ranging from methane to diesel, particularly those that may be biologically produced, although the present disclosure is not limited thereto and is not subject to the bio-derived content limitations set forth above. As used in this context, diesel refers to a hydrocarbon composition composed primarily of paraffins, aromatics, and naphthenes, containing hydrocarbons having about 12 to 20 carbon atoms, the composition having a boiling point range of about 170° C. to about 360° C. If a diesel composition is used, the diesel composition may include biodiesel, or alternatively or in addition, may include petroleum-derived diesel. A wide variety of types of other hydrocarbon compositions, including single component hydrocarbon compositions as well as multi-component hydrocarbon compositions, may be used.

[0038]

[0042] In various embodiments of the oxidative reforming operation of the integrated hydrogen production system and method of the present disclosure, the non-autothermal OR feedstock fuel may include biological and fossil fuel derived feedstocks, such as methane, methanol, ethanol, propanol, butanol, glycerol, ethylene glycol, diesel, or a blend of two or more of the above, but the present disclosure is not limited thereto. It will be recognized that inorganic compounds and materials may be present in the feedstock, such as phosphate and sulfur compounds, in various implementations of the non-autothermal OR operation. The non-autothermal OR feedstock is preferably composed primarily of biologically derived feedstocks, such as biomethane, biomethanol, and the like. Any suitable biofuel may be used in the non-autothermal OR feedstock.

[0039]

[0043] In various preferred embodiments of the non-autothermal oxidative reforming operation in the integrated hydrogen production system and method of the present disclosure, the non-autothermal OR feedstock is constituted by or includes alcohol. Among alcohols, ethanol is particularly advantageous, and can be renewable ethanol produced from corn, sugar beet, or other biomass without contributing to greenhouse gas emissions. Ethanol is abundantly available because it is widely produced and supplied as an additive to gasoline. With the expected future decline in gasoline-powered vehicles on the road, ethanol production will increasingly be allocated to other uses, which is a favorable situation for the implementation and use of the hydrogen production system and method of the present disclosure.

[0040]

[0044] The integrated non-autothermal oxidative reforming and water electrolysis operations performed in the systems and methods of the present disclosure enable the production of low-cost green hydrogen that can be used, for example, in fuel cells to generate electricity very efficiently and cleanly, with only water as a by-product.

[0041]

[0045] While the integrated non-autothermal oxidative reforming and water electrolysis operations of the present disclosure will be illustratively described hereinafter with reference to ethanol (C2H5OH) as the non-autothermal OR feedstock, it will be understood that the present disclosure is not limited thereto, and that corresponding implementations of the integrated non-autothermal oxygen reforming and water electrolysis systems and methods of the present disclosure may be carried out using any other suitable non-autothermal OR feedstock, including those disclosed by way of example above, as well as others including a wide variety of other hydrocarbon and hydrocarbyl feedstocks in specific embodiments, implementations, and applications of the present disclosure.

[0042]

[0046] In the integrated non-autothermal oxidative reforming and water electrolysis operation of the present disclosure, the non-autothermal oxidative reforming may be carried out in the presence of a suitable catalyst at a temperature that may be, for example, in the range of about 600° C. to about 1000° C., or other suitable temperature ranges. In this operation, C2H5OH is introduced into a non-autothermal reformer or reactor where the liquid is thermochemically reduced to shorter chain carbonaceous species. These carbonaceous compounds react with water vapor in the presence of a catalyst to produce a mixture of H2 and other compounds, such as carbon monoxide (CO), carbon dioxide (CO2), acetaldehyde (C2H4O), ethane (C2H5), ethylene (C2H4), and acetone (CH3COCH3).

[0043]

[0047] The catalyst used in the non-autothermal OR process may be of any suitable type, including, for example, a precious metal catalyst, a mixed metal oxide catalyst, a perovskite catalyst, a hexaaluminate catalyst, a pyrochlore catalyst, or any other useful oxidative reforming catalyst. Non-autothermal OR catalysts useful in certain applications of the disclosed systems and methods include, in various embodiments, catalysts including metals such as aluminum, zirconium, nickel, magnesium, gadolinium, yttrium, cobalt, cerium, ruthenium, precious metals, and the like. In various embodiments, catalysts such as the mixed metal oxide catalysts described in U.S. Pat. No. 10,688,472 may be used. In various other specific embodiments, the catalyst may be a ruthenium catalyst or a nickel catalyst supported on a support such as alumina. In yet other specific embodiments, the catalyst may be a platinum catalyst or a palladium catalyst. Other specific embodiments may use a non-autothermal oxidative reforming catalyst including one or more metals selected from Pt, Ni, W, Ru, Au, Pd, Mo, Cu, Sn, Rh, and V. In various further specific embodiments, the non-autothermal oxidative reforming catalyst may comprise one or more metals selected from Pd, Pt, Cu, Mn, and Rh. Further embodiments for performing non-autothermal oxidative reforming may use an oxidative reforming catalyst comprising a metal selected from Group VIII of the periodic table.

[0044]

[0048] The reforming process always produces carbon monoxide (CO), and the water-gas shift ("WGS") reaction is a key step in the reforming process. During the WGS reaction, CO is converted to CO2 and H2 by reaction with water steam.

[0045]

[0049] In the non-autothermal oxidative reforming operation of the present disclosure, steam and oxygen are fed together as oxidants to reform a hydrocarbon feedstock into an H2-rich product stream, which can be used, for example, in a fuel cell or other H2-powered device. Non-autothermal oxidative steam reforming (OSR) is a combination of partial oxidation and steam reforming, where oxygen and steam are fed into a non-autothermal reformer vessel to drive an endothermic steam reforming reaction using heat generated from the exothermic partial oxidation of a hydrocarbon (e.g., ethanol). By using oxygen generated from the water electrolysis reaction in the OSR reaction, the need for an air separation plant to generate oxygen for OSR can be avoided, which is advantageous in many implementations since air separation plants, whether cryogenic or by adsorption, are highly capital intensive in nature. Nevertheless, in various embodiments of the integrated non-autothermal oxidative reforming and electrolysis system of the present disclosure, an air separation plant or other source or source of oxygen can be used to supplement and / or mitigate the oxygen needs of the non-autothermal oxidative reforming process.

[0046]

[0050] Direct non-autothermal oxidative reforming of ethanol or other suitable feedstock may be carried out by co-feeding steam and oxygen to a reformer vessel containing an oxidative reforming catalyst and simultaneously introducing ethanol into the non-autothermal reformer vessel. In the non-autothermal reformer vessel, reaction (1) takes place as follows: C2H5OH+(3-2x)H2O+xO2→(6-2x)H2+2CO2ΔH 25℃ ≒ 0 kcal / mol, x ≒ 0.40 (1). In various embodiments of the present disclosure, the feedstock is ethanol and a non-autothermal oxidative reforming operation is performed, where 0 < x < 1.5. In various embodiments, 0.10 ≦ x ≦ 1.1; 0.3 ≦ x ≦ 0.9; 0.3 ≦ x ≦ 0.5; 0.75 ≦ x ≦ 0.85; or x can be within other ranges suitable for the non-autothermal reformer vessel operation in an attendant hydrogen gas generation system. In various specific embodiments, x can be, for example, about 0.4, 0.5, 0.65, 0.80, 1.0, or other suitable values suitable for performing the non-autothermal oxidative reforming operation.

[0047]

[0051] In this regard, it will be recognized that the stoichiometry of the non-autothermal oxidative reforming reaction will vary depending on the particular feedstock and feedstock blend. In general situations where the feedstock can be varied by the ethanol present or hydrocarbons other than ethanol, or where ethanol is present in a hydrocarbon multi-component feedstock, it is preferred to perform a non-autothermal oxidative reforming reaction of the hydrocarbon feedstock with oxygen and steam, where oxygen is present in the range of 5% to 95% by volume based on the total volume of oxygen and steam in the non-autothermal oxidative reforming reaction.

[0048]

[0052] The hydrogen generation operation according to the present disclosure may be performed in a combined reactor system in which a water electrolysis reactor is coupled with a non-autothermal oxidative reforming reactor, and the by-product oxygen from the electrolysis reactor is used in the non-autothermal oxidative reforming reactor to achieve optimal hydrogen generation. The combined reactor can be advantageously designed for flexible operation to utilize the variability of the feedstock and power costs to obtain the lowest cost hydrogen possible, thereby alleviating the dependence on low renewable electricity tariffs and enabling adjustment of the throughput of the electrolysis reactor and the non-autothermal oxidative reforming reactor.

[0049]

[0053] The advantages and features of the present disclosure are further illustrated with reference to the following examples, which should in no way be construed as limiting the scope of the present disclosure, but rather should be construed as an illustration of one embodiment in a particular application.

[0050]

[0054] Considering again reaction (1) above, in the operation of the coupled reactor system where x=0.40, no external heat source is required to drive the reaction, which is correspondingly thermally neutral. Thus, no external heat is generated that must be removed and dumped into the atmosphere or into another heat removal system or subsystem. As a result, ethanol is not consumed for heating, thereby making more ethanol feedstock available for conversion to hydrogen.

[0051]

[0055] At values ​​of x>0.40, the non-autothermal oxidative reforming becomes exothermic and additional heat production is potentially available for transport to other processes or end-use facilities. While values ​​of x greater than 0.40 reduce hydrogen production, when the non-autothermal oxidation reactor is integrated with other processes requiring heat, the combination allows higher overall thermal efficiencies and lower capital and operating costs to be realized.

[0052]

[0056] The integration of a water electrolyzer with a non-autothermal oxidative reforming operation in the hydrogen production system and method of the present disclosure allows electricity to be effectively used to split water into separate respective streams of hydrogen and oxygen. The electrolysis reaction is endothermic and requires the input of electrical power to split the water molecules, which occurs according to the following reaction (2): 2H2O→2H2+O2ΔH 25℃ ≒67kcal / mol(2)

[0053]

[0057] The electrolyzers used in the disclosed hydrogen production systems and methods can be of any suitable type suitable for splitting water molecules into separate streams of hydrogen and oxygen. Such electrolyzers can range from small, appliance-sized devices well suited for small-scale, distributed hydrogen production to large, centralized production facilities that can be directly linked to renewable or other forms of low-cost electricity production. Low-temperature alkaline electrolyzers or polymer electrolyte membrane (PEM) electrolyzers can be used in various embodiments of the hydrogen production system. In other embodiments of the hydrogen production system, high-temperature solid oxide electrolyzers can be used that exhibit high efficiency in terms of electricity consumption.

[0054]

[0058] Here, electrolyzers useful in the practice of the present disclosure may be of various types and may include, for example, polymer electrolyte membrane (PEM) electrolyzers, such as those commercially available from Plug Power Inc. (Latham, New York); alkaline electrolyzers, such as those commercially available from Nel ASA (Oslo, Norway); and solid oxide electrolyzers, such as those commercially available from Elcogen AS (Tallinn, Estonia).

[0055]

[0059] The integrated electrolysis and oxidative reforming system of the present disclosure may be configured as a stationary geographic location facility, i.e., a non-mobile system, thereby avoiding the drawbacks and disadvantages associated with corresponding mobile, e.g., vehicular, implementations. In such a stationary facility, the integrated electrolysis and oxidative reforming systems are advantageously co-located with one another in the same geographic location, thereby minimizing capital equipment expenditures and allowing economies of scale to be achieved. While co-located integration of the electrolysis system and the oxidative reforming system is preferred in most implementations, the electrolysis system and the oxidative reforming system are within a separation distance between each other that is less than at least one of 2.5 km, 2.4 km, 2.3 km, 2.2 km, 2.1 km, 2.0 km, 1.9 km, 1.8 km, 1.7 km, 1.6 km, 1.5 km, 1.4 km, 1.3 km, 1.2 km, 1.1 km, 1.0 km, 0.9 km, 0.8 km, 0.7 km, 0.6 km, 0.5 km, 0.4 km, 0.3 km, 0.2 km, 0.1 km, 0.05 km, and 0.025 km in various embodiments, and the electrolysis system and the oxidative reforming system may be integrated with each other by flow circuits, pipelines, and other integration infrastructure with significantly greater separation distances between the electrolysis system and the oxidative reforming system in the integration in other embodiments.

[0056]

[0060] This disclosure contemplates large, fixed-site integrated electrolysis and oxidative reforming systems, such as those producing 20,000-100,000 kg of hydrogen / day, as well as a wide variety of other integrated electrolysis and oxidative reforming systems configured and arranged to produce hydrogen at other, lesser production levels.

[0057]

[0061] In various embodiments, the present disclosure contemplates a modular, integrated electrolysis and oxidative reforming system capable of producing hydrogen at levels of, for example, approximately 100-2000 kg of hydrogen / day. Such a modular, integrated system is sufficiently compact to permit factory production of the system and mounting of the system on a skid or industrial container for easy transport and installation to hydrogen production sites for distributed generation of hydrogen, e.g., hydrogen fueling stations for automobiles operating with hydrogen fuel cells and / or hydrogen-fueled internal combustion engines.

[0058]

[0062] In various embodiments, the non-autothermal reactor system in an integrated oxidative reforming system includes a single non-autothermal adiabatic reactor vessel in which a staged assembly of catalyst beds is arranged, configured such that the exothermic reaction of partial oxidation occurs in a first stage, driving the endothermic reaction of steam reforming in a second stage resulting in a reduction in gas temperature from such endothermic second stage reaction, and a water-gas shift (WGS) catalyst is deployed in a high temperature, slightly exothermic third stage that converts carbon monoxide to hydrogen, such that the composition of the gas exiting the vessel is primarily hydrogen. In various embodiments, the concentration of hydrogen in the exhaust gas may be greater than at least one of 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 98 mol%, and 99 mol%, and in various embodiments, the concentration of hydrogen in the exhaust gas is within a range having a lower endpoint that is one of the values ​​above and an upper endpoint that is one of the values ​​above that exceeds the lower endpoint, for example, a range of 50 mol% to 95 mol%, or 55 mol% to 85 mol%, or 60 mol% to 80 mol%, or other suitable range.

[0059]

[0063] The products of the oxidative reforming operation in the integrated electrolysis and non-autothermal oxidative reforming system of the present disclosure are primarily hydrogen and carbon dioxide (collectively, greater than or equal to 60 mol% of the exhaust gas). In various embodiments, the combined concentration of hydrogen and carbon dioxide in the oxidative reforming exhaust gas may be greater than at least one of 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 98 mol%, and 99 mol%, and in various embodiments, the concentration of hydrogen and carbon dioxide in the oxidative reforming exhaust gas is within a range having a lower endpoint value that is one of the values ​​above and an upper endpoint value that is greater than the lower endpoint value. The integrated electrolysis and non-autothermal oxidative reforming system is desirably operated to produce a high purity hydrogen stream preferably having a hydrogen purity greater than at least one of 98 mol%, 98.5 mol%, 98.9 mol%, 99 mol%, 99.5 mol%, 99.9 mol%, 99.95 mol%, 98.99 mol%, and 99.999 mol%, or within a range where the lower endpoint is one of the above numerical values ​​and the upper endpoint is one of the above numerical values ​​greater than the lower endpoint.

[0060]

[0064] Producing a high purity hydrogen stream from an oxidative reforming system requires the provision of a separation system to remove carbon dioxide, unreacted hydrocarbons, and carbon monoxide from the hydrogen-containing stream produced by the oxidative reforming operation. After hydrogen separation, secondary products / waste products produced by hydrogen separation can be used to preheat the oxidative reforming reactants prior to the conversion process. If the waste stream from hydrogen separation has sufficient calorific value, oxygen from an electrolysis system can be used to combust the waste stream to obtain a flue gas of carbon dioxide and water vapor. The flue gas may be treated to condense the water vapor, and the carbon dioxide can be captured using conventional methods and equipment, and optionally sequestered by applicable sequestration techniques known in the art. Such operation of the integrated system results in an overall hydrogen production from the integrated system that is greenhouse gas emission negative.

[0061]

[0065] Referring now to the drawings, FIG. 1 is a schematic flow diagram of a hydrogen generation system 100 according to one embodiment of the present disclosure that integrates a non-autogenous thermal oxidative reforming process system 12 with a low temperature electrolysis system 14.

[0062]

[0066] The non-autothermal oxidative reforming system 12 includes a water-ethanol source ("hydrocarbon / H2O blend") from which an aqueous solution of ethanol is delivered in a water-ethanol supply line 16 having passage through a heat exchanger 20 to a feed mixer 18 for mixing with oxygen provided from an oxygen storage tank 73 in an oxygen supply line 44. The resulting ethanol / water / oxygen feed stream is passed in a feed delivery line 22 through a heat exchanger 24 to a non-autothermal oxidative reforming reactor 28.

[0063]

[0067] The non-autothermal oxidative reforming reactor 28, shown diagrammatically, includes an upper partial oxidation segment and is heated to a suitable temperature (T OR ) and pressure (P OR ) is a segmented adiabatic reactor containing a suitable catalyst for the partial oxidation of a feedstock introduced in the first partial oxidation segment (TS1 The temperature at the partial oxidation segment may range from about 700° C. to about 900° C. as appropriate for carrying out the partial oxidation of the feedstock. Proceeding in the gas flow direction through the adiabatic reactor, the gas flowing from the first partial oxidation segment is then heated to a temperature (T S2 ), the gas flows through an intermediate reforming segment containing a suitable steam reforming catalyst, and then from the intermediate (second) steam reforming segment, through a third segment of an adiabatic reactor containing a high temperature water gas shift catalyst, where the high temperature water gas shift reaction occurs at a temperature (T S3 ) to produce a hydrogen-containing reformate that exits the adiabatic reactor in non-autothermal oxidative reforming reactor exit line 30.

[0064]

[0068] In the adiabatic reactor, each of the partial oxidation, steam reforming, and water gas shift reactions is carried out at 1000 K for each partial oxidation (T S1 ), steam reforming (T S2 ), and the water-gas shift reaction (T S3 ) segment is T S1 >T S2 >T S3 The reaction is carried out catalytically at a temperature maintained such that

[0065]

[0069] The oxygen storage tank 73 for storing the oxygen produced by the low temperature electrolysis system 14 and used to supply oxygen to the non-autothermal oxidative reforming system 12 may be of a size and capacity appropriate to effectively buffer the oxygen production capacity of the low temperature electrolysis system 14, with oxygen being transferred from the low temperature electrolysis system to such buffer storage tank and then discharged from the buffer storage tank to the oxygen supply line 44 in an amount and rate required to supply the non-autothermal oxidative reforming system 12. In this manner, the low temperature electrolysis system and the non-autothermal oxidative reforming system may be selectively "matched" in operation to one another with respect to the operating conditions and throughput of both the electrolysis and non-autothermal oxidative reforming systems of the overall integrated system.

[0066]

[0070] In operation of the exemplary system of FIG. 1, where ethanol is used as the feed hydrocarbon, ethanol is catalytically reacted with oxygen and water in the non-autothermal oxidative reforming reactor 28 to form a mixture containing hydrogen, carbon monoxide, water, and carbon dioxide, which then undergoes a high temperature water-gas shift reaction whereby CO is converted to CO2 and H2 by reaction with steam obtained from water originally fed to the non-autothermal oxidative reforming system from a water-ethanol source. The resulting gas exits the non-autothermal oxidative reforming reactor 28 in an exhaust line 30, flows through the heat exchanger 20 to heat an aqueous solution of ethanol introduced into the system in the water-ethanol feed line 16, and then enters the low temperature water-gas shift reactor 34, where at least a portion of the CO remaining in the stream is converted to CO2 and H2. The resulting gas stream containing hydrogen and CO2 exits the low temperature water-gas shift reactor 34 in a low temperature water-gas shift reactor exhaust line 36 and enters a hydrogen gas purifier 38.

[0067]

[0071] In the hydrogen gas purifier 38, the water-gas shift reactor effluent stream is separated into hydrogen, which exits the purifier in a hydrogen gas discharge line 40, and CO2-containing tail gas, which exits the hydrogen gas purifier 38 in a tail gas discharge line 42. The hydrogen flows in the hydrogen gas discharge line 40 to a hydrogen gas reservoir 90 in the low-temperature electrolysis system 14 to supplement the hydrogen gas produced by low-temperature electrolysis of water in the polymer electrolyte membrane (PEM) electrolyzer 66.

[0068]

[0072] The low temperature electrolysis system 14, shown diagrammatically in Figure 1, includes a feed water source 50 from which the feed water is passed by the action of a feed water pump 52 through a water purifier / cleaner 54 to an oxygen-water phase separation and supply tank 56. The oxygen-water phase separation supply tank 56 provides water in a feed water line 58 which is passed by a circulation pump 60 through a heat exchanger 62 and an ion exchanger 64 to an electrolyzer 66, the cathode of which is connected by a suitable circuit to a transformer and rectifier.

[0069]

[0073] In the electrolyzer 66, the water is ionized into hydrogen and oxygen, and the oxygen is passed from the electrolyzer 66 to the oxygen-water phase separation and feed tank in line 68. The oxygen entering the oxygen-water phase separation and feed tank passes through the feed water therein and is discharged as an overhead stream in an oxygen demister tank 70 and an oxygen discharge line 72 which contains a flow control valve 74.

[0070]

[0074] From the oxygen discharge line 72, the product oxygen stream from the low temperature electrolysis system 14 travels to an oxygen storage tank 73, from which the oxygen is supplied in the oxygen supply line 44 to the non-autothermal oxidative reforming system 12 to provide oxygen for the non-autothermal oxidative reforming carried out in the non-autothermal oxidative reforming reactor 28.

[0071]

[0075] Hydrogen produced by the ionization reaction of water in the electrolyzer 66 exits the electrolyzer in a hydrogen output line 76 and flows to a gas-liquid separation vessel 78 where hydrogen gas is dissociated from the water, which is recycled to the electrolyzer. A portion of the water recycled to the electrolyzer may be flowed to the inlet of the circulation pump 60 in an electrolyzer recycle line 128, which includes a flow control valve 130. Hydrogen exits the gas-liquid separation vessel 78 as an overhead gas stream, which flows in a hydrogen delivery line 80 through a hydrogen demister vessel 82, a heat exchanger 84, a condensate trap 86, and a flow control valve 88 to a hydrogen gas reservoir 90, which also receives hydrogen from the non-autothermal oxidative reforming system in a hydrogen gas exit line 40, as described above.

[0072]

[0076] Hydrogen gas from a hydrogen gas storage 90 may be selectively withdrawn from the storage in a hydrogen discharge line 94 and flowed to a hydrogen compressor 92. The compressor compresses the withdrawn hydrogen to an appropriate pressure. The compressed hydrogen then flows from the compressor in a hydrogen supply line 96, which includes a flow control valve 98, to a downstream use or transportation destination, such as a hydrogen fuel cell, a hydrogen-utilizing chemical processing facility, a hydrogen transportation pipeline, or other use or processing destination.

[0073]

[0077] Here, the hydrogen production system 10 shown generally in FIG. 1 may be configured to enable the non-autothermal oxidative reforming system to operate in a thermally neutral manner (e.g., corresponding to x≈0.40 in reaction (1)), where the electrolyzer is sized and configured to provide the amount of oxygen required for the non-autothermal oxidative reforming of ethanol for such thermally neutral operation, such that no external heat source is required and no excess heat is generated.

[0074]

[0078] 1 may further include a process controller 132 having coupled thereto bidirectional signal transmission lines 134 and 136, shown diagrammatically to represent their coupling to process equipment components, such as pumps, compressors, flow control valves, heat exchangers, and sensors for sensing process conditions (e.g., temperature, pressure, flow rate, and composition, the sensed conditions being communicated to the process controller by signal transmission lines coupled to the sensors) for monitoring and controlling the process system. For such purposes, the process controller may include suitable signal processing components and controls, such as a computer, programmable logic control device, etc., as appropriate for monitoring and controlling the operations to be performed by the process controller.

[0075]

[0079] For example, the process controller may be configured to control the temperature in a single adiabatic reactor, described in more detail hereinafter in connection with FIG. 3 herein, whereby a partial oxidation reaction occurs in a first catalyst bed at a temperature in the range of about 700° C. to about 900° C., a steam reforming reaction occurs in a second catalyst bed at a temperature in the range of about 450° C. to about 850° C., and a high temperature water gas shift reaction occurs in a third catalyst bed at a temperature in the range of about 300° C. to about 420° C.

[0076]

[0080] In various embodiments, the process controller may be configured to regulate the operation of the electrolyzer and the non-thermally self-oxidative reforming system in a hydrogen generation system, whereby the non-thermally self-oxidative reforming system performs the reaction C2H5OH+(3 - 2x)H2O + xO2 → (6 - 2x)H2 + 2CO2, where 0 < x < 1.5, or in a further particular embodiment, 0.30 ≤ x ≤ 0.50, or in other embodiments, x has other values or ranges, for example, 0.10 ≤ x ≤ 1.1; 0.3 ≤ x ≤ 0.9; 0.3 ≤ x ≤ 0.5; or 0.75 ≤ x ≤ 0.85; or x may be, for example, about 0.4, 0.5, 0.65, 0.80, 1.0, or other suitable values.

[0077]

[0081] In various embodiments, the electrolyzer used in the hydrogen generation system may include a solid oxide electrolyzer, and the process controller may be configured to regulate the operation of the electrolyzer and the non-thermally self-oxidative reforming system, whereby the non-thermally self-oxidative reforming system generates excess heat for transfer to the solid oxide electrolyzer such that the solid oxide electrolyzer operates with a thermal efficiency greater than 50%.

[0078]

[0082] As a specific example, the hydrogen generation system 10 of FIG. 1 may be configured and arranged as a 1500 kg H2 / day hydrogen station for on-site refueling operations for fuel cell vehicles such as automobiles, trucks, vans, forklifts, buses, robotic transport caddies, and other power-driven and transportation systems. Table 1 below summarizes the inputs and outputs of a 0.5 megawatt (MW) low-temperature electrolyzer and the inputs and outputs of a non-thermally self-oxidative ethanol reformer operating at x = 0.40 (reaction (1)) in such an exemplary 1500 kg H2 / day hydrogen station.

[0079]

[0083]

Table 1

[0080]

[0084] If the CO2 produced from the non-autogenous thermal oxidative reformer in the hydrogen production system of FIG. 1 is derived from bioethanol and the electrolyzer uses an environmentally friendly power source, the overall system net carbon dioxide balance may approach zero. In various embodiments, the hydrogen production system of the present disclosure may incorporate or use a CO2 capture or CO2 sequestration system to obtain a net negative CO2 balance or emission. In various embodiments, each non-autogenous thermal oxidative reformer and low temperature electrolysis system may be configured and arranged to share various infrastructure components, such as, for example, water treatment systems, control systems, compression equipment, and hydrogen storage tanks. It will be recognized that the configuration, arrangement, components, and operation of the hydrogen production system may vary widely in the broad implementation of the present disclosure.

[0081]

[0085] FIG. 2 is a schematic flow diagram of a hydrogen production system 100 according to another embodiment of the present disclosure that integrates a non-autogenous thermal oxidative reforming process system 11 with a high temperature electrolysis system 126.

[0082]

[0086] The non-autothermal oxidative reforming system in Figure 2 is of the same generalized configuration as the non-autothermal oxidative reforming system in Figure 1, with the non-autothermal oxidative reforming reactor 28 supplied with oxygen in oxygen supply line 44 from oxygen storage tank 73, as described above in connection with the hydrogen production system of Figure 1. Correspondingly numbered components of the non-autothermal oxidative reforming system 11 should be understood to correspond to the same or similarly numbered components described above in connection with the hydrogen production system of Figure 1. The oxygen storage tank 73 in the system of Figure 2 may be used to selectively "buffer" the overall operation of the non-autothermal oxidative reforming system and the high temperature electrolysis system, similar to the function and operation of the oxygen storage tank 73 in the system of Figure 1 described above.

[0083]

[0087] 2 may use any suitable high temperature electrolyzer, such as, for example, a high temperature solid oxide electrolyzer 102 for ionizing water into hydrogen and oxygen. As shown diagrammatically, the high temperature solid oxide electrolyzer 102 is coupled by an appropriate circuit with a transformer and rectifier.

[0084]

[0088] Make-up water is supplied to the high temperature electrolysis system in make-up water supply line 110 and flows through heat exchanger 108 and heat exchanger 116 to the high temperature solid oxide electrolyzer 102. At the cathode of the high temperature solid oxide electrolyzer, a hydrogen / water vapor product stream is discharged in hydrogen / water vapor exhaust line 104, passes through heat exchanger 108, and then passes to knock-out pot 122, which may be operated at a temperature of, for example, 32° C. or other suitable temperature or within other suitable operating temperature ranges. The knock-out pot 122 discharges a condensed recycled water stream, and a product hydrogen stream, which is discharged through hydrogen exhaust line 124 and flows to the hydrogen gas storage 90.

[0085]

[0089] The high temperature solid oxide electrolyzer 102 produces an oxygen / water vapor mixture at its anode, e.g., with a 50 / 50 mole fraction of oxygen and water. The O2 / water vapor mixture is passed in oxygen / water vapor discharge line 106 through a heat exchanger 112 to an oxygen / water separator 114. The oxygen / water separator 114 discharges separated water and correspondingly separated oxygen into the oxygen supply line 44 for flow to the oxygen storage tank 73, from which the oxygen is fed to the non-autothermal oxidative reforming system 11.

[0086]

[0090] In the high temperature electrolysis system 126 , the sweep water may be passed through the heat exchanger 112 and then through the heat exchanger 118 , and the sweep water vapor may be supplied from the heat exchanger 118 to the high temperature solid oxide electrolyzer 102 .

[0087]

[0091] Thermal integration of the high temperature electrolysis system 126 and the non-autothermal oxidative reforming system 11 may be implemented using a heat recovery assembly 120, with the flow of hydrogen, carbon monoxide, carbon dioxide, and water flowing from the non-autothermal oxidative reforming reactor 28 through a heat exchanger in the heat recovery assembly 120, with recirculation of flue gas in a flow circuit including the heat exchanger 116, the heat exchanger 118, and the heat exchanger in the heat recovery assembly 120. The heat recovery assembly 120 may also include a heat recovery device for heat recovery ("Recuperation"). Such a heat recovery device may be of any suitable type, for example of a vertical flat panel structure, or of a horizontal flat panel structure, or of a cellular structure, or more generally of a cross-flow, parallel flow, or reflux type of the high temperature electrolysis system in various specific embodiments. Any suitable heat recovery elements and / or devices may be used in such a heat recovery assembly, including heat pipes, thermal wheels, heat sinks, and the like.

[0088]

[0092] In the generalized type of hydrogen production system shown in Figure 2, the high temperature electrolyser is sized to provide the necessary oxygen to the non-autothermal oxidative reforming system so that excess heat from the non-autothermal oxidative reforming reaction can be efficiently transferred and used to meet the thermal requirements of the high temperature electrolyser (the solid oxide electrolyser in the embodiment shown in Figure 2). By operating the non-autothermal oxidative reforming system to generate excess heat, the high temperature electrolyser can be operated at improved thermal efficiency, e.g., greater than 50%, and in various embodiments, approximately 75% or greater. Unlike PEM or alkaline electrolysers, the solid oxide electrolyser can be operated at the same pressure levels at which the non-autothermal oxidative reforming system is operated.

[0089]

[0093] In the hydrogen production system exemplary shown in FIG. 2, the product stream from the non-autothermal oxidative reforming reactor 28 is heated to a temperature T OR and pressure P ORThe electrolyzer heat exchanger is then passed through the high temperature electrolyzer heat exchanger at 1000 K to provide the heat required to convert the water to high temperature / high pressure steam. While passing through this heat exchanger, the product gas from the non-autothermal oxidative reforming is heated to a temperature T suitable for the low temperature water gas shift reaction required to convert carbon monoxide to carbon dioxide. WGS and flows to the low temperature water gas shift reactor 34. In the low temperature water gas shift reactor 34, the product stream undergoes a catalytic shift reaction to reduce the CO content in the product gas to a suitably low level, for example, less than 1% by volume based on the volume of the product gas.

[0090]

[0094] The product gas from the low temperature water gas shift reactor 34 flows to a hydrogen gas purifier 38 where the product gas is separated into hydrogen, which exits the purifier in a hydrogen gas discharge line 40, and a CO2-containing tail gas, which exits the hydrogen gas purifier 38 in a tail gas discharge line 42. The hydrogen is passed in the hydrogen gas discharge line 40 to a hydrogen gas storage 90 where such hydrogen gas is stored together with hydrogen gas produced by high temperature electrolysis of water in a high temperature solid oxide electrolyzer 102.

[0091]

[0095] The exhaust gas discharged from the hydrogen gas purifier 38 in the exhaust gas discharge line 42 flows to the oxygen / air burner 32 ("O2 / air burner"). The oxygen / air burner 32 is supplied with oxygen from an oxygen storage tank 73 flowing in an oxygen supply line 44 via a burner oxygen / air supply line 33. The oxygen / air burner 32 produces flue gas, which is discharged in a flue gas line 26 and flows through a heat exchanger 24 for heating an ethanol / water / oxygen stream that is passed to the non-autothermal oxidative reforming reactor 28, and the flue gas containing carbon dioxide and water (CO2 / H2O) is passed as exhaust gas to the carbon dioxide capture tank 46, where it is separated into a CO2 stream (discharged from the carbon dioxide capture tank 46 in a carbon dioxide discharge line 48) and a recycled water stream (discharged from the carbon dioxide capture tank 46 in a recycled water discharge line 49).

[0092]

[0096] The CO2 exhausted from carbon dioxide exhaust line 48 may be directed to a CO2 utilization facility, or a CO2 capture or sequestration facility, or other treatment or use.

[0093]

[0097] The recycled water stream discharged from the carbon dioxide capture tank 46 in recycled water discharge line 49 may be recycled to the electrolyzer in the hydrogen gas production system 100 and / or used to form an aqueous solution of ethanol and / or other hydrocarbons ("hydrocarbon / H2O blend"), which is combined with oxygen and flows as a feedstock to the adiabatic non-autothermal oxidative reforming reactor 28.

[0094]

[0098] In thermally integrated non-autogenous thermal oxidative reforming and high temperature electrolysis systems of the general type illustratively shown in FIG. 2, the shared equipment combined with the efficiency gains from thermal integration allows compact hydrogen production systems to be achieved with significantly lower capital costs than would be incurred by the use of either system alone.

[0095]

[0099] 2, similar to the system of FIG. 1 described above, may further include a process controller 140 having two-way signal transmission lines 142 and 144 coupled thereto, which are shown diagrammatically to represent the couplings thereof to process equipment components, e.g., pumps, compressors, flow control valves, heat exchangers, and sensors for sensing process conditions (e.g., temperature, pressure, flow rate, composition, the sensed conditions being communicated to the process controller by signal transmission lines coupled to the sensors) for monitoring and controlling the process system. The process controller may be configured and operated as described above for the process controller in FIG. 1, for example, to control the temperature in the single adiabatic non-autothermal oxidative reforming reactor so that the partial oxidation, steam reforming, and water gas shift reactions are performed at predetermined temperature conditions and / or to control other process conditions, such as flow rate, pressure, composition, etc., to achieve a desired output of hydrogen from the integrated oxidative reforming and electrolysis system in the hydrogen production system.

[0096]

[0100] For example, in various embodiments, the process controller in the hydrogen generation system of FIG. 2 may be configured to adjust the operation of the electrolyzer and the non-thermally self-oxidative reforming system in the hydrogen generation system, whereby the non-thermally self-oxidative reforming system performs the reaction C2H5OH + (3 - 2x)H2O + xO2 → (6 - 2x)H2 + 2CO2, where 0 < x < 1.5, or in a further specific embodiment, 0.30 ≦ x ≦ 0.50, or x is within another suitable range of values, for example, 0.10 ≦ x ≦ 1.1; 0.3 ≦ x ≦ 0.9; 0.3 ≦ x ≦ 0.5; or 0.75 ≦ x ≦ 0.85; or x can be, for example, about 0.4, 0.5, 0.65, 0.80, 1.0, or other suitable values.

[0097]

[0101] In addition to or instead of this, the process controller may be configured to adjust the operation of the high-temperature electrolyzer and the non-thermally self-oxidative reforming system, whereby the non-thermally self-oxidative reforming system generates excess heat for transfer to a high-temperature electrolyzer, such as a solid oxide electrolyzer, so that the high-temperature electrolyzer operates with a thermal efficiency exceeding 50%.

[0098]

[0102] Table 2 below summarizes the inputs and outputs of a 1.2 megawatt (MW) high-temperature electrolyzer and the inputs and outputs of a non-thermally self-oxidative ethanol reformer operating at x = 0.40 (reaction (1)) in such an exemplary 1500 kg of H2 / day hydrogen station.

[0099]

[0103]

Table 2

[0100]

[0104] The hydrogen production systems of the present disclosure may incorporate and employ a variety of hydrogen purification devices, materials, and techniques to achieve the desired purity and composition of the product hydrogen from such systems. For example, contaminants and impurities may be removed from the hydrogen product by the use of physical adsorbents, chemical adsorbents, condensation or solidification techniques, wet scrubbing, complexation and precipitation, or any other appropriate technique for the particular contaminant or impurity species involved.

[0101]

[0105] It will be appreciated that the hydrogen production systems of FIGS. 1 and 2 are shown schematic diagrams without reference to valves, pumps, compressors, etc. that may be implemented in the respective systems as they are physically constructed, arranged and operated.

[0102]

[0106] The integrated hydrogen production system of the present disclosure can be configured and operated to perform non-autothermal oxidative reforming in a flexible manner on a range of feedstocks that correspond to a variety of bio-derived carbon-based feedstocks, by appropriate design or selection of oxidative reformer equipment and non-autothermal oxidative reforming catalysts. Such design and selection can allow for the use of a variety of alternatively available feedstocks, such as, for example, biomethanol, biodiesel, and biomethane, but the present disclosure is not limited thereto.

[0103]

[0107] The integrated hydrogen production system of the present disclosure may be implemented such that the high temperature water-gas shift (HTWGS) reaction is carried out in a single adiabatic non-autothermal oxidative reforming reactor and the low temperature water-gas shift (LTWGS) reaction is carried out in a separate low temperature water-gas shift reactor, as exemplarily shown in connection with Figures 1 and 2. In other implementations of the integrated hydrogen production system of the present disclosure, the low temperature water-gas shift reaction may be carried out in an oxidative reforming reactor as a separate segment of the reactor downstream of the high temperature water-gas shift reaction segment, which in turn is downstream of the steam reforming segment, which in turn is downstream of the partial oxidation segment. It will be accordingly understood that the oxidative reforming reactor may vary in its components and structure within the broad scope of the present disclosure. Thus, the oxidative reforming reactor may be a segmented reactor including partial oxidation, steam reforming, and high temperature water-gas shift segments, along with any low temperature water-gas shift segments, as segments within a single reactor vessel. In such a single oxidative reforming reactor, the respective partial oxidation, steam reforming, and water gas shift reactions may be carried out in a single vessel with the catalyst for each reaction separated, for example, by a porous ceramic or metallic partition or other separating structure or arrangement.

[0104]

[0108] FIG. 3 is a schematic diagram of a non-autothermal segmented adiabatic reactor of a type useful for the hydrogen production systems and methods of the present disclosure, in one embodiment of the present disclosure.

[0105]

[0109] As shown, the segmented adiabatic reactor is shown in a vertically upright orientation with the upper inlet end connected to a feed conduit that delivers ethanol (and / or other hydrocarbon or feed components), water, and oxygen into the reactor vessel. The reactor vessel is of cylindrical shape with a circular cross section in a transverse plane perpendicular to the flow direction of gases flowing through the reactor vessel. An upper inlet end cap or flange is secured to the upper end of the cylindrical housing of the reactor vessel and coupled to the feed conduit, defining an internal inlet headspace for receiving the ethanol, water, and oxygen reactants for subsequent downward flow through the reactor to its lower discharge end.

[0106]

[0110] At the discharge end, a lower outlet end cap or flange is secured to the lower end of the cylindrical housing of the reactor vessel and defines an internal outlet plenum that receives primarily hydrogen and carbon dioxide reaction products and unreacted reactant species from the successive partial oxidation, steam reforming, and water gas shift reactions for discharge through a discharge conduit coupled to the lower outlet end cap or flange.

[0107]

[0111] The segmented adiabatic reactor may be formed of a non-conductive material and / or may be covered or coated with an insulating material or otherwise constructed and arranged to establish and maintain the thermal insulation of the reactor.

[0108]

[0112] In the interior volume of a segmented adiabatic reactor, different catalysts are arranged in vertically successive beds that may be physically separated from one another by physical separating elements or structures, such as screen elements, perforated disks, porous frits, or other separating structures or arrangements that allow for continuous fluid flow through successive beds without excessive pressure drop or hydrodynamic flow anomalies, such as channeling or dead spaces.

[0109]

[0113] The top catalyst bed comprises a partial oxidation catalyst (e.g., a catalyst comprising rhodium, palladium, platinum, rhenium, ruthenium, nickel, cobalt, or mixed metal oxides, or combinations or mixtures of metals or metal oxides) that mediates a primarily exothermic partial oxidation reaction of the reactants at a temperature that may range, for example, from 700 to 900°C.

[0110]

[0114] The next lower catalyst bed comprises a steam reforming catalyst (e.g., a catalyst comprising promoted nickel, ruthenium, rhenium, rhodium, copper zinc, cobalt, mixed metal oxides, or combinations or mixtures of metals or metal oxides) which mediates an endothermic steam reforming reaction of the partial oxidation reaction product from the first (top) catalyst bed, with the upper portion of the promoted nickel catalyst bed being at a temperature which may be in the range of, for example, 700-850°C, and the lower portion of the steam reforming catalyst bed being at a temperature which may be in the range of, for example, 400-550°C.

[0111]

[0115] Below the steam reforming catalyst bed, the next lower catalyst bed comprises a high temperature water gas shift catalyst (e.g., a catalyst comprising copper promoted iron, iron-chromium, copper, zinc, copper-zinc, nickel, iron oxide, chromium oxide, or other mixed metal oxides, or combinations or mixtures of metals or metal oxides) that mediates the high temperature water gas shift reaction of the endothermic steam reforming reaction products. The high temperature water gas shift catalyst bed is at a temperature that can range, for example, from 300 to 450 to 300°C.

[0112]

[0116] Although not shown in the reactor configuration illustrated in Figure 3, the reactor in various embodiments may further include an optional fourth catalyst bed containing a low temperature water gas shift catalyst located inside the adiabatic reactor, or a separate low temperature water gas shift reactor vessel containing a low temperature water gas shift catalyst may be provided, with product gas from the adiabatic reactor flowing to the separate low temperature water gas shift reactor. The low temperature water gas shift catalyst may be of any suitable type and may include, for example, a copper-based catalyst, such as copper, copper-zinc oxide, copper oxide, copper oxide-zinc oxide, copper oxide-zinc oxide-alumina, copper oxide-zinc oxide-chromium oxide, or other mixed metal oxides or mixtures of metals or metal oxides.

[0113]

[0117] The reaction is carried out by the sequential reactions of partial oxidation in a first catalyst bed, steam reforming in a second catalyst bed, and a high temperature water gas shift reaction in a third catalyst bed, and optionally a secondary low temperature water gas shift reaction in a fourth catalyst bed. C2H5OH+(3-2x)H2O+xO2→(6-2x)H2+2CO2, ΔH 298℃ = 0 kcal / mol, x = 0.36 and hydrogen and carbon dioxide product streams, further containing unreacted reactants from their respective reactions in the segmented adiabatic reactor, are discharged from the reactor in a product discharge conduit at the outlet end.

[0114]

[0118] It will be appreciated that the specific catalytic materials mentioned above in the description of the non-autothermal segmented adiabatic reactor are identified by way of example, and that other specific catalytic materials may be used in various embodiments of the hydrogen production systems and methods of the present disclosure.

[0115]

[0119] It should also be appreciated that although the reactor is illustratively shown and described with reference to Figure 3 as having a vertically oriented cylindrical configuration with a circular cross-section for downflow gas flow operation, the disclosure is not so limited and the reactor may be of any other suitable configuration, orientation, and flow configuration suitable for integration of the reactor with an electrolyzer in a hydrogen production system and method. The reactor may have any suitable size, shape, orientation, and configurational character (including fixed bed, fluidized bed, rotating bed, power belt bed, etc.), and the reactor may have any aspect ratio (e.g., length / diameter ratio) or other dimensional characteristics, with a cross-section approximately perpendicular to the flow direction that is geometrically regular or irregular, etc.

[0116]

[0120] FIG. 4 is a schematic diagram of the reactor interior showing an exemplary arrangement for minimizing pressure drop and / or enhancing heat transfer from one catalyst bed to the next in a segmented adiabatic reactor according to another embodiment of the present disclosure.

[0117]

[0121] The segmented reactor component shown in Figure 4 includes a partial oxidation segment, which may include a monolith formed of cordierite or other suitable monolith construction material, with a rhodium-based catalyst, or other suitable partial oxidation catalyst, supported on and / or in the monolith. The catalyst may be deposited in the pores of the monolith or otherwise incorporated into the monolith support in any suitable manner, such as by vapor deposition, solution impregnation, or other suitable technique. Here, the partial oxidation segment is configured to accept a fuel (e.g., ethanol or other hydrocarbon or feedstock), water vapor, and oxygen feedstock, along with gases preheated to a "light-off" temperature.

[0118]

[0122] After the partial oxidation segment, the next segment, the steam reforming segment, may include a coated metal alloy monolith or metal foam as a support for the steam reforming catalyst. The steam reforming segment may, for example, include an FeCr alloy monolith or foam with a nickel-based catalyst, or other suitable steam reforming catalyst, in and / or supported on the support. The steam reforming catalyst may be incorporated into the monolith or foam support by any suitable deposition, coating, or impregnation technique.

[0119]

[0123] Downstream from the steam reforming segment is the next segment, the water gas shift segment, which may comprise, for example, a bed of pellets or extrudates of a suitable support material containing a catalyst, such as an Fe-Cr catalyst, supported on and / or in a support. The catalyst may be incorporated into the support material feedstock by internal blending or mixing prior to pelletizing or extruding the feedstock, or in other suitable manner, such as vapor deposition, solution impregnation, or other incorporation techniques.

[0120]

[0124] It should be understood that each of the segmented reactor components in the above description is exemplary in nature and that other components, supports, substrates, catalysts, and configurations may be variously used in other embodiments of the present disclosure. The segmented components may be arranged and bonded in the adiabatic reactor as appropriate to facilitate heat transfer through the reactor and provide an acceptable pressure drop for gas flowing through the reactor from the reactor inlet upstream of the partial oxidation segment to the reactor outlet downstream of the water-gas shift segment.

[0121]

[0125] In addition to the feedstock-flexible nature of the hydrogen production system of the present disclosure, as described previously herein, the hydrogen production system of the present disclosure may be configured and operated to effectively "turn up" or "turn down" the non-autothermal oxidative reforming system and the electrolysis system to optimize hydrogen production from each unit based on the current price of the feedstock (bioethanol, biomethanol, biodiesel, biomethane, etc.) and the current electricity price. In this regard, the production of green hydrogen from renewable energy is associated with variable electricity prices. For example, the hydrogen production system may be configured to be easily reconfigured if a high-grade ethanol feedstock is replaced with a lower-grade ethanol or other biofuel. As a further example, the hydrogen production system may be flexibly configured to accommodate alternative uses of the heat generated in the operation of the overall system.

[0122]

[0126] It will thus be appreciated that the hydrogen production system of the present disclosure may be flexibly configured and arranged to accommodate a variety of different potentially available feedstocks, that high thermal efficiency may be achieved because combustion of the feedstock for steam reforming is not required, and that significantly simplified design and operation may be achieved through the reduction of vessels, pipes, valves, heat exchangers, etc.

[0123]

[0127] Thus, the present disclosure provides a hydrogen generation system that advantageously integrates a non-autogenous thermal oxidative reforming system with a water electrolysis system to enable low-cost production of green hydrogen to be achieved. The hydrogen generation system allows oxygen produced as a by-product of the water electrolysis reaction to be used in a non-autogenous thermal oxidative reforming system that processes ethanol or other bio-based feedstocks, thereby enabling the combined non-autogenous thermal oxidative reforming and electrolysis system to produce green hydrogen in a very cost-effective manner. Such combined non-autogenous thermal oxidative reforming and electrolysis systems can be flexibly operated in a variety of modes that selectively maximize either the non-autogenous thermal oxidative reforming or the electrolysis system depending on the cost of feedstock and power. The combined non-autogenous thermal oxidative reforming and electrolysis system of the present disclosure produces low-cost green hydrogen that can be used in fuel cells to generate electricity in a clean and highly efficient manner, with water as the only by-product.

[0124]

[0128] The present disclosure accordingly provides, in various flexibly configured implementations, a combined hydrogen production system including a water electrolyzer and a non-autothermal catalytic oxidative reforming reactor configured to receive oxygen from the water electrolyzer. The present disclosure further provides, in various flexibly configured implementations, a hydrogen production method including (i) electrolyzing water to produce hydrogen and oxygen, and (ii) conducting a non-autothermal oxidative reforming reaction with the oxygen from the electrolysis.

[0125]

[0129] The electrolysis and non-autothermal oxidative reforming in such systems and methods may be configured to operate at any suitable pressure conditions, including atmospheric, superatmospheric, and subatmospheric conditions, and may be configured to match the electrolysis and non-autothermal oxidative reforming operations to accommodate variable energy supply conditions, variable temperature conditions, and variable feedstock conditions. In addition to supplying the non-autothermal oxidative reforming operation, oxygen produced in the electrolysis operation may be transported from the process system to another process system, or to other oxygen-using processes or systems. The non-autothermal oxidative reforming operation may be combined with carbon capture or carbon sequestration systems and methods to provide environmental credits, such as carbon emission credits, or other operational benefits.

[0126]

[0130] In various embodiments, electrolysis may be performed continuously, intermittently, or in other regulated manner to accommodate fluctuations in electricity costs, operating optimally when electricity is cheapest. Hydrogen produced in the electrolysis may be used to generate electricity, which may then be transferred to a power storage device, such as a large battery installation, for buffering the subsequent power needs of the electrolysis operation.

[0127]

[0131] FIG. 5 is a schematic diagram of a hydrogen production system including an integrated oxidative reforming and electrolysis plant that is further integrated with an ethanol refiner and a CO2 processing or carbon capture system according to another embodiment of the present disclosure.

[0128]

[0132] Ethanol refiners produce ethanol as a fermentation product from a fermentable feedstock. The fermentable feedstock can be plant material containing sugars that allow fermentation to produce ethanol, or other starch- and sugar-based feedstocks, or cellulosic feedstocks that include cellulose, hemicellulose, and lignin. A variety of grain materials can be used as feedstocks for ethanol refiners, such as corn, rye, and wheat. Corn is a very commonly used feedstock for ethanol production, and ethanol refiners using corn as a fermentable feedstock currently supply large amounts of ethanol for use as a gasoline additive and for use in a wide range of consumer products.

[0129]

[0133] FIG. 5 in a schematic diagram of an ethanol refinery shows ethanol refinery components that may traditionally be present in an ethanol refinery, but that are removed in the integration of the ethanol refinery with the integrated oxidative reforming and electrolysis system of the present disclosure.

[0130]

[0134] Specifically, such removed components include downstream distillation columns that have become unnecessary due to the direct use in the redox system of the dilute ethanol-water mixture distillate fraction obtained from the initial upstream distillation. In this manner, a simplified, truncated distillation unit can be used.

[0131]

[0135] Additional components of a conventional ethanol refinery that are eliminated in the further integration of the oxidative reforming and electrolytic hydrogen production systems with the ethanol refinery include (i) molecular sieve processing units used to remove water, which may be present, for example, at levels of approximately 5% by volume in the ethanol produced by conventional distillation equipment; (ii) gasoline denaturation processing used for compliance with regulatory requirements for the use of ethanol as a gasoline additive, or processing of ethanol with other denaturants for use in other applications such as hand sanitizer, camping stove fuel, flavorings, etc.; and (iii) ethanol storage facilities traditionally used to hold the bulk of the ethanol produced in the ethanol refinery.

[0132]

[0136] Thus, further integration of the disclosed oxidative reforming and electrolytic hydrogen production system with a significantly smaller, simplified ethanol refinery achieves a significant reduction in the ethanol refinery footprint, and a corresponding reduction in the capital equipment and operating costs of the ethanol refinery.

[0133]

[0137] Such a simplified ethanol refinery may include the illustrated components shown in the embodiment of Figure 5 of an initial grain receiving and storage facility, where corn or other feedstock delivered to the ethanol refinery plant is placed in a storage silo or other container from which it is transferred to a grinding unit. The ground feedstock is then passed to a heating unit, and the heated product is then introduced to a liquefaction unit, where the heated material is subjected to partial hydrolysis to reduce its viscosity for subsequent fermentation in a fermentation unit. The feedstock slurry from the liquefaction unit that is passed to the fermentation unit then undergoes fermentation under controlled temperature and pressure conditions, and the fermentate from the fermentation unit then moves to a centrifuge unit for separation of oil and solids for use in, for example, animal feed or other products, and recovery of an ethanol-water solution that is then passed to a distillation unit.

[0134]

[0138] In the distillation unit, the ethanol-water solution is distilled to reduce its water content, and then the resulting water-reduced ethanol-water solution, which may contain, for example, 40-50% water by volume, is flowed to an integrated oxidative reforming and electrolysis plant as feedstock for the oxidative reforming operation, which includes partial oxidation, steam reforming, and water-gas shift reaction in a single adiabatic reactor of the oxidative reforming system.

[0135]

[0139] The ethanol refinery in the fermentation operation produces CO2 tail gas, which, together with the CO2 tail gas of the integrated oxidative reforming and electrolysis system, can be flowed to a CO2 processing or carbon capture plant that can be configured for packaging of the CO2 as a carbonation gas or chemical synthesis reactant, or for delivery of the CO2 to a pipeline or tanker facility, or for carbon capture processing of the CO2 for carbon sequestration or remediation.

[0136]

[0140] In such further integrated oxidative reforming and electrolysis systems and ethanol refineries, the oxidative reforming and electrolysis plants can be operated such that waste heat generated in the oxidative reforming or electrolysis operations is transported to the fermentation and / or distillation units, so that the entire integrated facility is thermally managed in a highly efficient manner.

[0137]

[0141] The above-described further integration of an integrated oxidative reforming and electrolysis system with an ethanol refinery achieves highly advantageous production of hydrogen gas that leverages existing ethanol refinery infrastructure and simplifies new ethanol refinery construction and operation, particularly when the integrated oxidative reforming and electrolysis system is co-located with the ethanol refinery, for example, in a stationary geographic location facility where the separation distance between the ethanol refinery and the integrated oxidative reforming and electrolysis system is the same or similar to the above-described separation distances between the co-located electrolyzer and non-autothermal oxidative reforming system facilities.

[0138]

[0142] As a specific example of an integrated oxidative reforming and electrolysis system in a 31,250 kg H2 / day hydrogen production system including a 10.5 MW low temperature electrolyzer operating at x=0.40 (reaction (1)) and a non-autothermal ethanol oxidative reformer integrated with a 40,000 gallon / day ethanol refinery, where all of the ethanol production of the ethanol refinery is directed to the production of hydrogen in the further integrated system, Table 3 below lists the operational inputs and outputs for such a further integrated hydrogen production system.

[0139]

[0143] [Table 3]

[0140]

[0144] Thus, further integration of the integrated oxidative reforming and electrolysis system with the ethanol refinery provides various potential benefits in the construction and operation of the ethanol refinery, as well as synergies between the oxidative reforming and electrolysis system integrated with the ethanol refinery. Specifically, such further integration (i) eliminates the need for a complete conventional distillation assembly, since the oxidative reforming and electrolysis system operates with the dilute ethanol feedstock produced by the ethanol refinery, (ii) allows the CO2 tail gas from the oxidative reforming and electrolysis system to be processed by the CO2 storage and transport facility at the ethanol refinery, or alternatively, the CO2 capture facility at the ethanol refinery (which are provided for the processing of the CO2 tail gas from the ethanol refinery), or allows carbon capture of such tail gas from the ethanol refinery, (iii) eliminates the molecular sieve, denaturant addition, and ethanol storage that would otherwise be required at the ethanol refinery, and (iv) allows the by-product heat from the integrated oxidative reforming and electrolysis system to be beneficially used in the fermentation and distillation operations carried out at the ethanol refinery.

[0141]

[0145] Accordingly, the present disclosure contemplates further integrated systems in which an ethanol refinery is integrated with the hydrogen production system of the present disclosure, where the ethanol refinery produces ethanol as a fermentation product from a fermentable feedstock, e.g., corn or other plant or feedstock material, and where the ethanol produced by the ethanol refinery comprises at least a portion of the feedstock fuel for the non-autothermal oxidative reforming system.

[0142]

[0146] The present disclosure further contemplates additional integrated systems in which the ethanol refinery and hydrogen production system are further integrated with a CO2 processing or carbon capture system, where the CO2 processing or carbon capture system is configured to receive CO2 gas from each of the ethanol refinery and the hydrogen production system.

[0143]

[0147] It will therefore be understood that electrolysis and non-autothermal oxidative reforming may be integrated in various ways and in various configurations for green hydrogen production within the broad scope of the present disclosure, and that electrolysis and non-autothermal oxidative reforming may be collocated with each other and with other processes and equipment to accomplish hydrogen production, oxygen production, non-autothermal oxidative reforming, power generation, biomass conversion, CO2 production, and various other operations in an efficient, cost-effective, and environmentally friendly manner.

[0144]

[0148] In practicing the present disclosure, a preferred implementation of the method of the present disclosure may be configured in various embodiments as a hydrogen production method, comprising: electrolyzing water to produce hydrogen and oxygen; and non-autothermal catalytic oxidative reforming a feedstock fuel with the oxygen and water to produce hydrogen, wherein the feedstock fuel comprises a fuel selected from the group consisting of oxygenates, hydrocarbons, and mixtures thereof, and the feedstock fuel has a bio-derived content ranging from 5% to 100% by volume based on the total volume of the feedstock fuel; the reforming is carried out in a single adiabatic reactor into which the hydrocarbon feedstock fuel, oxygen, and water are introduced and into which the produced hydrogen is discharged; the single adiabatic reactor comprises successive catalyst beds contacted sequentially in a flow through the reactor, including (i) a first catalyst bed comprising a partial oxidation catalyst, (ii) a second catalyst bed comprising a steam reforming catalyst, (iii) a third catalyst bed comprising a high temperature water gas shift catalyst, and optionally (iv) a fourth catalyst bed comprising a low temperature water gas shift catalyst. Such preferred method implementations may further implement or incorporate any one or more of the following applicable features (1)-(12):

[0149] (1) The biosourced content of the fuel feedstock is within a range where the lower endpoint is 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%, and the upper endpoint is one of the above numbers above the lower endpoint;

[0150] (2) the feedstock fuel contains biologically produced hydrocarbons;

[0151] (3) the feedstock fuel contains a biologically produced oxygenate;

[0152] (4) the feedstock fuel comprises ethanol;

[0153] (5) the electrolysis is carried out in an electrolytic cell selected from the group consisting of a polymer electrolyte membrane cell, an alkaline cell, and a solid oxide cell;

[0154] (6) The partial oxidation catalyst in the first catalyst bed contains a rhenium catalyst, the steam reforming catalyst in the second catalyst bed contains a nickel catalyst with a promoter supported thereon, the high temperature water gas shift catalyst in the third catalyst bed contains an iron catalyst with copper as a promoter, and the low temperature water gas shift catalyst in any optional fourth catalyst bed, if present in a single adiabatic reactor, contains a monolith catalyst coated with copper / zinc, and if any optional fourth catalyst bed is not present in a single adiabatic reactor, it is present in a low temperature water gas shift reactor external to the single adiabatic reactor and contains a monolith catalyst coated with copper / zinc;

[0155] (7) The partial oxidation reaction is carried out in the first catalyst bed at a temperature in the range of about 700 °C to about 900 °C, the steam reforming reaction is carried out in the second catalyst bed at a temperature in the range of about 400 °C to about 850 °C, the high temperature water gas shift reaction is carried out in the third catalyst bed at a temperature in the range of about 300 °C to about 450 °C, and the low temperature water gas shift reaction, if present in a single adiabatic reactor, is carried out in any optional fourth catalyst bed, or if any optional fourth catalyst bed is not present in a single adiabatic reactor and is present in a low temperature water gas shift reactor external to the single adiabatic reactor, it is carried out at a temperature in the range of about 150 °C to about 350 °C;

[0156] (8) The reforming includes the execution of the reaction C2H5OH+(3 - 2x)H2O+xO2→(6 - 2x)H2+2CO2, where 0 < x < 1.5, or in a further specific embodiment, 0.30 ≦ x ≦ 0.50, or x is within another suitable range of values, for example, 0.10 ≦ x ≦ 1.1; 0.3 ≦ x ≦ 0.9; 0.3 ≦ x ≦ 0.5; or 0.75 ≦ x ≦ 0.85; or x can be, for example, about 0.4, 0.5, 0.65, 0.80, 1.0, or other suitable values;

[0157] (9) The produced hydrogen discharged from the reactor is in the exhaust gas stream at a concentration of at least 60 mol%;

[0158] (10) The reforming is thermally neutral and the electrolysis provides all of the oxygen required by the reforming;

[0159] (11) the electrolysis is carried out in a solid oxide electrolyzer, where reforming is carried out to generate excess heat, and the excess heat generated by the reforming is transferred to the solid oxide electrolyzer such that the solid oxide electrolyzer operates at a thermal efficiency greater than 50%; and

[0160] (12) The optional fourth catalyst bed is not present in the single adiabatic reactor, but is present in a low temperature water-gas shift reactor external to the single adiabatic reactor.

[0145]

[0161] In practicing the present disclosure, a preferred implementation of the system of the present disclosure may be configured, in various embodiments, as a hydrogen production system including an electrolyzer configured to receive water and produce hydrogen and oxygen therefrom; and a non-autothermal oxidative reforming system including a single adiabatic reactor configured to receive oxygen from the electrolyzer, a feed fuel from a feed fuel source, and water from a water source, the reactor including successive catalyst beds contacted in sequence in a flow through the reactor, the successive catalyst beds including (i) a first catalyst bed including a partial oxidation catalyst, (ii) a second catalyst bed including a steam reforming catalyst, and a second catalyst bed including a steam reforming catalyst. (iii) a third catalyst bed comprising a high temperature water gas shift catalyst, and optionally (iv) a fourth catalyst bed comprising a lower temperature water gas shift catalyst, whereby a feed fuel from a feed fuel source together with oxygen and water from the electrolyzer is catalytically oxidatively reformed in the reactor to produce hydrogen, the reactor configured to discharge the produced hydrogen, the feed fuel source configured to provide a feed fuel comprising a fuel selected from the group consisting of oxygenates, hydrocarbons, and mixtures thereof, the feed fuel having a bio-derived content in the range of 5% to 100% by volume based on the total volume of the feed fuel. Such preferred system implementations may further implement or incorporate any one or more of the following applicable features (1) to (13):

[0162] (1) the feed fuel source includes a supply tank, flow circuit, or reservoir containing the feed fuel;

[0163] (2) The electrolyzer and the nonautogenous thermal oxidative reforming system are co-located in a fixed geographic location facility with a separation distance between them of less than at least one of the following: 2.5 km, 2.4 km, 2.3 km, 2.2 km, 2.1 km, 2.0 km, 1.9 km, 1.8 km, 1.7 km, 1.6 km, 1.5 km, 1.4 km, 1.3 km, 1.2 km, 1.1 km, 1.0 km, 0.9 km, 0.8 km, 0.7 km, 0.6 km, 0.5 km, 0.4 km, 0.3 km, 0.2 km, 0.1 km, 0.05 km, and 0.025 km;

[0164] (3) the hydrogen production system is in a modular form mounted on a skid or industrial container for transportation to and installation at the hydrogen production site, the system being configured to produce hydrogen at a rate in the range of 100-2,000 kg hydrogen / day;

[0165] (4) The feedstock fuel in the feedstock fuel source has a bio-based content within a range where the lower endpoint is one of the above numbers above the lower endpoint: 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%;

[0166] (5) the optional fourth catalyst bed is not present in the single adiabatic reactor but is present in a low temperature water-gas shift reactor external to the single adiabatic reactor in the hydrogen production system;

[0167] (6) The feedstock fuel in the feedstock fuel supply contains biologically produced hydrocarbons or biologically produced oxygenates;

[0168] (7) the feedstock fuel in the feedstock fuel supply comprises ethanol;

[0169] (8) the electrolyzer comprises an electrolyzer selected from the group consisting of a polymer electrolyte membrane electrolyzer, an alkaline electrolyzer, and a solid oxide electrolyzer;

[0170] (9) the partial oxidation catalyst in the first catalyst bed comprises a rhenium catalyst, the steam reforming catalyst in the second catalyst bed comprises a promoted nickel catalyst, the high temperature water gas shift catalyst in the third catalyst bed comprises a copper promoted iron catalyst, and if present, the low temperature water gas shift catalyst in the optional fourth catalyst bed comprises a copper / zinc coated monolith catalyst, and if the optional fourth catalyst bed is not present in the single adiabatic reactor, it is present in a low temperature water gas shift reactor external to the single adiabatic reactor and comprises a copper / zinc coated monolith catalyst;

[0171] (10) the hydrogen production system includes a process controller configured to control temperatures in the reactors such that the partial oxidation reaction occurs in the first catalyst bed at a temperature in the range of about 700° C. to about 900° C., the steam reforming reaction occurs in the second catalyst bed at a temperature in the range of about 400° C. to about 850° C., the high temperature water gas shift reaction occurs in the third catalyst bed at a temperature in the range of about 300° C. to about 450° C., and the low temperature water gas shift reaction occurs in the optional fourth catalyst bed if present in the single adiabatic reactor, or at a temperature in the range of about 150° C. to about 350° C. if the optional fourth catalyst bed is not present in the single adiabatic reactor but is present in a low temperature water gas shift reactor external to the single adiabatic reactor;

[0172] (11) The reactor is of vertically elongated configuration configured for downward flow of gas therethrough, with a first catalyst bed at a top-most position in the series overlaying a second catalyst bed which in turn overlays a third catalyst bed which in turn overlays an optional fourth catalyst bed, if present, which is at a bottom-most position in the series, preferably with the successive catalyst beds in the reactor separated from one another by physical separating elements or structures;

[0173] (12) The feedstock fuel in the feedstock fuel supply source includes ethanol, and the hydrogen generation system further includes a process controller configured to adjust the operation of the electrolyzer and the non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system performs the reaction C2H5OH+(3 - 2x)H2O+xO2→(6 - 2x)H2+2CO2, where 0 < x < 1.5, or in a further specific embodiment, 0.30 ≦ x ≦ 0.50, or x is within another suitable range of values, for example, 0.10 ≦ x ≦ 1.1; 0.3 ≦ x ≦ 0.9; 0.3 ≦ x ≦ 0.5; or 0.75 ≦ x ≦ 0.85; or x can be, for example, about 0.4, 0.5, 0.65, 0.80, 1.0, or other suitable values;

[0174] (13) The electrolyzer is a solid oxide electrolyzer, and the hydrogen generation system further includes a process controller configured to adjust the operation of the electrolyzer and the non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system generates excess heat for transfer to the solid oxide electrolyzer so that the solid oxide electrolyzer operates with a thermal efficiency exceeding 50%.

[0146]

[0175] In one particular embodiment (hereinafter referred to as "Embodiment 1"), the present disclosure provides a thermally integrated hydrogen production system, comprising: (A) an electrolyzer configured to receive water and produce hydrogen gas and oxygen gas therefrom; (B) an oxygen storage tank configured to receive oxygen gas from the electrolyzer; (C) a single adiabatic reactor configured to receive oxygen gas from the oxygen storage tank, a feed fuel from a feed fuel source containing a feed fuel, and water from a water source, wherein the single adiabatic reactor comprises successive catalyst beds that are contacted sequentially in flow through the single adiabatic reactor, the successive catalyst beds including (i) a first catalyst bed comprising a partial oxidation catalyst, (ii) a second catalyst bed comprising a steam reforming catalyst, and (iii) a third catalyst bed comprising a high temperature water gas shift catalyst, whereby a feed fuel from the feed fuel source together with oxygen from the oxygen storage tank and water from the water source are catalytically oxidatively reformed in the single adiabatic reactor to produce an oxidatively reformed gas, which is primarily hydrogen, and the single adiabatic reactor is configured to exhaust the produced oxidatively reformed gas. an oxidative reforming system, (D) a first heat exchanger configured to receive the produced oxidatively reformed gas from the single adiabatic reactor and remove heat therefrom to produce a reduced temperature oxidatively reformed gas; (E) a low temperature water gas shift reactor configured to receive the reduced temperature oxidatively reformed gas from the first heat exchanger and convert at least a portion of the carbon monoxide in the reduced temperature oxidatively reformed gas to carbon dioxide to produce a low temperature water gas shift reaction gas with a reduced carbon monoxide content, the low temperature water gas shift reactor including a fourth catalyst bed including a low temperature water gas shift catalyst; (F) a hydrogen gas purifier configured to receive the low temperature water gas shift reaction gas with a reduced carbon monoxide content from the low temperature water gas shift reactor and produce separated hydrogen gas, and a carbon dioxide-containing exhaust gas; (G) a hydrogen gas storage configured to receive hydrogen gas from the electrolyzer and separated hydrogen gas from the hydrogen gas purifier; (H) a burner configured to combust the carbon dioxide-containing exhaust gas produced by the hydrogen gas purifier to obtain a flue gas;(I) a second heat exchanger configured to receive flue gas from the burner for heating oxygen gas from the oxygen storage tank, feed fuel from the feed fuel source, and water from the water source prior to introduction into the single adiabatic reactor; and (J) a process controller configured and arranged to regulate operation of the electrolyzer and the non-autothermal oxidative reforming system in the thermally integrated hydrogen production system and regulate the throughput of each of the electrolyzer and the non-autothermal oxidative reforming system to control the temperature in the single adiabatic reactor, wherein the feed fuel included in the feed fuel source comprises a fuel selected from the group consisting of oxygenates, hydrocarbons, and mixtures thereof, and the feed fuel has a bio-derived content in the range of 5% to 100% by volume, based on the total volume of the feed fuel;

[0147]

[0176]

[0023] Embodiment 1 may be implemented with any one or more of the following features: (1) the raw fuel supply includes a supply tank, flow circuit, or reservoir containing the raw fuel; (2) the electrolyzer and the non-autogenous thermal oxidative reforming system are 2.5 km, 2.4 km, 2.3 km, 2.2 km, 2.1 km, 2.0 km, 1.9 km, 1.8 km, 1.7 km, 1.6 km, 1.5 km, 1.4 km, 1.3 km, 1.2 km, 1.1 km, 1.0 km, 0.9 km, 0.8 km, 0.7 km, 0.6 km, 0.5 km, 0.4 km, 0.3 km, 0.2 km, 0.1 km, 0.0 km, 0.1 km, 0.2 km, 0.3 km, 0.4 km, 0.5 km, 0.6 km, 0.7 km, 0.8 km, 0.9 ...9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, 0.9 km, (3) the hydrogen production system is modular and mounted on a skid or industrial container for transportation to and installation at the hydrogen production site, and the system is configured to produce hydrogen at a rate ranging from 100 to 2000 kg of hydrogen / day; (4) the feedstock fuel source contains a feedstock fuel that is less than or equal to the lower endpoint values ​​of 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, 200%, 210%, 220%, 230%, 240%, 250%, 260%, 270%, 280%, 290%, 300%, 310%, 320%, 330%, 340%, 350%, 360%, 370%, 380%, 390%, 400%, 410%, 420%, 430%, 440%, 450%, 460%, 470%, 480%, 500%, 510%, 520%, 530%, 540%, 550%, 560%, 570%, 580%, 590%, 600%, 700%, 850%, 900%, 950%, 1000%, 1000%, 1100%, 1200%, 1300%, 1400%, 1500%, 1600%, 1700%, 1800%, 1900%, 2000%, 21 %, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%, with the upper endpoint being one of the above values ​​exceeding the lower endpoint; (5) a process controller is constructed and arranged to adjust the throughput of each of the electrolyzer and the nonautothermal oxidative reforming system in response to fluctuations in the feedstock fuel and fluctuations in electricity costs; (6) the feedstock fuel included in the feedstock fuel source is comprised of a biologically produced hydrocarbon or a biologically produced oxygen-containing hydrocarbon. (7) the feed fuel in the feed fuel supply comprises ethanol; (8) the electrolyzer comprises an electrolyzer selected from the group consisting of a polymer electrolyte membrane electrolyzer, an alkaline electrolyzer, and a solid oxide electrolyzer; (9) the partial oxidation catalyst in the first catalyst bed comprises a rhodium catalyst, the steam reforming catalyst in the second catalyst bed comprises a promoted nickel catalyst, the high temperature water gas shift catalyst in the third catalyst bed comprises a copper promoted iron catalyst, and the low temperature water gas shift catalyst in the fourth catalyst bed comprises a copper / zinc coated monolith catalyst;(10) A process controller is configured and arranged to control the temperature in a single adiabatic reactor, whereby a partial oxidation reaction is carried out in a first catalyst bed at a temperature in the range of about 700 °C to about 900 °C, a steam reforming reaction is carried out in a second catalyst bed at a temperature in the range of about 450 °C to about 850 °C, a high-temperature water-gas shift reaction is carried out in a third catalyst bed at a temperature in the range of about 300 °C to about 450 °C, and a low-temperature water-gas shift reaction is carried out in a fourth catalyst bed at a temperature in the range of about 150 °C to about 350 °C; (11) The single adiabatic reactor is of a vertically elongated configuration configured for a downward flow of gas therethrough, with the first catalyst bed at the uppermost position in the continuous catalyst bed covering the second catalyst bed, which in turn covers the third catalyst bed, and the third catalyst bed being at the lowermost position in the continuous catalyst bed; (12) The continuous catalyst beds in the single adiabatic reactor are separated from each other by physical separation elements or structures; (13) The feed fuel contained in the feed fuel source includes ethanol, and the process controller is configured and arranged to adjust the operation of the electrolyzer and the non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system carries out the reaction C2H5OH+(3 - 2x)H2O+xO2→(6 - 2x)H2+2CO2, where x is defined by any of 0 < x < 1.5; 0.10 ≦ x ≦ 1.1; 0.3 ≦ x ≦ 0.9; 0.3 ≦ x ≦ 0.5; 0.75 ≦ x ≦ 0.85, or x is about 0.4, 0.5, 0.65, 0.80, or 1.0; (14) The electrolyzer is a solid oxide electrolyzer, and the process controller is configured and arranged to adjust the operation of the electrolyzer and the non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system generates excess heat for transfer to the solid oxide electrolyzer such that the solid oxide electrolyzer operates with a thermal efficiency greater than 50%; (15) An ethanol purifier that produces ethanol as a fermentation product from a fermentable feedstock, where the ethanol purifier is configured to supply at least a portion of the feed fuel for the non-autothermal oxidative reforming system; (16) The electrolyzer and the non-autothermal oxidative reforming system are configured to transport waste heat to the fermentation and distillation apparatus of the ethanol purifier;(17) a CO2 processing or carbon capture system configured to receive CO2 gas from each of the ethanol refinery and the non-autothermal oxidative reforming system;

[0148]

[0177] In another specific embodiment (hereinafter referred to as "Embodiment 2"), the present disclosure relates to a method of producing hydrogen comprising operating a thermally integrated hydrogen production system as described immediately above to perform a hydrogen production method comprising: electrolyzing water to produce hydrogen gas and oxygen gas therefrom; and non-autothermal catalytic oxidative reforming a feedstock fuel with the oxygen gas and water from a water source to produce hydrogen.

[0149]

[0178] Embodiment 2 can be implemented by any one or more of the following features: (1) The bio-derived content of the raw material fuel has a lower limit endpoint value of 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%, and an upper limit endpoint value within a range that is one of the above values exceeding the lower limit endpoint value; (2) The raw material fuel contains biologically produced hydrocarbons; (3) The raw material fuel contains biologically produced oxygen-containing additives; (4) The raw material fuel contains ethanol; (5) The electrolysis is carried out in an electrolyzer selected from the group consisting of a polymer electrolyte membrane electrolyzer, an alkaline electrolyzer, and a solid oxide electrolyzer; (6) The partial oxidation catalyst in the first catalyst bed contains a rhodium catalyst, the steam reforming catalyst in the second catalyst bed contains a nickel catalyst supported with a promoter, the high-temperature water gas shift catalyst in the third catalyst bed contains an iron catalyst with copper as a promoter, and the low-temperature water gas shift catalyst in the fourth catalyst bed contains a monolith catalyst coated with copper / zinc; (7) The partial oxidation reaction is carried out in the first catalyst bed at a temperature in the range of about 700°C to about 900°C, the steam reforming reaction is carried out in the second catalyst bed at a temperature in the range of about 400°C to about 850°C, the high-temperature water gas shift reaction is carried out in the third catalyst bed at a temperature in the range of about 300°C to about 450°C, and the low-temperature water gas shift reaction is carried out in the fourth catalyst bed in the low-temperature water gas shift reactor at a temperature in the range of about 150°C to about 350°C; (8) Here, x is defined by any of 0 < x < 1.5; 0.10 ≤ x ≤ 1.1; 0.3 ≤ x ≤ 0.9; 0.3 ≤ x ≤ 0.5; 0.75 ≤ x ≤ 0.85, or x is about 0.4, 0.5, 0.65, 0.80, or 1.(9) hydrogen produced in the nonautothermal catalytic oxidative reforming is discharged from the single adiabatic reactor in an exhaust gas stream at a concentration of at least 60 mol %; (10) the nonautothermal catalytic oxidative reforming is thermally neutral and electrolysis provides all of the oxygen required by the nonautothermal catalytic oxidative reforming; (11) electrolysis is performed in a solid oxide electrolyzer, where the nonautothermal catalytic oxidative reforming is performed to generate excess heat, and the excess heat generated by the nonautothermal catalytic oxidative reforming is transferred to the solid oxide electrolyzer such that the solid oxide electrolyzer operates at a thermal efficiency greater than 50%; (12) the throughput of each of the electrolyzer and the nonautothermal oxidative reforming system is (13) producing ethanol as a fermentation product from the fermentable feedstock in the ethanol refinery and providing ethanol from the ethanol refinery as at least a portion of the feedstock fuel for the non-autothermal oxidative reforming system; (14) the electrolyzer and the non-autothermal oxidative reforming system are configured to transport waste heat to the fermentation and distillation units of the ethanol refinery; and (15) processing the CO2 gas in a CO2 processing or carbon capture system configured to receive the CO2 gas from each of the ethanol refinery and the non-autothermal oxidative reforming system.

[0150]

[0179] In various other embodiments of the present disclosure, any one or more of features (1)-(17) defined above for embodiment 1 and any one or more of features (1)-(15) defined above for embodiment 2 may be independently implemented in the systems and methods of the present disclosure described in paragraphs

[0010] -

[0017] herein as further embodiments of the present disclosure. [Explanation of symbols]

[0151]

[0180] A list of drawing reference numbers for the drawings of this disclosure is provided below. 10 Hydrogen Gas Generation System 11 Non-autogenous thermal oxidative reforming systems 12. Non-autogenous thermal oxidative reforming systems 14 Low-temperature electrolysis system 16 Water-ethanol supply line 18 Raw material mixer 20 Heat exchanger 22 Raw material delivery line 24 Heat exchanger 26 Flue Gas Line 28 Non-autothermal Oxidative Reforming Reactor 30 Non-autothermal oxidative reforming reactor discharge line 32 Burner 33 Burner oxygen / air supply line 34 Low Temperature Water Gas Shift Reactor 36 Low temperature water gas shift reactor discharge line 38 Hydrogen gas purifier 40 Hydrogen gas exhaust line 42 Exhaust gas exhaust line 44 Oxygen Supply Line 46 Carbon Dioxide Capture Tank 48 Carbon Dioxide Emission Line 49 Recycled water discharge line 50 Water source 52 Water Pump 54 Water Purifier / Purifier 56 Oxygen-water phase separation and supply tank 58 Water Supply Line 60 Water Circulation Pump 62 Heat exchanger 64 Ion Exchanger 66 PEM electrolyzer 68 Oxygen exhaust line 70 Oxygen demister tank 72 Oxygen exhaust line 73 Oxygen Storage Tank 74 Flow Control Valve 76 Hydrogen Output Line 78 Gas-liquid separation tank 80 Hydrogen Delivery Line 82 Hydrogen Demister Tank 84 Heat exchanger 86 Condensate Trap 88 Flow Control Valve 90 Hydrogen gas storage tank 92 Hydrogen Compressor 94 Hydrogen Discharge Line 96 Hydrogen Supply Line 98 Flow Control Valve 100 Hydrogen Gas Generation System 102 High temperature solid oxide electrolyzer 104 Hydrogen / water vapor exhaust line 106 Oxygen / Water Vapor Exhaust Line 108 Heat exchanger 110 Make-up water supply line 112 Heat exchanger 114 Oxygen / Water Separator 116 Heat exchanger 118 Heat exchanger 120 Heat Recovery Assembly 122 Knockout Pot 124 Hydrogen Discharge Line 126 High Temperature Electrolysis System 128 Electrolyzer Recycle Line 130 Flow control valve 132 Process Controller 134 Bidirectional signal transmission line 136 Bidirectional signal transmission line 140 Process Controller 142 Bidirectional signal transmission line 144 Bidirectional signal transmission line

[0152]

[0069] Although the present disclosure has been described herein with reference to certain aspects, features, and exemplary embodiments, it will be understood that the utility of the present disclosure is not so limited, but extends to and encompasses many other variations, modifications, and alternative embodiments, as would be suggested to one skilled in the art of the present disclosure based on the description herein. Correspondingly, the present disclosure as hereinafter claimed is intended to be broadly understood and construed as including all such variations, modifications, and alternative embodiments within its spirit and scope.

Claims

1. 1. A thermally integrated hydrogen production system comprising: an electrolyzer configured to receive water and produce hydrogen gas and oxygen gas from the water; an oxygen storage tank configured to receive the oxygen gas from the electrolyzer; a non-autothermal oxidative reforming system comprising: a single adiabatic reactor configured to receive oxygen gas from the oxygen storage tank, a feedstock fuel from a feedstock fuel supply source containing the feedstock fuel, and water from a water supply source, the single adiabatic reactor comprising successive catalyst beds contacted sequentially in flow through the single adiabatic reactor, the catalyst beds comprising (i) a first catalyst bed comprising a partial oxidation catalyst, (ii) a second catalyst bed comprising a steam reforming catalyst, and (iii) a third catalyst bed comprising a high temperature water gas shift catalyst, whereby the feedstock fuel from the feedstock fuel supply source together with the oxygen from the oxygen storage tank and the water from the water source are catalytically oxidatively reformed in the single adiabatic reactor to produce an oxidatively reformed gas that is primarily hydrogen, and the single adiabatic reactor configured to discharge the produced oxidatively reformed gas; a first heat exchanger configured to receive the produced oxidatively reformed gas from the single adiabatic reactor and remove heat from the gas to produce a reduced temperature oxidatively reformed gas; a low temperature water-gas shift reactor configured to receive the reduced temperature oxidatively reformed gas from the first heat exchanger and to convert at least a portion of the carbon monoxide in the reduced temperature oxidatively reformed gas to carbon dioxide to produce a low temperature water-gas shift reaction gas having a reduced carbon monoxide content, the low temperature water-gas shift reactor comprising a fourth catalyst bed comprising a low temperature water-gas shift catalyst; a hydrogen gas purifier configured to receive the low temperature water gas shift reaction gas having a reduced carbon monoxide content from the low temperature water gas shift reactor and to produce separated hydrogen gas and a carbon dioxide-containing tail gas; a hydrogen gas reservoir configured to receive the hydrogen gas from the electrolyzer and the separated hydrogen gas from the hydrogen gas purifier; a burner configured to combust the carbon dioxide-containing exhaust gas produced by the hydrogen gas purifier to obtain a flue gas; a second heat exchanger configured to receive the flue gas from the burner for heating the oxygen gas from the oxygen storage tank, the feed fuel from the feed fuel source, and the water from the water source prior to introduction into the single adiabatic reactor; a process controller configured and arranged to coordinate operation of the electrolyzer and the non-autothermal oxidative reforming system in the thermally integrated hydrogen production system and to adjust the throughput of each of the electrolyzer and the non-autothermal oxidative reforming system to control the temperature in the single adiabatic reactor; A thermally integrated hydrogen generation system comprising:

2. The hydrogen generation system of claim 1 , wherein the source of raw fuel comprises a supply tank, a flow circuit, or a reservoir containing the raw fuel.

3. 2. The hydrogen generation system of claim 1, wherein the process controller is constructed and arranged to adjust the throughput of each of the electrolyzer and the non-autothermal oxidative reforming system in response to fluctuations in the feedstock fuel and fluctuations in electricity costs.

4. The hydrogen generation system of claim 1 , wherein the feedstock fuel contained in the feedstock fuel supply comprises a hydrocarbon, an oxygenate, or ethanol.

5. 10. The hydrogen generation system according to claim 1, wherein the electrolyzer comprises an electrolyzer selected from the group consisting of a polymer electrolyte membrane electrolyzer, an alkaline electrolyzer, and a solid oxide electrolyzer.

6. 2. The hydrogen generation system of claim 1, wherein the partial oxidation catalyst in the first catalyst bed comprises a rhodium catalyst, the steam reforming catalyst in the second catalyst bed comprises a promoted nickel catalyst, the high temperature water gas shift catalyst in the third catalyst bed comprises a copper promoted iron catalyst, and the low temperature water gas shift catalyst in the fourth catalyst bed comprises a copper / zinc coated monolith catalyst.

7. 2. The hydrogen generation system of claim 1, wherein the process controller is constructed and arranged to control temperatures in the single adiabatic reactor such that a partial oxidation reaction occurs in the first catalyst bed at a temperature in a range of about 700°C to about 900°C, a steam reforming reaction occurs in the second catalyst bed at a temperature in a range of about 450°C to about 850°C, a high temperature water gas shift reaction occurs in the third catalyst bed at a temperature in a range of about 300°C to about 450°C, and a low temperature water gas shift reaction occurs in the fourth catalyst bed at a temperature in a range of about 150°C to about 350°C.

8. 2. The hydrogen generation system of claim 1, wherein the single adiabatic reactor is in a vertically elongated configuration configured for downward flow of gas therethrough, and wherein the first catalyst bed at an uppermost position in the series of catalyst beds overlies the second catalyst bed, which in turn overlies the third catalyst bed, and the third catalyst bed is at a lowermost position in the series of catalyst beds.

9. The hydrogen generation system of claim 1 , wherein the successive catalyst beds in the single adiabatic reactor are separated from each other by a physical separation element or structure.

10. the feedstock fuel contained in the feedstock fuel supply comprises ethanol, and the process controller is constructed and arranged to regulate operation of the electrolyzer and the non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system C ２ H ５ OH+(3-2x)H ２ O+xO ２ →(6-2x)H ２ +2CO ２ 2. The hydrogen generation system according to claim 1, wherein:

11. 11. The hydrogen generation system of claim 10, wherein the process controller is constructed and arranged to coordinate operation of the electrolyzer and the non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system carries out the reaction, wherein 0.30<x<0.

50.

12. 2. The hydrogen generation system of claim 1, wherein the electrolyzer is a solid oxide electrolyzer, and the process controller is constructed and arranged to coordinate operation of the electrolyzer and a non-autothermal oxidative reforming system, whereby the non-autothermal oxidative reforming system generates excess heat for transfer to the solid oxide electrolyzer such that the solid oxide electrolyzer operates at a thermal efficiency greater than 50%.

13. 10. A method of producing hydrogen comprising operating the thermally integrated hydrogen production system of claim 1 to perform a hydrogen production method, comprising: electrolyzing water to produce hydrogen gas and oxygen gas therefrom; non-autothermal catalytic oxidative reforming of a feedstock fuel with said oxygen gas and water from said water source to produce hydrogen; A method for producing hydrogen comprising:

14. 14. The method for generating hydrogen according to claim 13, wherein the hydrogen produced in the non-autothermal catalytic oxidative reforming is discharged from the single adiabatic reactor in an exhaust gas stream at a concentration of at least 60 mol%, or the non-autothermal catalytic oxidative reforming is thermally neutral and the electrolysis provides all of the oxygen required by the non-autothermal catalytic oxidative reforming.

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