Method, apparatus and system for producing hydrogen and non-gaseous products for industrial applications, energy production and related power generation

Abstract

The invention relates to the treatment of carbonaceous materials, in particular for hydrogen production. In particular, the invention relates to the production of hydrogen, for example as an input to industrial manufacturing applications or as a fuel source for related power generation. In one form, the present invention provides a method of producing hydrogen comprising the step of reacting a composition of a solid carbonaceous material and a catalyst comprising an alpha-phase iron-based material adapted to generate an exothermic reaction with the solid carbonaceous material.

Description

[0001] Related Applications

[0002] This application claims priority to Australian Provisional Patent Application No. 2022900174, entitled “Method, Apparatus and System for Producing Hydrogen and Non-Gaseous Products for Industrial Applications, Energy Production, and Associated Electric Power Generation”, filed on January 31, 2022 in the name of BXB Technologies Pty Ltd, Australian Provisional Patent Application No. 2022901378, entitled “PAK450 Metallic Material”, filed on May 23, 2022 in the name of Henley-Smith et al., and Australian Provisional Patent Application No. 2022901396, entitled “Reduction of Metallic Ores”, filed on May 24, 2022 in the name of Henley-Smith et al., the specifications of which are incorporated herein by reference in their entirety for all purposes. Technical Field

[0003] The present invention relates to the treatment of carbonaceous materials, especially for hydrogen production. In particular, the present invention relates to the production of hydrogen, for example as an input for industrial manufacturing applications or as a fuel source for related power generation. It will be convenient to describe the invention below in relation to a thermal reaction between a carbonaceous material and an alpha-phase iron catalyst (comprising one or a combination of ferrimagnetic iron oxides and alpha ferrites), from which non-gaseous products and a variety of gases are released, one of which is hydrogen for use as a fuel gas. However, it should be understood that the present invention is not limited to this use. Background Art

[0004] Throughout the specification, the word "inventor" used in the singular may be considered to refer to one (singular) inventor or more than one (plural) inventors of the present invention.

[0005] It should be understood that any discussion of documents, devices, acts or knowledge in this specification is included to explain the context of the invention. In addition, the discussion throughout this specification is due to the inventor's appreciation and / or the inventor's recognition of certain relevant technical problems. In addition, any discussion of materials such as documents, devices, acts or knowledge in this specification is included to explain the context of the invention according to the inventor's knowledge and experience, and therefore, any such discussion should not be taken as an admission that any material formed part of the prior art base or common general knowledge in the relevant field in Australia or elsewhere on or before the priority date of the present disclosure and the claims herein.

[0006] There are many known methods for producing hydrogen as a fuel and energy source. For example, "green" hydrogen production methods include electrolysis, which uses an electric current to split water into hydrogen and oxygen. If the input electricity is generated by a renewable resource (such as solar or wind power), the hydrogen produced will also be considered renewable. It is said that by 2050, the green hydrogen market could generate at least $12 trillion in revenue - more than any industry we have today. 1 "Grey / brown" hydrogen production involves coal reforming / gasification processes that convert lignite into carbon monoxide (CO), hydrogen (H2) and carbon dioxide (CO2). Typically, this is achieved through pyrolysis, where the material reacts at temperatures between about 900°C and about 1,150°C. 2 As stated, grey hydrogen production is essentially the same as “blue” hydrogen production, except that the CO2 byproduct is released into the atmosphere. “Blue” hydrogen production typically involves natural gas reforming, where hydrogen is produced by reacting natural gas with high-temperature steam. This process is considered the cheapest, most efficient, and most commonly used. Natural gas reforming accounts for no less than about 70% of the hydrogen currently produced. In addition, according to Petrofac 2 , “pink” hydrogen production is similar to green hydrogen in that it is made through electrolysis but uses nuclear power as the energy source, and another type of hydrogen made through electrolysis is “yellow” hydrogen, where the electrolysis is achieved solely through solar energy, unlike green hydrogen which can use a combination of renewable energy sources such as wind or solar.

[0007] In particular, hydrogen is considered environmentally friendly because the combustion of hydrogen by the end consumer does not produce any CO2 emissions. However, it should be noted that greenhouse gas emissions may be generated during the production and supply of hydrogen.

[0008] Hydrogen production using current technology involves high capital expenditures (CAPEX), high operating expenditures (OPEX), high levels of CO2 emissions, high temperatures (approximately >900°C-1,000°C), and high energy requirements per kg of hydrogen produced.

[0009] Examples showing the deficiencies of existing technologies for renewable and alternative energy production are as follows:

[0010] Solar energy and coal / gas, high CAPEX and high OPEX.

[0011] ·Coal and natural gas steam reforming to produce hydrogen produces a large amount of CO2 emissions.

[0012] The production of each kilogram of hydrogen requires a large amount of energy input.

[0013] · Little or no useful or commercial by-products.

[0014] Wind-solar farms require large land areas and infrastructure.

[0015] Solar power operates only about 20-30% of the time, and wind power is also limited by its operating hours.

[0016] Depending on the location, the energy from solar panels and wind power is limited and not open to the elements in terms of operating hours. Therefore, solar panels can only generate electricity when the sun is shining, and turbines can only operate when the wind is blowing.

[0017] · New distribution infrastructure is required.

[0018] Carbon capture and storage (CCS) increases the cost per kilogram of energy and the cost of energy use.

[0019] Electrolysis systems require the use of large amounts of specially treated water, which is an inefficient use of a precious resource.

[0020] Throughout the 1960s, 1970s and 1980s, in conjunction with the polymer industry and the historic oil / energy crisis, research and development in coal hydrogenation has been conducted. The activity was primarily aimed at increasing the yield of various alkanes. However, there has also been interest in dehydrogenating coal products. 3 The reverse process has been investigated, in which hydrogen is released during dehydrogenation. An example of this activity can be found in Yokono et al. 4 The publication was designed to evaluate catalysts for coal liquefaction, i.e., the conversion of coal into liquid hydrocarbons (i.e., liquid fuels and petrochemicals), in which Yokono et al. conducted a large number of hydrogen evolution pyrolysis reactions on coal samples at a temperature of about 450°C using a series of different Fe2O3-metal oxide catalysts in a 10:1 weight ratio to each other to produce a yield of about 1 ton of coal / kg of hydrogen.

[0021] Interest in the production of hydrogen for fuel has increased significantly since the 21st century. Huffman5 The statement discussed the production of H2 from C1, i.e., single carbon atom molecules (i.e., methane (CH4), carbon monoxide (CO), carbon dioxide (CO2), and methanol (CH3OH)). The statement indicated that gaseous alkanes had been catalyzed using a catalyst consisting of an iron oxide / metal complex in the form of Fe-M (where M = Ni, Mo, or Pd).

[0022] Hydrocarbons were studied and the catalyst showed excellent activity and longevity for the non-oxidative dehydrogenation of gaseous alkanes, producing pure hydrogen in one step without the production of CO or CO2. However, the method disclosed by Huffman is far from an efficient method for producing H2 from solid carbonaceous materials.

[0023] One example of the many hydrogen production methods that have been developed is disclosed in U.S. Pat. No. 7,588,676 (Reichman et al.) Reichman et al. are directed to producing hydrogen from carbonaceous materials by electrochemical reaction in the presence of a base catalyst, wherein carbonate and / or bicarbonate ions are produced as byproducts.

[0024] Hazer Group 6 The plan is to convert natural gas into hydrogen. However, the process disclosed by the Hazer Group involves the production of hydrogen from gaseous hydrocarbons using iron ore as a catalyst at high temperatures and does not address the need to produce H2 from solid carbonaceous materials such as coal or waste organic materials and plastics, etc.

[0025] Other examples of industrial processes that may form relevant prior art are as follows.

[0026] U.S. Patent Application No. 2011 / 0024687 (White et al.) is of general interest in the field of catalysis. The method disclosed by White et al. comprises alternately contacting an oxygen-supported catalyst with a reducing substance or an oxidizing gas at a lower partial pressure, and then contacting the oxidizing gas or an oxidizing gas at a higher partial pressure, whereby the catalyst is alternately reduced and then regenerated to an oxidized state. In certain embodiments disclosed by White et al., when the feedstock is treated in the reduction phase, carbon dioxide and hydrogen are produced as product gases. However, White et al. require reactions involving oxidized catalysts and, in addition, require a pressurized environment.

[0027] U.S. Patent Application No. US20140163120 (Kyle) is directed to a method for converting carbon-containing compounds (e.g., coal, methane, or other hydrocarbons) into liquid hydrocarbon fuels. The method disclosed by Kyle utilizes a high-pressure, high-temperature reactor that operates on a mixture of carbon compounds, catalysts, and steam, including CO2 and a carbon source. Microwave energy is directed into the reactor. The catalyst, preferably magnetite, will serve as a heating medium for the microwave energy, and the temperature of the reactor will rise to a level that effectively converts the carbon and steam into hydrogen and carbon monoxide.

[0028] U.S. Patent Application No. 2018 / 0195006 (Dayton et al.) is directed to a method for converting biomass to hydrocarbon fuels using pyrolysis. Dayton et al. disclose a method for converting a biomass starting material (e.g., a lignocellulosic material) into a stable liquid intermediate with a low oxygen content that can be refined to make a liquid hydrocarbon fuel. More specifically, the method can be a catalytic biomass pyrolysis method in which a deoxygenating catalyst is used in a reactor while subjecting the biomass to pyrolysis conditions. The stream exiting the pyrolysis reactor is The bio-oil comprises a bio-oil having a low oxygen content, and the stream may be subjected to further steps (eg, separation and / or condensation) to separate the bio-oil.

[0029] European patent application No. EP3138892 (Synthopetrol et al.) is dedicated to the production of liquid biofuels and discloses the use of a heterogeneous solid catalyst to carry out a hydrotreatment reaction of gases derived from the pyrolysis of a substrate, wherein the heterogeneous solid catalyst comprises or consists of a metal complex connected to a magnetic carrier by covalent bonds and / or van der Waals interactions, the hydrotreatment reaction being carried out with hydrogen and the gas in the presence of the catalyst and producing a gas phase, which, through a cooling step, leads to the production of a liquid phase formed by liquid biofuel.

[0030] U.S. Patent No. 10,106,407 (Siriwardane et al.) is directed to the production of synthesis gas from methane by oxidation. The embodiment disclosed by Siriwardane et al. includes delivering a metal ferrite oxygen carrier to a fuel reactor, wherein the metal ferrite oxygen carrier comprises MFe x O y, wherein 1≤x≤3 and 3≤y≤5, and wherein M comprises a Group II alkaline earth metal; and a metal ferrite oxygen carrier conveying a gas stream containing methane to a fuel reactor, maintaining the fuel reactor at a reduction temperature sufficient to reduce a portion of the metal ferrite oxygen carrier and oxidize a portion of the methane-containing gas stream. Embodiments also include producing a gaseous product containing H2 and CO gases in the fuel reactor; extracting a product stream from the fuel reactor, wherein the gaseous product comprises the product stream, and wherein at least>50vol% of the product stream comprises CO and H2; in an oxidation reactor, oxidizing the reduced carrier by contacting the reduced carrier with an oxidizing gas at an oxidation temperature, wherein the oxidizing gas consists of oxygen, and wherein the oxidation temperature is sufficient to produce an oxidation reaction, wherein the reactants of the oxidation reaction comprise a portion of oxygen, a portion of the M component, and a portion of Fe c O d component, wherein the oxidation product comprises a portion of MFe x O y and transferring the heat generated in the oxidation reactor to the fuel reactor for the reaction of the metal ferrite with methane.

[0031] CN101891149A (ENN Technology Development Co., Ltd.) relates to a continuous method for preparing combustible gas from a slurry of high-concentration carbon-containing organic matter. The method can be continuously carried out by reducing pressure and continuously discharging the reaction product. The pressure reduction and continuous discharge operation are implemented by using at least two buffer tanks or at least one pressure reducing valve operated in parallel. The disclosure of CN101891149A also relates to an apparatus for preparing combustible gas from a slurry of high-concentration carbon-containing organic matter.

[0032] Qian et al. "Methane decomposition to produce CO x-free hydrogen and nano-carbon over metal catalysts: A review" International Journal of Hydrogen Energy, 2020. Volume 45, pages 7981-8001 discloses a method for producing hydrogen and nano-carbon by catalytic decomposition of methane (CDM). However, it is worth noting that CDM for COx-free hydrogen production is still in its infancy. With the current huge COx emissions, the urgency of industrial-scale CDM is more important than ever. This review studies the progress of CDM on Ni-based catalysts, precious metal catalysts, carbon catalysts, and iron-based catalysts, especially on cheap iron-based catalysts, indicating that CDM is a promising and feasible method for large-scale hydrogen production at a moderately inexpensive cost. In addition, the latest research on the reaction mechanism and kinetics of metal catalysts is outlined. Progress shows that with increasing temperature, the catalyst deactivation rate will be faster than the CDM deactivation rate. This review also evaluates the role of various parameters on the performance of CDM catalysts, such as metal loading effect, influence of support, hydrogen reduction, methane reduction and methane / hydrogen carburization. Catalyst deactivation caused by carbon deposition is the main challenge faced in the CDM method. As an interesting method, a molten metal reactor is proposed to continuously remove solid carbon on the floating surface to overcome the deactivation defect. In addition, in addition to the common fixed bed electric heating reactor and fluidized bed reactor, this review also elaborates on specific CDM reactors using alternative heat sources (such as plasma and solar energy). The development of efficient catalysts and the optimization of reactors are necessary prerequisites for the industrial-scale production of CDM.

[0033] Stolyarchuk et al. "FERRITES MFe2O4 (M=Mg,Mn,Fe,Zn)AS CATALYSTS FOR STEAMREFORMING OF ETHANOL." Theoretical and Experimental Chemistry, 2016, Vol. 52, No. 4, pp. 246-251 discloses a discussion of ferrites as catalysts for steam reforming of ethanol. As discussed by Stolyarchuk et al., the steam reforming (SRE) of ethanol of composite magnesium, manganese, iron and zinc oxides at 823K was studied. X-ray phase analysis showed that the catalytically active phase was composed of ferrites of the corresponding metals with a spinel structure. The hydrogen yield of manganese ferrite and magnesium ferrite was greater than 80% in the absence of CO in the reaction products.

[0034] Takenaka et al. "Production of pure hydrogen from methane mediated by the redox of Ni-and Cr-added iron oxides." Journal of Catalysis. 2004, Vol. 228, pp. 405-416 discuss the production of pure hydrogen from methane by the redox of iron oxides to which Ni and Cr are added. In this study, the preferred effect of adding Ni and Cr species to iron oxides on redox reactions was reported. Compared with iron oxides containing both Cu and Cr species, iron oxides containing both Ni and Cr species can be reduced with methane at a lower temperature and then oxidized with water vapor to repeatedly produce pure hydrogen with high reproducibility. In addition, the role of Ni and Cr species added to the iron oxide samples in the redox reaction is examined based on the local structure of these additives.

[0035] US Patent No. 8,920,525 (Despen et al.) discloses a method and system for converting biomass into a high-carbon bioreagent in a pyrolyzed solid form.

[0036] The above discussion of the background art is intended only to facilitate an understanding of the present invention. The discussion does not constitute an acknowledgement or admission that any of the material referred to is or was ever part of the common general knowledge as at the priority date of the application. Summary of the invention

[0037] It is an object of the present invention to alleviate at least one of the disadvantages associated with the related art.

[0038] In general, the present invention provides a method for producing hydrogen, comprising the following steps:

[0039] A composition of a solid carbonaceous material and a catalyst comprising an alpha-phase iron-based material suitable for producing an exothermic reaction with the solid carbonaceous material is reacted.

[0040] The method may include the following steps:

[0041] combining a mixture of solid carbonaceous material and a catalyst;

[0042] The mixture is reacted by heating the mixture to a temperature of at least about 100°C.

[0043] In a preferred embodiment of the present invention, the catalyst comprises alpha ferrite.

[0044] The catalyst may include one or a combination of the following:

[0045] ferrimagnetic iron oxides;

[0046] Ferrite;

[0047] magnetite.

[0048] Preferably, the magnetite comprises Fe3O4 and the ferrite comprises FeO.

[0049] The mixture of solid carbonaceous material and catalyst may include:

[0050] about 90 weight percent solid carbonaceous material and;

[0051] About 10% by weight of catalyst.

[0052] The step of reacting the mixture may include heating the mixture to a temperature of up to about 1,000°C.

[0053] The method may further comprise the following steps:

[0054] The mixture of solid carbonaceous material and catalyst is reacted to produce a supply of alpha ferrite for further catalytic reactions.

[0055] The reaction step may be performed in a furnace, in a reaction chamber, or in a retort.

[0056] The method may further comprise the following steps:

[0057] The furnace is operated to a temperature of no greater than about 1,000°C to maintain the exothermic reaction of the mixture of solid carbonaceous material and catalyst.

[0058] The method may further comprise the following steps:

[0059] The mixture is dried prior to the step of reacting the mixture to produce an anhydrous composition comprising the carbonaceous material and the catalyst.

[0060] The drying step may be performed at about 35°C. The method may also include one or more of the following steps:

[0061] extruding the mixture to form granules of the mixture prior to the drying step;

[0062] The mixture is molded prior to the drying step to form the mixture into a molded shape for optimized heat transfer.

[0063] The solid carbonaceous material may include one or a combination of the following:

[0064] coal;

[0065] sugar and / or sugar cane;

[0066] corn;

[0067] plastic;

[0068] rubber;

[0069] Waste sludge; and

[0070] scrap.

[0071] The above-mentioned plastic may include one or a combination of the following:

[0072] Polyvinyl chloride (PVC);

[0073] Polyethylene terephthalate (PET);

[0074] Low density polyethylene (LDPE), and;

[0075] High-density polyethylene (HDPE).

[0076] The above-mentioned coal may include one or a combination of the following:

[0077] peat;

[0078] lignite; and

[0079] Subbituminous coal.

[0080] The above waste materials may include one or a combination of the following:

[0081] Rubber products;

[0082] Food and organic waste; and,

[0083] Plastic waste.

[0084] Preferably, for lignite, a typical analysis is as follows:

[0085] Composition analysis

[0086]

[0087] Preferably, the mixture further comprises about 2% by weight of a binder. The binder may further comprise one or a combination of the following:

[0088] cement;

[0089] flour;

[0090] Sodium silicate;

[0091] Corn flour.

[0092] The binder may be formed from an aqueous sodium silicate solution comprising:

[0093] Na2SiO4 mixed at a typical ratio of about 100 g to 1 liter of water at about 60°C.

[0094] The byproducts of the reaction step include hydrogen (H2) and at least one or a combination of:

[0095] Carbon monoxide (CO);

[0096] Carbon dioxide (CO2)

[0097] Methane (CH4);

[0098] Ethane (C2H6); and,

[0099] Carburizing coke.

[0100] The method may further comprise the following steps:

[0101] extracting byproducts of the step of reacting the mixture as synthesis gas and solid byproducts respectively;

[0102] cooling the syngas;

[0103] Separation of hydrogen from synthesis gas.

[0104] The step of separating hydrogen from the synthesis gas may include one or a combination of the following:

[0105] Liquefaction technology; and,

[0106] membrane and filtration technologies;

[0107] Vapor phase and gas phase recovery technologies;

[0108] Enrichment and separation techniques, including catalytic reactions of chemicals.

[0109] The combined steps may include:

[0110] mixing a composition comprising a solid carbonaceous material, a catalyst, and a binder until the composition has a thick paste-like consistency;

[0111] extruding a composition having a paste-like consistency into granules, and / or,

[0112] The composition, which has a paste-like consistency, is molded into molded shapes for optimized heat transfer.

[0113] In general, the present invention also provides an apparatus for producing hydrogen, comprising:

[0114] a reactor having a furnace and a reaction chamber, the reactor being adapted to react a water-free mixture of solid carbonaceous material and a catalyst to a temperature of at least about 100° C. and at most about 1,000° C. to produce synthesis gas and solid byproducts, the catalyst comprising an alpha-phase iron-based material adapted to produce an exothermic reaction with the solid carbonaceous material;

[0115] a cooling system for cooling the synthesis gas;

[0116] A collection system for separating hydrogen from the synthesis gas and collecting the separated hydrogen.

[0117] In the device disclosed herein, the catalyst preferably comprises alpha ferrite. In addition, the catalyst may comprise one or a combination of the following:

[0118] ferromagnetic iron oxides;

[0119] Ferrite;

[0120] magnetite.

[0121] As with the methods disclosed herein, when using the disclosed apparatus, the magnetite may comprise Fe3O4 and the ferrite may comprise FeO. Similarly, when using the apparatus, the mixture may comprise about 90 wt% solid carbonaceous material and about 10 wt% catalyst.

[0122] The apparatus may include a conveyor for handling solid byproducts, wherein the conveyor includes magnetic rollers for separating magnetic particles from non-magnetic particles for one or a combination of:

[0123] Used as industrial components, and;

[0124] Their reuse as catalysts.

[0125] The apparatus may further include a control system operatively connected to one or more of the reactor, the cooling system, and the collection system, wherein the control system includes:

[0126] a furnace burner or heating element controller operatively connected to at least one temperature sensor located within the reaction chamber to control the reaction temperature of the anhydrous mixture of carbonaceous material and catalyst;

[0127] at least one temperature sensor located between the cooling system and the collection system to measure the temperature of the syngas at the collection point;

[0128] at least one pressure gauge located within the collection system; and,

[0129] A display for displaying operating parameters of the device based on measurements from one or a combination of the temperature sensor and the pressure gauge.

[0130] In general, the present invention also provides a modification of a coal-fired power station, wherein the coal-fired power station includes an input coal fuel processing device, a generator, the generator is adapted to be firstly connected to a turbine to drive the generator, and secondly connected to a power distribution network to distribute the power generated by the generator, characterized in that:

[0131] This modification comprises the apparatus of any one of claims 23, 27 or 28, the apparatus being first operatively connected to an input coal fuel processing apparatus as a supply of carbonaceous material and second operatively connected to a turbine for a supply of separated hydrogen.

[0132] Embodiments of the present invention include control means adapted to control the production of hydrogen, said means comprising: processor means adapted to operate according to a predetermined instruction set, said means in conjunction with said instruction set being adapted to perform and control the method steps disclosed herein.

[0133] The control means is preferably adapted to control one or a combination of the following:

[0134] The temperature of at least one of the following:

[0135] a reaction mixture and;

[0136] furnace;

[0137] The flow rate of gaseous products of the reaction step;

[0138] Analysis of gaseous products of reaction steps;

[0139] pressure, and;

[0140] The mechanical speeds of the plant equipment used to carry out the method steps disclosed herein.

[0141] Embodiments may also include a computer program product comprising:

[0142] A computer usable medium having computer readable program code and computer readable system code embodied on said medium for controlling hydrogen production within a data processing system, said computer program product comprising:

[0143] The computer readable code in the computer usable medium is used to perform the method steps disclosed herein.

[0144] The computer program product may be adapted to control one or a combination of the following:

[0145] The temperature of at least one of the following:

[0146] a reaction mixture, and;

[0147] furnace;

[0148] The flow rate of the gaseous products of the reaction step;

[0149] Analysis of gaseous products of reaction steps;

[0150] pressure, and;

[0151] The mechanical speeds of the plant equipment used to carry out the method steps disclosed herein.

[0152] A further embodiment may provide a method of producing hydrogen comprising the steps of:

[0153] combining a mixture of a carbonaceous material and a catalyst comprising one or a combination of a ferrimagnetic iron oxide and a ferrite;

[0154] The mixture is reacted by heating the mixture to a temperature of at least about 100°C.

[0155] Preferably, the step of reacting the mixture comprises heating the mixture to a temperature not exceeding between about 110°C and about 1,000°C.

[0156] In a preferred embodiment, the catalyst comprises one or a combination of magnetite and alpha ferrite. The magnetite may comprise Fe3O4, and the alpha ferrite may comprise FeO.

[0157] Preferably, the mixture includes about 90% by weight carbonaceous material and about 10% by weight catalyst.

[0158] In a preferred embodiment, the method may further comprise the step of reacting the mixture of carbonaceous material and magnetite to produce a supply of alpha ferrite.

[0159] The step of reacting the mixture may be carried out in a furnace in a reaction chamber or retort. The furnace may be operated to a temperature of up to about 1,000° C. The reaction of the mixture becomes an exothermic reaction.

[0160] A further embodiment of the present invention includes a step of drying the mixture prior to the step of reacting the mixture to produce an anhydrous composition comprising a carbonaceous material and a catalyst. The drying step may be performed at about 35°C. Prior to the drying step, the mixture is prepared or molded into a shape that promotes optimal heat transfer. Preferably, the mixture is extruded prior to the drying step to form the mixture into particles. Alternatively, the mixture may be chopped and prepared to be molded into other shapes.

[0161] According to an embodiment of the present invention, the carbonaceous material includes one or a combination of the following:

[0162] coal;

[0163] sugar and / or sugar cane;

[0164] corn;

[0165] Plastics, such as polyvinyl chloride (PVC), polyethylene terephthalate (PET), low-density polyethylene (LDPE), and high-density polyethylene (HDPE);

[0166] rubber;

[0167] Waste sludge; and

[0168] scrap.

[0169] Waste materials may include food waste.

[0170] In a preferred embodiment, the coal comprises one or a combination of peat, lignite; and sub-bituminous coal.

[0171] Preferably, the waste material comprises one or a combination of the following:

[0172] Rubber products;

[0173] Food and organic waste; and,

[0174] Plastic waste.

[0175] In a preferred embodiment, for lignite, a typical analysis is as follows:

[0176] Composition analysis

[0177]

[0178] In a preferred embodiment of the present invention, the mixture further comprises about 2% by weight of a binder. The binder may comprise one or a combination of the following:

[0179] cement;

[0180] flour;

[0181] Sodium silicate;

[0182] Corn flour.

[0183] The binder is preferably formed from an aqueous sodium silicate solution comprising Na2SiO4 mixed at a typical ratio of about 100 g to 1 liter of water at about 60°C.

[0184] The byproducts of the step of reacting the mixture may include hydrogen (H2) and at least one or a combination of:

[0185] water;

[0186] Carbon monoxide (CO);

[0187] Carbon dioxide (CO2);

[0188] Methane (CH4);

[0189] Ethane (C2H6); and,

[0190] Carburized coke.

[0191] In a preferred embodiment, in addition to the primary reaction, the methane produced during the process can be further reacted with a catalyst that decomposes CH4 molecules to produce hydrogen.

[0192] In a preferred embodiment, the method may further comprise the following steps:

[0193] extracting the product of the step of reacting the mixture as synthesis gas and a solid by-product;

[0194] cooling the syngas;

[0195] Separation of hydrogen from synthesis gas.

[0196] The step of separating hydrogen from the synthesis gas may include one or a combination of the following:

[0197] Liquefaction technology; and,

[0198] membrane and filtration technologies;

[0199] Vapor phase and gas phase recovery technologies;

[0200] Enrichment and separation techniques, including catalytic reactions of chemicals.

[0201] Preferably, the combining step comprises:

[0202] mixing a composition comprising a carbonaceous material, a catalyst, and a binder until the composition has a thick paste-like consistency;

[0203] The composition having a paste-like consistency was extruded into granules.

[0204] An embodiment of the present invention also provides an apparatus for producing hydrogen, comprising:

[0205] a reactor having a furnace and a reaction chamber, the reactor being adapted to react a water-free mixture of a carbonaceous material and a catalyst comprising one or a combination of a ferrimagnetic iron oxide and a ferrite by heating the mixture to a temperature of at least about 100°C and no more than about 1,000°C to produce a synthesis gas and a solid byproduct;

[0206] a cooling system for cooling the synthesis gas;

[0207] A collection system for separating hydrogen from the synthesis gas and collecting the separated hydrogen.

[0208] The disclosed apparatus is suitable for carrying out the methods of the embodiments of the invention described herein.

[0209] Preferably, the apparatus comprises a conveyor for handling the solid byproduct, wherein the conveyor comprises magnetic rollers for separating magnetic particles from non-magnetic particles for one or a combination of:

[0210] Used as industrial components, and;

[0211] Their reuse as catalysts.

[0212] The apparatus may further include a control system operatively connected to one or more of the reactor, the cooling system, and the collection system, wherein the control system includes:

[0213] a furnace burner controller operatively connected to at least one temperature sensor located within the reaction chamber to control a reaction temperature of the anhydrous mixture of carbonaceous material and catalyst;

[0214] at least one temperature sensor located between the cooling system and the collection system to measure the temperature of the syngas at the collection point;

[0215] at least one pressure gauge located within the collection system; and,

[0216] A display for displaying operating parameters of the device based on measurements of one or a combination of the temperature sensor and the pressure gauge.

[0217] Embodiments of the present invention may also provide a modification of a coal-fired power station, wherein the coal-fired power station comprises an input coal fuel processing device, a generator adapted to be firstly connected to a turbine to drive the generator, and secondly connected to a distribution network to distribute the electricity generated by the generator, characterized in that:

[0218] The modification includes an apparatus of embodiments disclosed herein in a first operative connection to an input coal fuel processing apparatus as a supply of carbonaceous material and in a second operative connection to a turbine for supplying separated hydrogen.

[0219] An embodiment of the present invention provides a control device suitable for controlling the production of hydrogen, the control device comprising:

[0220] A processor adapted to operate according to a predetermined instruction set, the apparatus in combination with which is adapted to execute and control the method steps disclosed herein.

[0221] Preferably, the control device is suitable for controlling one or a combination of the following:

[0222] The temperature of at least one of the following:

[0223] a reaction mixture and;

[0224] furnace;

[0225] The flow rate of the gaseous products of the reaction step;

[0226] Analysis of gaseous products of reaction steps;

[0227] pressure, and;

[0228] The mechanical speed of a plant for carrying out the method steps of any one of claims 1 to 22.

[0229] A preferred embodiment also provides a computer program product comprising:

[0230] A computer usable medium having computer readable program code and computer readable system code embodied thereon, the computer readable program code and computer readable system code for controlling hydrogen production within a data processing system, the computer program product comprising:

[0231] The computer readable code in the computer usable medium is used to execute the method steps disclosed herein.

[0232] Preferably, the computer program product is adapted to control one or a combination of the following:

[0233] The temperature of at least one of the following:

[0234] a reaction mixture, and;

[0235] furnace;

[0236] The flow rate of the gaseous products of the reaction step;

[0237] Analysis of gaseous products of reaction steps;

[0238] pressure, and;

[0239] The mechanical speeds of the plant equipment used to perform the method steps disclosed herein.

[0240] In essence, embodiments of the present invention arise from the recognition that by selecting an alpha phase iron based catalyst that promotes an exothermic reaction with a carbonaceous material, a large amount of H2 evolution is observed at low temperatures. In the course of conducting reduction experiments for mining applications on different ore types, the inventors utilized a range of coal types and catalyst mixtures containing a combination of at least one ferromagnetic iron oxide and one or more of ferrites (i.e., alpha ferrites). This led the inventors to experiment with varying or different ratios of alpha ferrite and Fe3O4 as a combination of ferrite and / or magnetite based catalysts at different temperatures to successfully generate H2 supplies from a variety of carbonaceous materials.

[0241] Further aspects and preferred forms are disclosed in the description and / or defined in the accompanying claims, forming a part of the description of the invention.

[0242] Advantages provided by embodiments of the present invention include the following:

[0243] Low operating expenditure (OPEX) and low capital expenditure (CAPEX) can be achieved due to the low complexity of the equipment and chemical processes involved.

[0244] Higher yields (kWhH2 / kg coal) than other coal-based processes.

[0245] Reduce power consumption per kg of H2.

[0246] The process involves very low CO2 emissions which can be obtained in the gas separation at the end of the process.

[0247] • Current coke manufacturing systems have high CO2 emission levels, while the preferred embodiment has low CO2 emissions.

[0248] Ultrapure water byproduct for advanced industries such as semiconductor manufacturing.

[0249] • Solid by-products can be used in improved industrial applications, such as improved components for catalytic converters.

[0250] • The preferred embodiment involves an exothermic process which reduces its own processing energy.

[0251] Production rates can be upgraded to production volumes to match any known steam reforming and wind or solar system.

[0252] - Unlike other "green" technologies involving energy generating components that may have a significant composition of rare earth metals, the components making up the implementation of embodiments of the present invention are extremely low in rare earth metals.

[0253] For example, the energy required to produce hydrogen is relatively low, about 5kW / kg H2, compared to about 65kW / kg H2 required for “green, brown and blue hydrogen” production.

[0254] No CO2 is released into the atmosphere, compared to the large amounts of CO2 indirectly released into the atmosphere in known “brown and blue hydrogen” production technologies.

[0255] Produces pure water, CO2 and clean coke byproducts, whereas known “green hydrogen” production technologies produce little or no useful byproducts.

[0256] No new power distribution infrastructure is required.

[0257] • The production plant according to the preferred embodiment can be operated 24 / 7.

[0258] From the specific embodiments given below, further application scope of the embodiments of the present invention will become obvious. However, it should be understood that the specific embodiments and specific examples, although indicating preferred embodiments of the present invention, are given by way of illustration only, because according to the specific embodiments, various changes and modifications within the spirit and scope disclosed herein will become obvious to those skilled in the art. BRIEF DESCRIPTION OF THE DRAWINGS

[0259] Those skilled in the relevant art may better understand the further disclosure, objectives, advantages and aspects of the preferred embodiments and other embodiments of the present invention by referring to the following description of the embodiments in conjunction with the accompanying drawings, which are given by way of illustration only and do not limit the disclosure herein, wherein:

[0260] Figure 1 is a method flow chart showing a preferred embodiment of the present invention;

[0261] Figure 2 is a schematic diagram of an apparatus for carrying out a preferred embodiment of the present invention;

[0262] Figure 3 yes Figure 2 A schematic diagram of an apparatus comprising a control and monitoring device according to a preferred embodiment of the present invention;

[0263] Figure 4 is a schematic diagram of an apparatus for recovering catalyst and solid by-product materials according to a preferred embodiment of the present invention;

[0264] Figure 5 is a schematic diagram of a heat exchange device for recovering a synthesis gas product according to a preferred embodiment of the present invention;

[0265] FIG6A is a diagram of an existing power infrastructure according to the prior art;

[0266] Figure 6B is a diagrammatic representation of the modification of an existing electrical infrastructure in accordance with a preferred embodiment of the present invention. DETAILED DESCRIPTION

[0267] Embodiments of the present invention utilize the release of hydrogen from hydrocarbon compounds, involving a chemical reaction enhanced by a catalyst at a relatively low temperature of about 110°C. The catalytic reaction produces a solid containing pure carbon and a synthesis gas, which can be decomposed into hydrogen in particular. Therefore, small amounts of other gases are easily collected, such as methane CH4, carbon monoxide CO, carbon dioxide CO2, and ethane C2H4. As will be appreciated by those skilled in the art, this gas separation can be effectively performed by one or a combination of the following methods: liquefaction technology; membrane and filtration technology; vapor phase and gas phase recovery technology; and enrichment and separation technology, including the addition of elements such as platinum, palladium, cobalt and nickel to catalyze the reaction. Byproducts of the process include ultrapure water for some carbonaceous materials and coke. In the context of this specification, the term "ultrapure water" is used with reference to a preferred embodiment utilizing lignite as a raw carbonaceous material, and "ultrapure water" refers to water removed from ancient lignite during drying and preparation for catalysis. Ultrapure water removed from lignite has the highest levels of purity for all contaminant types, including organic and inorganic compounds; dissolved and particulate matter; volatile and non-volatile; reactive and inert; hydrophilic and hydrophobic; and dissolved gases.

[0268] In one aspect, preferred embodiments of the present invention relate to the thermochemical catalytic reaction of lignite as the preferred coal-derived carbonaceous material reactant for the production of hydrogen. In another aspect, preferred embodiments of the present invention relate to the thermochemical catalytic reaction of plastics, rubber, freshly grown food feedstock (such as corn and sugar cane), and / or other organic wastes as the preferred waste-derived carbonaceous material reactants for the production of hydrogen.

[0269] In a preferred embodiment, a method for producing hydrogen using coal, particularly lignite, is provided, wherein the method utilizes the chemical reactivity of lignite. The release of hydrogen is promoted by using certain catalytic compounds at low temperatures. The process is preferably carried out at low temperatures using a chemical process, which in turn uses an alpha-phase iron-based catalyst, wherein the preferred catalyst may include one or a combination of alpha ferrite and at least one ferromagnetic iron oxide, or a combination of ferromagnetic iron oxide and ferrite, to initiate an exothermic reaction. The reaction produces a large amount of hydrogen. An increase in the amount of heat applied enhances the catalytic process. Once the temperature of the carbonaceous material and the catalyst is raised to above 110°C, the release of H2 may reach an optimal production level as the heat increases, depending on the raw materials used.

[0270] By comparison with known hydrogen production technologies, the preferred embodiments of the present invention utilize carbon-based precursors, catalysts, other organic raw materials, and recycled resources that are heated to begin the reaction at a temperature in the range of about 110° C. to about 115° C., and then as the temperature of the reaction materials increases, the process becomes exothermic, continuously producing H2 without requiring further energy input. This is in contrast to known hydrogen production methods, including green, gray / brown, and blue hydrogen production methods. In addition, in the process of the preferred embodiment described above, CO2 is produced at a level between about 1% and about 10%, and can be captured (e.g., bottled) for use as an industrial product.

[0271] A preferred embodiment involves the reaction of lignite or other carbonaceous materials over a catalyst in the production of hydrogen fuel gas, wherein the catalyst comprises a combination of one or more magnetites as a source of Fe3O4 and a ferrite (or preferably alpha ferrite) comprising FeO.

[0272] In a preferred embodiment of the present invention, the resulting reaction byproducts include a material residue including carburized coke "coke" of various densities and weights, depending on the raw carbonaceous material used. In the context of this specification, the material residue is a coke material that is pure carbon and includes a residue of a catalyst material and some ash. This residual coke material can be used for carburization in green steelmaking processes, filter media, automotive catalytic converters, etc. For example, the alpha ferrite component in this residual coke material can be separated and used to replace platinum in a catalytic converter. In this case, an improved catalytic converter using the alpha ferrite material of the residual coke material can start the reaction at a starting temperature of about 110°C, rather than at the current temperature of 300°C in the current form of a conventional catalytic converter. In a preferred embodiment of the present invention, the alpha ferrite coke produced as a byproduct is a cheaper and viable alternative to the current way of manufacturing and producing automotive catalytic converters. Another component of the byproduct residue is pure carbon, which can be used in steelmaking and filter media as a cheaper alternative to the current manufacturing process. Furthermore, the manufacture of these carbon-based materials occurs without the CO2 emissions of current manufacturing methods.

[0273] Typical NATA laboratory spectrometer analysis results for the residual solids are inserted in Table 1 below.

[0274]

[0275] Table 1

[0276] refer to Figure 1, which shows one embodiment of the invention, a raw material input material, having an exemplary composition of an alpha phase iron-based catalyst of typically about 90% lignite and typically about 10% alpha ferrite constituting the composition, is mixed with water and a binder. Other embodiments may involve an alpha phase iron-based catalyst comprising a combination of magnetite and ferrite (i.e., alpha ferrite). The preferred binder for this reaction is a sodium silicate compound mixed with water, the composition of which accounts for about 2% of the total weight of the production batch. Several binder compositions have been tested with compositions comprising cement, flour, sodium silicate, and corn flour. In another embodiment, organic waste is used instead of lignite as a reactant source of hydrogen, and the preferred binder comprises a solution of hot water at about 60°C and sodium silicate Na2SiO4 mixed, at a ratio of 100 grams of Na2SiO4 to 1 liter of water. This water is used to add to the mixing process, but it is not always used in its entirety, just until the mixture is uniform and stable, providing the appropriate consistency for preparing the reactants.

[0277] The lignite and catalyst components are weighed to obtain the corresponding net weight percentages for each process batch. The mixture is combined using a paddle mixer or the like to form a uniform consistency, for example, a consistency of about 60% moisture content per 5 tonne load in 1 hour. Basically, the mixture will form a "dry blend" such that the mixture is ready when it can form a uniform clay-like material that can be extruded through a die. At this consistency, the mixture is ready for further processing.

[0278] Then, in order to facilitate the efficient processing of the following steps, the combined mixture is then extruded in an extruder to produce a granular material ready for drying and heat treatment. When the mixture is uniform and has a suitable moisture content, the product is extruded to provide particles of the desired size. For example, the mixture can be processed in an extruder at a rate of 1 ton / hour through a die that produces 8mm particles. For example, in a laboratory-scale plant, 25mm round particles are produced. The combined mixture is then dried in an air recirculating drying oven or an equivalent oven to the extent that the mixture contains less than about 5% moisture. In the example of drying, the granular mixture is placed on one or more trays with recirculating air at about 35°C until the mixture contains less than about 5% moisture. Preferably, one or more trays are placed on a rack and designed to allow free-flowing hot air (about 35°C) to pass through the surface of the tray or each tray. Before heating, the dried mixture can be weighed again.

[0279] refer to Figure 1 and Figure 2, the dried combined mixture is then heat treated and may be placed in a retort within a furnace, wherein the furnace is heated to an operating set point of about 110°C to about 1000°C to control the optimum temperature to effectively release H2. In this regard, the hydrogen production reaction will begin with a reactant temperature of about 100°C. During the heating process, the retort is placed in the furnace and the dried particles are then placed in the retort. A sealing cover is then placed on the retort flange. The cover of the retort is then closed and securely fastened with bolts to achieve a gas-tight effect. The syngas outlet pipe is then connected to the cooling inlet and finally one or more thermocouples are connected to the retort cover. The process is controlled and monitored at Figure 3 is shown in more detail in . Figure 2 A suitable furnace as shown is shown. The furnace may be a steel structure insulated with a suitable form of refractory insulation. An exemplary insulation material may be an alumina based ceramic fiber. One suitable form of such insulation material is the commercially available Fibrefrax TM Thermal insulation material.

[0280] The raw materials are placed in the retort. The hermetically sealed retort is placed in the furnace. Then, a gas burner causes the flame to enter the bottom of the furnace.

[0281] The process is used to break down the chemical components of hydrocarbons to release hydrogen and deposit carbon.

[0282] Those skilled in the art will appreciate that the relative volumes of the resulting gases are optimized by the pressure, residence time, and temperature of the system. The system will be optimized to produce the most H2 and the least CO2 and CO.

[0283] In a preferred embodiment, the catalyst comprises magnetite consisting primarily of Fe3O4 and which may also be recovered after the thermal treatment is completed. Figure 4 An exemplary configuration of a conveyor is shown which can be used to recover catalyst using the ferrimagnetic iron oxide properties of the catalyst component, wherein a preferred embodiment involves a magnetite catalyst. Magnetic particles are separated in and through the conveyor. Figure 4 An exemplary configuration of a conveyor that can be used to recover catalyst from a reaction is shown. As shown, magnetic rollers are used to separate magnetic particles from non-magnetic particles for their reuse. The recovered iron mixture consists of a ferrite-based catalyst.

[0284] Generally speaking, the products of the chemical reactions that occur with heating are as follows:

[0285] High value solids inclusion as by-products;

[0286] oCarburized coke – pure carbon.

[0287] Synthetic gas products, i.e. syngas or fuel gas mixtures, contain:

[0288] oCarbon monoxide CO;

[0289] oCarbon dioxide CO2;

[0290] oMethane CH4;

[0291] oEthane C2H6, and;

[0292] oHydrogen gas H2.

[0293] The ratios of the various products can vary with different input reactants and conditions. Carbon monoxide, CO; typically up to 10% of the product, and can be bottled and sold to industry. Carbon dioxide, CO2; typically around 15%-24%, and can also be bottled and sold to industry. Methane, CH4; typically up to about 40%, and produced to industrial standard purity, can be harvested and sold to industry. Ethane, C2H6; typically up to about 8%, also to industrial standard purity, and can be harvested and sold to industry. Carburized coke; typically up to about 45% of the original quality, also to industrial standard purity, and can also be harvested and sold commercially.

[0294] Since the solid byproduct component comes from the catalytic reaction, the solid byproduct can have a variety of industrial uses. For example, the ferrite material component can be used as an effective substitute for platinum in automotive catalytic converters. Advantageously, the solid byproduct used in the catalytic converter will start to react at 110°C to decompose hydrocarbons in the exhaust gas, compared to platinum, which does not start to react until 300°C, which allows hydrocarbons to be emitted into the atmosphere until the vehicle engine is hot. The solid byproduct can also be used as a carburiser in foundry and steelmaking operations, replacing existing carburisers. One of the benefits is that the byproduct can be safely loaded into the charge with an electromagnet. It can be used as a filtering compound in water treatment and chemical manufacturing industries. It is also envisioned that the solid byproduct can be used as a raw material for making graphene.

[0295] refer to Figure 2 or Figure 3 According to the preferred embodiment, any known gas burner or heat source as understood by those skilled in the art can be used in the H2 production process. For example, a heat source using induction or electrical elements may be suitable as a substitute for the gas burner. The retort containing the reactant material is then placed in the furnace. The furnace cover is bolted to the retort flange and sealed with a gasket. Figure 2 It is shown that, according to the setting, the burner combustion exhaust gas will be discharged from the flue. In operation, the following steps are performed according to the preferred embodiment.

[0296] When the gas burner is ignited, its flame transfers the heat generated to the retort shell, heating the retort contents. The furnace controller regulates the gas input to maintain the set temperature of the contents.

[0297] Thermocouples measure the temperature of the contents inside the retort, e.g. Figure 3 The thermocouple is located approximately at the top center of the sealing plate, 100 mm above the bottom of the retort. As heat is increased, the released gases are exhausted from the retort and piped to a cooling system, such as Figure 2 Shown. Figure 5 An exemplary cooling system is shown in FIG, wherein syngas enters the cooling system at a gas inlet and passes through a gas cooling chamber. During the passage through the gas cooling chamber, the syngas is cooled by cooling water passing through an external cooling medium chamber, wherein the cooling water enters the external cooling medium chamber at a cooling water inlet and leaves the external cooling medium chamber via a cooling water outlet.

[0298] After cooling, the gas passes through a water seal. The water seal acts as a reflux seal and scrubber. As will be appreciated by those skilled in the art, an aluminum foil gas collection bag can be used to sample the generated gas. Sampling was performed during the experiment according to the following design table.

[0299]

[0300]

[0301]

[0302] During the trial production, gases have been collected as required for analysis at a NATA approved laboratory.

[0303] Experimental Results

[0304] The following is a typical report from a NATA-accredited laboratory that provided testing in an experiment to show the accuracy of this invention.

[0305] Analysis of samples J / N 21920 Test 1 and J / N 21920 Test 2 taken on September 20, 2021 was conducted on September 20, 2021 7 .

[0306] Concentration (mol%) Component J / N 21920

[0307] Test 1

[0308] Hydrogen 37.02

[0309] Methane 7.71

[0310] Ethane 0.14C6+0.248

[0311] Carbon dioxide 18.67

[0312] Oxygen plus argon*1.43

[0313] Nitrogen 26.92

[0314] As a precursor step, the ferrite-based catalyst can be produced by reacting a magnetite source of Fe3O4 with a carbonaceous material in the form of coal (i.e., lignite). This reaction produces conditions for the formation of alpha ferrite, as shown in the iron-carbon phase diagram of Figure 1 below.

[0315]

[0316] Another preferred embodiment of the present invention involves replacing lignite with a raw material input containing one or a combination of waste materials of food matter, tires or plastic processed products. For example, it is envisioned that this embodiment can also be used to extract H2 from plastics and tires. In this embodiment, similar chemical reactions can be used to produce hydrogen from food, tire and plastic waste. The hydrogen production process also involves one or a combination of input materials of waste food, tires and plastics in combination with magnetite catalyst and suitable and different binders, which better bind the catalyst to food, tires and plastics rather than coal. In this regard, as described above, organic waste is used instead of lignite as a reactant source of hydrogen, and the preferred binder comprises a solution of hot water at about 60°C and sodium silicate Na2SiO4 mixed, with a ratio of 100 grams of Na2SiO4 to 1 liter of water. This water is used to add to the mixing process, but it is not always used in full, just until the mixture is uniform and stable, providing a suitable consistency for preparing the reactants.

[0317] It should also be understood that, compared to existing green energy solutions, embodiments of the present invention can be directly integrated with existing coal-fired power plants to produce zero CO2. Figure 6B The envisaged modification of the coal-fired power station and its infrastructure may take the form of a coal-fired power station comprising an input coal fuel handling device, a steam generating boiler adapted to be firstly connected to a steam turbine to drive a generator and secondly connected to a distribution network to distribute the electricity generated by the generator, wherein the modification is characterized in that the modification comprises Figure 2 and / or Figure 3 An apparatus is provided that is first operatively connected to an input coal fuel processing apparatus as a supply of carbonaceous material and second operatively connected to a turbine for supplying separated hydrogen.

[0318] In Figure 6A and Figure 6BThe modification of the coal-fired power station and its infrastructure illustrated in the example can include the devices described herein for similar industries that need to maintain 24 / 7 operation to help reduce the demand for traditional models of high carbon emission fuels. Such examples include, but are not limited to, industries such as galvanizing plants, cement manufacturing, aluminum refineries, steel mills (glass furnaces), etc. Due to the hydrogen content in the synthesis gas, the process of converting carbonaceous materials into synthesis gas or its by-products helps to reduce the carbon footprint. Synthesis gas can be mixed into existing fuel supplies or used specifically as a substitute for other plants and equipment.

[0319] Adapted technology can be expanded to include installation of hydrogen injection systems in stationary and mobile diesel engines. Augmenting diesel injection with direct injection of syngas produced according to embodiments of the present invention will significantly reduce emitted carbon (e.g., about 25%) compared to direct diesel emissions.

[0320] Certain embodiments of the present invention may enable existing coal mining infrastructure to remain operational into the future, where instead of burning coal in a coal-fired boiler to produce steam for a steam turbine, an apparatus according to a preferred embodiment may replace the boiler to convert the incoming coal into its equivalent mass of hydrogen for use in a hydrogen-fired turbine to generate electricity. In this way, the existing distribution infrastructure currently extending from conventional coal-fired power stations may also remain operational into the future.

[0321] Although the present invention has been described in conjunction with specific embodiments of the present invention, it will be appreciated that the present invention is capable of further modification. This application is intended to cover any variation, use or modification of the present invention, which generally follows the principles of the present invention, and includes deviations from the present disclosure that are known or customary practice in the field to which the present invention belongs and that can be applied to the essential features set forth above.

[0322] Since the present invention can be implemented in many forms without departing from the spirit of the essential characteristics of the present invention, it should be understood that unless otherwise specified, the above embodiments are not limitations of the present invention, but should be broadly interpreted within the spirit and scope of the present invention defined by the appended claims. The described embodiments are to be considered in all respects as merely illustrative and not restrictive.

[0323] Various modifications and equivalent arrangements are intended to be included in the spirit and scope of the present invention and the appended claims. Therefore, the specific embodiments should be understood to illustrate many ways in which the principles of the present invention can be put into practice. In the following claims, any device-plus-function clause is intended to cover structures that perform defined functions, including not only structural equivalents, but also equivalent structures. For example, although nails and screws may not be structural equivalents, because nails use cylindrical surfaces to fix wooden parts together, and screws use spiral surfaces to fix wooden parts together, in the case of fastening wooden parts, nails and screws are equivalent structures. In addition, as an example of a specific embodiment of the present invention, it is envisioned that the specific ratio of the component input reactant material of the present invention is modified and modified to provide the optimal production of the obtained product of the inventive method according to different conditions (such as conditions related to temperature and pressure).

[0324] Sections I-VII below provide guidance for interpreting this specification.

[0325] I. Terminology

[0326] The term "product" means any machine, article of manufacture, and / or composition of matter, unless expressly stated otherwise.

[0327] The term "process" refers to any industrial process, algorithm, methodology, etc., unless expressly stated otherwise.

[0328] The term "anhydrous" means, with respect to any combination or mixture of materials disclosed herein, free of water or moisture to at least 5% or less water by weight.

[0329] Each process (whether referred to as a method, algorithm or otherwise) inherently includes one or more steps, and therefore all references to the "step" or "steps" of a process have an inherent premise basis when merely reciting the term "process" or similar terms. Therefore, any reference to the "step" or "steps" of a process in the claims has a sufficient premise basis.

[0330] The term "invention" and the like means "one or more inventions disclosed in this specification" unless explicitly stated otherwise.

[0331] The terms “an embodiment,” “embodiment,” “embodiments,” “the embodiment,” “the embodiments,” “one or more embodiments,” “some embodiments,” “certain embodiments,” “one embodiment,” “another embodiment,” etc. mean “one or more (but not all) embodiments of the disclosed invention,” unless expressly stated otherwise.

[0332] The term "variation" of the present invention refers to an embodiment of the present invention unless explicitly stated otherwise.

[0333] Reference to "another embodiment" when describing an embodiment does not mean that the referenced embodiment is mutually exclusive of another embodiment (eg, an embodiment described before the referenced embodiment) unless explicitly stated otherwise.

[0334] The terms "including", "comprising" and variations thereof mean "including but not limited to", unless expressly stated otherwise.

[0335] The terms "a", "an" and "the" mean "one or more" unless expressly stated otherwise.

[0336] The term "plurality" means "two or more" unless expressly stated otherwise.

[0337] The term "herein" means "in this specification, including anything that may be incorporated by reference", unless explicitly stated otherwise.

[0338] When the phrase "at least one" modifies multiple things (such as an enumerated list of things), the phrase means any combination of one or more of those things, unless otherwise expressly stated. For example, the phrase "at least one of a widget, a car, and a wheel" means (i) a widget, (ii) a car, (iii) a wheel, (iv) a widget and a car, (v) a widget and a wheel, (vi) a car and a wheel, or (vii) a widget, a car, and a wheel. When the phrase "at least one" modifies multiple things, the phrase does not mean "one of each of the multiple things."

[0339] Numerical terms such as "one", "two", etc., when used as cardinality to indicate the quantity of something (e.g., one widget, two widgets), mean the quantity indicated by the numerical term, but not at least the quantity indicated by the numerical term. For example, the phrase "one widget" does not mean "at least one widget", so the phrase "one widget" does not cover, for example, two widgets.

[0340] The phrase "based on" does not mean "based only on," unless explicitly stated otherwise. In other words, the phrase "based on" describes both "based only on" and "based at least on." The phrase "based at least on" is equivalent to the phrase "based at least in part on."

[0341] The term "represents" and similar terms are not exclusive unless expressly stated otherwise. For example, the term "represents" does not mean "represents only" unless expressly stated otherwise. In other words, the phrase "the data represents a credit card number" describes both "the data represents only a credit card number" and "the data represents a credit card number and the data also represents something else."

[0342] The term "therefore" is used herein only to precede a clause or other phrase, and only expresses the intended result, object, or consequence of the things explicitly stated previously. Therefore, when the term "therefore" is used in a claim, the clause or other words modified by the term "therefore" will not establish a specific further limitation on the claim, nor will it otherwise limit the meaning or scope of the claim.

[0343] The term "eg" and similar terms mean "for example", and therefore do not limit the term or phrase to which it is interpreted. For example, in the sentence "a computer sends data (e.g., instructions, data structure) via the Internet", the term "eg" explains that "instructions" are an example of "data" that a computer can send via the Internet, and also explains that "data structure" is an example of "data" that a computer can send via the Internet. However, both "instructions" and "data structure" are examples of "data", and things other than "instructions" and "data structure" may also be "data".

[0344] The term "ie" and similar terms mean "that is", thereby limiting the term or phrase to which it is interpreted. For example, in the sentence "the computer sends data (ie instructions) over the Internet", the term "ie" explains that the "instructions" are the "data" that the computer sends over the Internet.

[0345] Any given numerical range should include integers and fractions within the range. For example, the range "1 to 10" should be interpreted as specifically including integers (e.g., 2, 3, 4, ... 9) and non-integers (e.g., 1.1, 1.2, ... 1.9) between 1 and 10.

[0346] II. Determination

[0347] The term "determine" and its grammatical variations (e.g., determine a price, determine a value, determine an object that meets certain criteria) are used in an extremely broad sense. The term "determine" encompasses a wide variety of actions, and thus "determine" may include calculating, computing, processing, deriving, investigating, searching (e.g., searching in a table, database, or other data structure), ascertaining, and the like. Furthermore, "determining" may include receiving (e.g., receiving information), accessing (e.g., accessing data in a memory), and the like. Furthermore, "determining" may include resolving, selecting, choosing, establishing, and the like.

[0348] The term "determine" does not mean certainty or absolute precision, and thus "determine" may include estimation, inference, prediction, guesswork, and the like.

[0349] The term "determining" does not necessarily imply a mathematical manipulation, the use of numerical methods, or the use of an algorithm or procedure.

[0350] The term "determining" does not imply that any particular apparatus must be used. For example, a computer is not necessarily required to perform the determination.

[0351] III. Instructions

[0352] The term "indication" is used in an extremely broad sense. The term "indication" may include, among other things, a sign, a representation or a symbol of something else.

[0353] The term "indicative" may be used to refer to any indicia and / or other information that indicates or is associated with a subject, item, entity, and / or other object and / or idea.

[0354] As used herein, the phrases "indicative information" and "indicia" may be used to refer to any information that represents, describes, and / or is otherwise associated with a relevant entity, subject, or object.

[0355] Information indicia may include, for example, symbols, codes, references, links, signals, identifiers and / or any combination thereof and / or any other information representation associated with the information.

[0356] In some embodiments, the mark of information (or indication of information) can be or include the information itself and / or any part or component of the information. In some embodiments, the indication can include a requirement, request, broadcast and / or any other form of information collection and / or dissemination.

[0357] IV. Sentence Form

[0358] Where a limitation in the first claim will cover one feature as well as more than one feature (e.g., a limitation such as “at least one widget” covers one widget as well as more than one widget), and where in a second claim that is dependent on the first claim, the second claim uses the definite article “said” to refer to the limitation (e.g., “said widget”), this does not mean that the first claim covers only one feature nor that the second claim covers only one feature (e.g., “said widget” may cover one widget as well as more than one widget).

[0359] When an ordinal number (e.g., "first," "second," "third," etc.) is used as an adjective before a term, the ordinal number is used only (unless otherwise expressly stated) to indicate a particular characteristic, such as to distinguish the particular characteristic from another characteristic described by the same or similar term. For example, a "first widget" may be so named solely to distinguish it from, for example, a "second widget." Thus, the mere use of the ordinals "first" and "second" before the term "widget" does not indicate any other relationship between the two widgets, nor any other characteristics of either or both widgets. For example, the mere use of the ordinals "first" and "second" before the term "widget" (1) does not indicate that either widget precedes or follows any other widget in order or position; (2) does not indicate that either widget occurs or acts before or after any other widget in time; and (3) does not indicate that either widget ranks higher or lower in importance or quality than any other widget. Furthermore, the mere use of an ordinal number does not impose a numerical limit on the characteristics identified by the ordinal number. For example, the mere use of the ordinal numbers "first" and "second" before the term "widget" does not indicate that there must not be more than two widgets.

[0360] When a single device or article is described herein, more than one device / article (whether or not they work in conjunction) may alternatively be used in place of the single device / article described. Thus, functionality described as being possessed by one device may alternatively be possessed by more than one device / article (whether or not they work in conjunction).

[0361] Similarly, where more than one device or article is described herein (whether or not they work in conjunction), a single device / article may alternatively be used in place of the more than one device or article described. For example, multiple computer-based devices may be replaced with a single computer-based device. Thus, various functions described as being possessed by more than one device or article may alternatively be possessed by a single device / article.

[0362] The functions and / or features of the described single devices may alternatively be embodied by one or more other devices that are described but not explicitly described as having such functions / features. Therefore, other embodiments need not include the described devices themselves, but may include one or more other devices that will have such functions / features in those other embodiments.

[0363] V. Disclosed Examples and Terms Are Not Limiting

[0364] Neither the title nor the abstract in this specification is intended to be considered as limiting the scope of the one or more inventions disclosed in any way. The titles and section titles provided in the specification are for convenience only and should not be considered as limiting the present disclosure in any way.

[0365] Many embodiments are described in this application, which are presented for illustrative purposes only. The described embodiments are not, nor are they intended to be, limiting in any sense. It is apparent from the disclosure that one or more inventions disclosed herein are widely applicable to many embodiments. One of ordinary skill in the art will recognize that one or more inventions disclosed herein can be practiced with various modifications and substitutions, such as structural, logical, software, and electrical modifications. Although specific features of one or more inventions disclosed herein can be described with reference to one or more specific embodiments and / or accompanying drawings, it should be understood that these features are not limited to use in reference to one or more specific embodiments or accompanying drawings describing them, unless otherwise expressly stated.

[0366] This disclosure is not a literal description of all embodiments of the one or more inventions. Furthermore, this disclosure is not a list of features of the one or more inventions that must be present in all embodiments.

[0367] Devices described as being in communication with each other need not be in continuous communication with each other unless explicitly stated otherwise. Rather, such devices need only communicate with each other when necessary or desired, and may not actually be exchanging data or material most of the time. For example, a machine communicating with another machine over the Internet may not transmit data to the other machine for long periods of time (e.g., weeks at a time). Furthermore, devices in communication with each other may communicate directly or indirectly through one or more intermediaries. The same may apply to industrial machinery and equipment.

[0368] The description of an embodiment with multiple components or features does not mean that all or even any such components / features are required. Instead, various optional components are described to illustrate various possible embodiments of the invention. Unless otherwise expressly stated, no component / feature is necessary or required.

[0369] Although process steps, operations, algorithms, etc. can be described in a particular order, such a process can be configured to work in a different order. In other words, any order or sequence of steps that can be clearly described does not necessarily indicate that these steps are required to be performed in that order. The steps of the process described herein can be performed in any practical order. In addition, some steps can be performed simultaneously, although described or implied as not occurring at the same time (for example, because one step is described after another step). In addition, illustrating a process by describing in the accompanying drawings does not mean that the illustrated process excludes other variations and modifications to the process, nor does it mean that the illustrated process or any of its steps is necessary for the one or more inventions, and it does not mean that the illustrated process is preferred.

[0370] Although a process may be described as including multiple steps, it does not mean that all or any steps are preferred, necessary or required. Various other embodiments within the scope of one or more of the inventions described include other processes that omit some or all of the steps described. Unless otherwise explicitly stated, there are no necessary or required steps.

[0371] Although a process may be described in isolation or without reference to other products or methods, in an embodiment, the process may interact with other products or methods. For example, such interaction may include linking one business model to another business model. Such interaction may be provided to enhance the flexibility or desirability of the process.

[0372] Although a product may be described as comprising a plurality of components, aspects, qualities, properties and / or features, this does not indicate that any or all of the plurality are preferred, necessary or required. Various other embodiments within the scope of one or more of the inventions described include other products that omit some or all of the plurality.

[0373] An enumerated list of items (which may or may not be numbered) does not imply that any or all of the items are mutually exclusive, unless expressly stated otherwise. Likewise, an enumerated list of items (which may or may not be numbered) does not imply that any or all of the items are comprehensive of any category, unless expressly stated otherwise. For example, the enumerated list "computers, laptops, PDAs" does not imply that any or all of the three items in the list are mutually exclusive, nor does it imply that any or all of the three items in the list are comprehensive of any category.

[0374] The enumerated listing of items (which may or may not be numbered) does not imply that any or all of the items are equivalent or readily interchangeable.

[0375] All embodiments are illustrative and are not intended to be an accomplished or enabled invention or any embodiment, as the case may be.

[0376] When used in this specification, "comprises / comprising" and "includes / including" are used to specify the presence of stated features, integers, steps or components, but do not exclude the presence or addition of one or more other features, integers, steps, components or groups thereof. Therefore, unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise", "comprising", "includes", "including" and the like should be interpreted in an inclusive sense rather than an exclusive or exhaustive sense; that is, in the sense of "including but not limited to".

[0377] Process Authentication Examples

[0378] Certification test results of working embodiments of the present invention are for raw materials of lignite and LDPE plastics, respectively.

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Claims

1. A method for producing hydrogen, comprising the following steps: A composition of a solid carbonaceous material and a catalyst comprising an alpha-phase iron-based material suitable for producing an exothermic reaction with the solid carbonaceous material is reacted.

2. The method according to claim 1, wherein the method comprises the following steps: combining a mixture of said solid carbonaceous material and said catalyst; The mixture is reacted by heating the mixture to a temperature of at least about 110°C.

3. The method of claim 1 or 2, wherein the catalyst comprises alpha ferrite.

4. The method according to claim 1, 2 or 3, wherein the catalyst comprises one or a combination of: ferrimagnetic iron oxides; Ferrite; magnetite.

5. The method of claim 4, wherein the magnetite comprises Fe3O4 and the ferrite comprises FeO.

6. The method according to any one of claims 2 to 5, wherein the mixture of the solid carbonaceous material and the catalyst comprises: about 90 weight percent solid carbonaceous material and; About 10% by weight of catalyst.

7. The method of any one of claims 2 to 6, wherein the step of reacting the mixture comprises heating the mixture to a temperature of up to about 1,000°C.

8. The method according to any one of claims 1 to 7, further comprising the following steps: The mixture of the solid carbonaceous material and the catalyst is reacted to produce a supply of alpha ferrite for further catalytic reaction.

9. The method according to any one of claims 1 to 8, wherein the reacting step is carried out in a furnace in a reaction chamber or retort.

10. The method according to claim 9, further comprising the steps of: The furnace is operated to a temperature of no greater than about 1,000°C to maintain an exothermic reaction of the mixture of the solid carbonaceous material and the catalyst.

11. The method according to any one of claims 2 to 10, further comprising the following steps: The mixture is dried prior to the step of reacting the mixture to produce an anhydrous composition comprising the carbonaceous material and the catalyst.

12. The method of claim 11, wherein the drying step is performed at about 35°C.

13. The method according to claim 11 or 12, further comprising one or more of the following steps: extruding the mixture to form granules from the mixture prior to the drying step; The mixture is molded prior to the drying step to form the mixture into a molded shape for optimizing heat transfer.

14. The method according to any one of claims 1 to 13, wherein the solid carbonaceous material comprises one or a combination of: coal; sugar and / or sugar cane; corn; plastic; Tires and rubber products; Waste sludge; and scrap.

15. The method according to claim 14, wherein the plastic comprises one or a combination of the following: Polyvinyl chloride (PVC); Polyethylene terephthalate (PET); Low density polyethylene (LDPE), and; High-density polyethylene (HDPE).

16. The method according to claim 14 or 15, wherein the coal comprises one or a combination of the following: peat; lignite; and, Subbituminous coal.

17. The method of claim 14, 15 or 16, wherein the waste material comprises one or a combination of: Tires and rubber products; Food and organic waste; and, Plastic waste.

18. The method according to claim 16, wherein for lignite, the following composition analysis is included: Composition analysis 19. The method of any one of claims 2 to 18, wherein the mixture further comprises about 2% by weight of a binder.

20. The method of claim 16, wherein the adhesive comprises one or a combination of: cement; flour; Sodium silicate; Corn flour.

21. The method according to claim 16, wherein the binder is formed from an aqueous sodium silicate solution comprising: Na2SiO4 mixed at a typical ratio of about 100 g to 1 liter of water at about 60°C.

22. The method according to any one of the preceding claims, wherein the byproducts of the reaction step comprise hydrogen (H2) and at least one or a combination of: Carbon monoxide (CO); Carbon dioxide (CO2) Methane (CH4); Ethane (C2H6); and, Carburized coke.

23. The method according to claim 22, further comprising the steps of: extracting byproducts of the step of reacting the mixture as synthesis gas and solid byproducts, respectively; cooling the syngas; Hydrogen is separated from the synthesis gas.

24. The method of claim 23, wherein the step of separating hydrogen from the synthesis gas comprises one or a combination of: Liquefaction technology; and, membrane and filtration technologies; Vapor and gas phase recovery technologies; Enrichment and separation processes involving catalytic reactions of chemicals.

25. The method according to any one of claims 19 to 21, wherein the step of combining comprises: mixing a composition comprising the solid carbonaceous material, a catalyst, and a binder until the composition has a thick paste-like consistency; extruding the composition having a paste-like consistency into granules, and / or The composition, which has a paste-like consistency, is molded into molded shapes for optimizing heat transfer.

26. An apparatus for producing hydrogen, comprising: a reactor having a furnace and a reaction chamber, the reactor being adapted to react a water-free mixture of solid carbonaceous material and a catalyst by heating the mixture to a temperature of at least about 110° C. and at most about 1,000° C. to produce synthesis gas and a solid byproduct, the catalyst comprising an alpha-phase iron-based material adapted to produce an exothermic reaction with the solid carbonaceous material; a cooling system for cooling the synthesis gas; A collection system for separating hydrogen from the synthesis gas and collecting the separated hydrogen.

27. The device of claim 26, wherein the catalyst comprises alpha ferrite.

28. The device according to claim 26 or 27, wherein the catalyst comprises one or a combination of: ferrimagnetic iron oxides; Ferrite; magnetite.

29. The apparatus of claim 28, wherein the magnetite comprises Fe3O4 and the ferrite comprises FeO.

30. The device according to any one of claims 23 to 25, wherein the mixture comprises: about 90 weight percent solid carbonaceous material and; About 10% by weight of catalyst.

31. Apparatus according to any one of claims 26 to 30, comprising a conveyor for handling the solid byproduct, wherein the conveyor comprises magnetic rollers for separating magnetic particles from non-magnetic particles for one or a combination of: Used as industrial components, and; Their reuse as catalysts.

32. The apparatus of any one of claims 26 to 31, further comprising a control system operatively connected to one or more of the reactor, the cooling system, and the collection system, wherein the control system comprises: a furnace burner or heating element controller operatively connected to at least one temperature sensor located within the reaction chamber to control the reaction temperature of the anhydrous mixture of carbonaceous material and catalyst; at least one temperature sensor located between the cooling system and the collection system to measure the temperature of the syngas at a collection point; at least one pressure gauge located within the collection system; and, A display for displaying operating parameters of the device based on measurements of one or a combination of the temperature sensor and the pressure gauge.

33. A modification of a coal-fired power station, wherein the coal-fired power station comprises an input coal fuel processing device, a generator, the generator being adapted to be first connected to a turbine to drive the generator, and second connected to a power distribution network to distribute the power generated by the generator, characterized in that: The modification comprises an apparatus as claimed in any one of claims 23, 27 or 28 in a first operative connection with an input coal fuel processing apparatus as a supply of carbonaceous material and in a second operative connection with a turbine to supply separated hydrogen.

34. A control device suitable for controlling hydrogen production, the control device comprising: Processor means adapted to operate according to a predetermined instruction set, said means in combination with said instruction set being adapted to perform and control the method steps according to any one of claims 1 to 25.

35. A control device according to claim 34, wherein the control device is adapted to control one or a combination of the following: The temperature of at least one of the following: a reaction mixture, and; furnace; The flow rate of gaseous products of the reaction step; Analysis of gaseous products of reaction steps; pressure, and; Mechanical speed of a plant for carrying out the method steps according to any one of claims 1 to 25.

36. A computer program product comprising: A computer usable medium having computer readable program code and computer readable system code embodied thereon, the computer readable program code and computer readable system code for controlling hydrogen production within a data processing system, the computer program product comprising: The computer readable code in the computer usable medium is for performing the method steps as claimed in any one of claims 1 to 25.

37. A computer program product according to claim 36, wherein the computer program product is adapted to control one or a combination of: The temperature of at least one of the following: a reaction mixture, and; furnace; The flow rate of gaseous products of the reaction step; Analysis of gaseous products of reaction steps; pressure, and; The mechanical speed of a plant for carrying out the method steps of any one of claims 1 to 25.

38. A method, process or protocol as herein disclosed.

39. An apparatus, system and / or device as herein disclosed.

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