Process for reducing organic material to produce methane and / or hydrogen

Abstract

A process for reducing organic material to produce methane and / or hydrogen is disclosed, which includes: (a) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, where the reduction chamber is substantially oxygen-free, and heating the reduction chamber to produce a temperature increase within the organic material from ambient temperature to up to 425°C under positive pressure at a rate of up to about 8°C per minute to form a first gaseous mixture containing methane, hydrogen, acid, and partially reduced volatile organic molecules; (b) heating the first gaseous mixture to a temperature of about 675°C to about 875°C in the presence of an excess of hydrogen gas to form a second gaseous mixture containing methane, hydrogen, and acid; and (c) neutralizing the second gaseous mixture with a base. In another aspect, the process includes: (a1) contacting an organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, wherein the reduction chamber is substantially oxygen-free; and heating the reduction chamber to produce a temperature increase within the organic material from ambient temperature to up to 425°C under positive pressure at a rate of up to about 8°C per minute to form a first gaseous mixture comprising methane, hydrogen, an acid, and partially reduced volatile organic molecules; and (b1) neutralizing the first gaseous mixture with a base.

Description

[Technical field]

[0001] The present invention relates to a process for the reduction of organic material to produce methane and / or hydrogen. More specifically, the present invention relates to a process for the reduction of organic material to produce methane and / or hydrogen as end products using excess hydrogen under controlled reaction conditions. [Background technology]

[0002] In recent years, many countries and international commissions have proposed or issued regulations regarding the production of energy from alternative or renewable sources and the need to significantly reduce greenhouse gases (GHGs) and other factors contributing to global warming.

[0003] In 2014, the United States Environmental Protection Agency (US EPA) created the "Clean Power Plan" policy aimed at reducing carbon pollution from power plants. Power plants are the largest source of carbon dioxide (CO2) emissions in the United States, accounting for about one-third of the nation's greenhouse gas emissions. The plan was designed to reduce carbon pollution, especially CO2 emissions, from the power sector by 30% by 2030. The US EPA's New Source Performance Standards (NSPS) for GHG emissions from power plants specify a limit of 636 kgCO2 / MWh for coal-fired power plants and 454 kgCO2 / MWh for natural gas combustion turbine power plants. These types of standards result in increased demands to improve existing power and energy production efficiency, as well as to explore new methods for energy production from non-fossil fuel sources.

[0004] Globally, measures have been taken to address the growing concerns of GHG emissions and global warming. The Kyoto Protocol was adopted in 1997 and came into force in 2005. Currently, there are 192 parties to the Kyoto Protocol. In the first commitment period of the Kyoto Protocol (2008-2012), developed countries (Annex B of the Protocol) committed to reducing GHG emissions by at least 5% compared to 1990 levels. The Kyoto Protocol was eventually extended in 2012, and a second commitment period (2013-2020) was agreed by the parties, in which Annex B countries committed to reducing their respective emissions by a total of 18% by 2020 compared to 1990 levels. The European Union committed to a 20% reduction. Global efforts to reduce GHGs create demand for cleaner and more efficient methods of energy production, waste reduction, and pollution prevention. Therefore, incentives for technologies to address these issues are currently in high demand.

[0005] Natural gas is a widely used fuel for power generation. Cogeneration, gas turbines, and steam turbines produce electricity. Natural gas contains a high concentration of methane and burns cleaner than all other fossil fuels such as oil, coal, gasoline, and diesel. This cleaner combustion produces fewer greenhouse gases (GHG) per unit of energy emitted. Therefore, power generation using natural gas is considered the cleanest hydrocarbon energy source available. Natural gas is also widely used as a base for the manufacture of products such as plastics, fertilizers, fabrics, antifreeze, and other chemicals. Natural gas can be compressed to form compressed natural gas (CNG) for use in automobiles as a clean alternative fuel to gasoline and diesel. Additionally, steam reforming of natural gas can be used to produce hydrogen.

[0006] Hydrogen has a variety of uses. It is a clean-burning fuel that produces no greenhouse gases. It is a clean primary feedstock for the chemical industry, along with carbon monoxide (CO), to produce clean synthetic diesel, naphtha, jet A, and lubricants using the Fischer-Tropsch process. Hydrogen is also used in hydrogen-based fuel cells to generate electricity.

[0007] Natural gas derived from sustainable sources such as wood, food waste, sewage, or cellulose from switchgrass is considered renewable energy and is now a commodity known as renewable natural gas (RNG). Additionally, electricity generation from RNG, which is created from sustainable organic sources rather than fossil fuels, is now considered carbon neutral and therefore the cleanest source of carbon-based fuel available.

[0008] As governments begin to offer incentives and subsidies that signal a desire to reduce the demand for fossil fuels and lower overall emissions from the power sector, the generation of these types of natural gas products is becoming more attractive. Additionally, generating energy from these organic wastes allows for diversion from landfills. Fuel and energy generation also minimizes fugitive GHG emissions from the decomposition of these wastes.

[0009] Gasification is one process commonly used for the conversion of organic or fossil fuel-based carbonaceous materials. Coal gasification is a common application. However, commercial coal gasifiers are primarily designed to produce "synthesis gas," which contains high concentrations of carbon monoxide, hydrogen, and carbon dioxide, with minimal methane content. Methane and other products can be produced from this synthesis gas, but require additional chemical processing. Another problem with gasification is that large amounts of GHGs are produced from the process, requiring adequate carbon sequestration.

[0010] Incineration is another waste treatment process that may be used to destroy organic waste. Incineration involves the burning of organic materials at high temperatures, converting the material into heat, ash, and flue gases. Depending on the facility, incineration may be used to generate electricity. As a result of the high temperatures required for incineration, incineration may be used to destroy certain hazardous wastes, including pathogens and toxins. Incineration is very capital intensive, expensive to operate, and requires large facilities. The environmental impacts of incineration, such as the production of toxic metal oxides, GHGs, NOx, SOx, dioxins, and furans, are also a concern.

[0011] Anaerobic digestion is a common process used to treat biodegradable waste such as sewage sludge. Anaerobic digestion involves microorganisms that break down materials in the absence of oxygen. This process is used to manage waste and produce fuel from volatile hydrocarbons called "biogas", which is considered a renewable energy source. The biogas produced consists primarily of methane, CO2, and other trace polluting gases. This biogas can be used directly as fuel or upgraded to "biomethane". The digestate resulting from this process can be used for land agriculture as fertilizer, but certain toxic chemicals remain that are currently of regulatory concern. Anaerobic digesters have high initial capital costs, as they require large tanks and other process vessels. Anaerobic digestion also requires long residence times and generally only breaks down more volatile organic materials, resulting in reduced gas production and increased residues compared to other technologies. Additionally, the operating conditions of anaerobic digestion, such as pH, temperature, salinity, and alkalinity, need to be tightly controlled to operate properly.

[0012] Below is a group of patents related to commercial endeavors of gasification, plasma gasification, and steam reforming: TSANGARIS, Andreas, and Marc BACON, PCT Patent Application No. 2008 / 138118; TSANGARIS, Andreas, and Marc BACON, PCT Patent Application No. 2008 / 138117; TSANGARIS,Andreas,and Margaret SWAIN,PCT Case No. / 2008 / 117119. TSANGARIS,Andreas,and Marc BACON,PCT registration number 2008 / 104088. TSANGARIS,Andreas,and Marc BACON,PCT registration number 2008 / 104058. TSANGARIS, Andrew, Margaret SWAIN, Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Thomas Edward WAGLER, Scott Douglas BASHAM, Mao Pei CUI, Zhiyuan SHEN Ashish CHOTALIYA, Japan SONI, Alisdair Alan MCLEAN, Geoffrey DOBBS, Pascale Bonnie MARCEAU and Xiaoping ZOU.PCT Register / 2008 / 011213. TSANGARIS,Andreas,and Margaret SWAIN,PCT registration number 2007 / 143673. TSANGARIS,Andreas,Margaret SWAIN,Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Thomas Edward WAGLER, Scott, Douglas BASHAM, Zhiyuan SHEN, Geoffrey DOBBS, Mao Pei CUI, and Alisdair Alan MCLEAN TSANGARIS, Andrew, Margaret SWAIN, Douglas Michael FEASBY, Scott Douglas BASHAM, Ashish CHOTALIYA, and Pascale Bonnie MARCEAU, PCT registration number 2007 / 1 TSANGARIS,Andreas,Margaret SWAIN,Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Thomas Edward WAGLER, Xiaoping ZOU, Alisdair Alan MCLEAN, and Pascale Bonnie MARCEAU TSANGARIS, Andrew, Margaret SWAIN, Douglas Michael FEASBY, Scott Douglas BASHAM, Nipun SONI, and Pascale Bonnie MARCEAU, PCT registration number 2007 / 1 TSANGARIS, Andrew, Margaret SWAIN, Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Scott Douglas BASHAM, Alisdair Alan McLEAN, and Pascale Bonnie MARCEAU TSANGARIS,Andreas and Margaret SWAIN.PCT Registration No. 2007 / 131234. TSANGARIS,Andreas,Kenneth C. CAMPBELL,and Michael D.FEASBY and Ke LI,PCT Application Note 2006 / 128286. TSANGARIS,Andreas,Kenneth C. CAMPBELL,Michael D.FEASBY,and Ke LI,PCT Grant No. 2006 / 128285. TSANGARIS,Andreas V.,and Kenneth C.CAMPBELL; TSANGARIS, Andreas V., George W. CARTER, Jesse Z., SHEN, Michael D. FEASBY, and Kenneth C. CAMPBELL, PCT Patent Application No. 2004 / 072547; ZWIERSCHKE, Jayson, and Ernest George DUECK, PCT Patent Application No. / 2006 / 076801; SHETH, Atul C. PCT Patent Application No. / 2007 / 143376. MELNICHUK, Larry Jack, and Karen (Sue) Venita Kelly. U.S. Patent No. 7,728,182; Other patents related to the destruction of hazardous waste include: Abdullah, Shahid. Method for Degradation of Polychlorinated Biphenyls in Soil. U.S. Patent No. 5,932,472; Almeida, Fernando Carvalho. U.S. Patent No. 6,767,163; Anderson, Perry D., Bhuvan C. Pant, Zhendi Wang, et al. U.S. Pat. No. 5,118,429; Baghel, Sunita S., and Deborah A. Haitko. U.S. Patent No. 5,382,736. Balko, Edward N., Jeffrey B. Hoke, and Gary A. Gramiccioni. U.S. Patent No. 5,177,268; Batchelor, Bill, Alison Marie Hapka, Godwin Joseph Igwe, et al. U.S. Pat. No. 5,789,649; Bender, Jim. U.S. Patent No. 6,117,335; Boles, Jeffrey L., Johnny R. Gamble, and Laura Lackey. U.S. Patent No. 6,599,423; Bolsing, Friedrich, and Achim Habekost. Process for the Reductive Dehalogenation of Halogenated Hydrocarbons. U.S. Patent No. 6,649,044; Cutshall, Eule R., Gregory Felling, Sheila D. Scott, et al. U.S. Pat. No. 5,197,823; Dellinger, Harold Barrett, and John L. Graham. U.S. Patent No. 5,650,549; Driemel, Klaus, Joachim Wolf, and Wolfgang Schwarz. Process for Nonpolluting Destruction of Polychlorinated Waste Materials. U.S. Patent No. 5,191,155. Farcasiu, Malvina, and Steven C. Petrosius. U.S. Patent No. 5,369,214; Friedman, Arthur J., and Yuval Halpern. U.S. Patent No. 5,290,432; Ginosar, Daniel M., Robert V. Fox, and Stuart K. Janikowski. U.S. Patent No. 6,984,768; Gonzalez, Luciano A., Henry E. Kowalyk, and Blair F. Sim. U.S. Patent No. 6,414,212; Gonzalez, Luciano A., Dennis F. Mullins, W. John Janis, et al. U.S. Patent No. 6,380,454; Greenberg, Richard S., and Thomas Andrews. U.S. Patent No. 6,319,328; Levin, George B. U.S. Patent No. 5,602,298; U.S. Patent No. 5,100,638, Newman, Gerard K., Jeffrey H. Harwell, and Lance Lobban. U.S. Patent No. 6,241,856; Potter, Raleigh Wayne, and Michael Fitzgerald. U.S. Patent No. 6,213,029; U.S. Patent No. 6,112,675; Quimby, Jay M. U.S. Statutory Invention Registration No. H2198H; Reagen, William Kevin, and Stuart Kevin Janikowski. U.S. Patent No. 5,994,604; Rickard, Robert S. U.S. Patent No. 5,103,578; Ruddick, John NR, and Futong Cui. U.S. Patent No. 5,698,829; Schulz, Helmut W. U.S. Patent No. 5,245,113; Sparks, Kevin A., and James E. Johnston. U.S. Patent No. 5,695,732; Zachariah, Michael R., and Douglas P. DuFaux. U.S. Patent No. 5,936,137.

[0013] The use of hydrogen to treat hazardous wastes such as polychlorinated biphenyls (PCBs) has been considered for some time. This was called gas-phase reduction. Chemistry and Industry, vol. 102 (19), Oct. 3, 1983, pp. 759-760, Letchworth Herts, R. Louw et al., “Thermal Hydrodechlorination of (Poly) Chlorinated Organic Compounds”.

[0014] U.S. Patent No. 5,050,511 by Hallett, DJ and Campbell, KR describes the treatment of organic wastes, such as halogenated organic compounds, using gas phase chemical reduction. The reaction occurs in a reducing atmosphere at elevated temperatures above about 600°C, preferably above 875°C. The patent contemplates direct injection of liquid wastes, waste slurries, and pulverized solid wastes into a high temperature atmosphere containing excess hydrogen. The materials then undergo chemical oxidation with gaseous oxidants at temperatures above about 1000°C.

[0015] Hallett, DJ and McEwen, CS, US Pat. No. 8,343,241, describes a process focused on the use of a gas phase reduction process to produce methane rich gas from organic materials.

[0016] New processes for the reduction of organic materials to produce methane and / or hydrogen are needed.

[0017] This background information is provided for the purpose of making known information believed by the applicant to be of possible relevance to the present invention. No admission is necessarily intended, nor should it be construed, that any of the preceding information constitutes prior art against the present invention. Summary of the Invention

[0018] Described herein is a process for the reduction of organic material to produce methane and / or hydrogen.

[0019] In one aspect, a process is provided for reducing organic material to produce methane and / or hydrogen, the process comprising: (a) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, the reduction chamber being substantially free of oxygen, and heating the reduction chamber to effect a temperature increase from ambient to up to 425° C. under positive pressure at a rate of up to about 8° C. per minute within the organic material to form a first gaseous mixture comprising methane, hydrogen, an acid, and partially reduced volatile organic molecules; (b) heating the first gaseous mixture in the presence of an excess of hydrogen gas to a temperature of about 675° C. to about 875° C. to form a second gaseous mixture comprising methane and / or hydrogen, and an acid; and (c) neutralizing the second gaseous mixture with a base.

[0020] In another aspect, a process is provided for reducing organic material to produce methane, the process comprising: (a1) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, where the reduction chamber is substantially free of oxygen, and heating the reduction chamber to effect a temperature increase from ambient temperature to up to 425° C. under positive pressure at a rate of up to about 8° C. per minute within the organic material to form a first gaseous mixture comprising methane, hydrogen, an acid, and partially reduced volatile organic molecules; and (b1) neutralizing the first gaseous mixture with a base.

[0021] Other features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the present disclosure, are given by way of illustrative example only. Various changes and modifications within the spirit and scope of the present disclosure will become apparent to those skilled in the art from these detailed descriptions. [Brief description of the drawings]

[0022] For a better understanding of the present invention, together with other aspects and further features thereof, reference is made to the following descriptions which should be used in conjunction with the accompanying drawings, in which:

[0023] [Figure 1] FIG. 1 is a schematic diagram of one embodiment of the process of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The present disclosure relates to the generation of energy from both renewable and non-renewable organic materials. In particular, the present disclosure relates to a process in which organic molecules are reduced using excess gaseous hydrogen as the preferred reducing agent. The reduction of organic molecules occurs from materials in solid, liquid, or gaseous states. Energy is produced primarily in the form of hydrogen, methane, or a combination of the two. Synthetic and renewable natural gas can be produced. The process also provides for the recycling and recovery of metals, elemental carbon, and silica.

[0025] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0026] As used in this specification and claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0027] As used herein, the term "comprising" is understood to mean that the following list is not exhaustive and may or may not include any other additional suitable items, such as, for example, one or more further features, components, ingredients, and / or elements, as appropriate.

[0028] As used herein, terms of degree such as "substantially," "about," and "approximately" refer to a reasonable amount of deviation from the modified term such that the end result is not significantly altered. These terms of degree should be construed to include a deviation of at least ±5% of the modified term if this deviation does not negate the meaning of the word that the term modifies.

[0029] As used herein, the term "organic material" refers to any organic compound, biomass, microorganisms, toxic mixtures, or any carbon-based compound or mixture that can be converted to methane gas. Exemplary organic materials may include organic waste, biomass, chemical warfare agents, pathogens, and munitions. The term "organic waste" refers to materials that require treatment before disposal. Treatment of organic waste may be required because the material is toxic, infectious, explosive, an environmental pollutant, or the like. Examples of organic wastes include, but are not limited to, sewage sludge, municipal and industrial solid waste or garbage, landfill gas, agricultural wastes such as from poultry, cattle, swine, or other livestock wastes (such as manure or rendering wastes), corn and other crops contaminated with mold and associated toxins such as vomitoxin, organic solvents such as halogenated organic solvents, halogenated organic compounds such as polychlorinated biphenyls, hexachlorobenzene, chlorinated pesticides, brominated flame retardants, fluorinated propellants, or fluorinated refrigerants, organophosphorus compounds such as pesticides, plastics such as tires, polyethylene, automobile shredder residue (ASR), refinery and chemical manufacturing / processing wastes such as still bottoms, contaminated soils, fossil fuels such as lignite, subbituminous, or bituminous coal, bitumen, bitumen containing asphaltene molecules (high in sulfur), crude oil, peat, or bituminous processing wastes from tar sands, oil, crude oil, and peat, etc. Organic materials also include biomass, such as wood waste, paper waste, cardboard waste, wood chips, pulp waste, or agricultural biomass (such as from switchgrass, sugarcane residues, or corn stover or residues). Organic materials also include chemical warfare agents, such as halogenated or organophosphorus chemical warfare agents (such as mustard gas, sulfur mustard, sarin, and VX nerve gas). Organic materials also include pathogens, including viruses or bacteria (such as anthrax or E. coli bacteria).Organic materials also include munitions such as rockets or shells containing explosive organic materials such as 2,4,6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and the propellants may also be processed provided strict temperature ranges are observed such that explosive temperatures (explosion temperatures) are avoided.

[0030] As used herein, the term "partially reduced volatile organic molecules" refers to volatile organic molecules that have not been completely reduced to methane.

[0031] As used herein, the term "coal" includes all forms of easily combustible black or brownish sedimentary rock, such as lignite (or brown coal), sub-bituminous coal, and bituminous coal.

[0032] As used herein, the term "substantially oxygen-free" refers to the conditions used in the process of dehalogenation, desulfurization, and hydrogen reduction of organic compounds in the absence of oxygen. The advantage of carrying out the reaction in the absence of oxygen is to avoid oxidation of organic compounds and metals, which may result in undesirable by-products. Thus, the oxygen content in the sealed chamber is less than about 0.10% by volume, optionally less than about 0.08% by volume, and preferably less than about 0.04% by volume.

[0033] As used herein, the term "excess amount" refers to the amount of hydrogen gas mixed with the organic material in excess of the amount required for stoichiometry. The excess amount of hydrogen remaining after completion of the reduction reaction is about 5% to about 80%, preferably about 10% to about 55%, and more preferably about 15% to about 30% (in mole percent).

[0034] As used herein, the terms "mixing" and "well mixed" refer to uniformly mixing organic molecules with excess hydrogen such that the organic material is completely dehalogenated and reduced by hydrogen gas. Thorough mixing allows the hydrogen gas to bombard the organic compounds in the organic material from all directions, driving the dehalogenation, desulfurization, and reduction reactions to near completion. If the volatilized organic material is not well mixed with an excess of hydrogen gas, the compounds in the organic material will not be completely dehalogenated and reduced, resulting in the formation of aromatic and partially aromatic molecules by condensation into tar-like materials, including polycyclic aromatic hydrocarbons. Mixing is achieved by ensuring conditions that induce turbulence.

[0035] As used herein, the term "dehalogenate" refers to a process in which an organic compound containing a halogen atom, such as iodine, fluorine, chlorine, or bromine, reacts with hydrogen, resulting in the loss of the halogen atom from the organic compound and its replacement with a hydrogen atom.

[0036] As used herein, the term "desulfurize" refers to a process in which an organic compound containing sulfur atoms reacts with hydrogen, resulting in the loss of sulfur atoms from the organic compound and their replacement with hydrogen atoms. This reaction also produces hydrogen sulfide (HS).

[0037] As used herein, the term "neutralize" means adjusting the pH of a solution to about neutral (pH 7), or to a pH that is not harmful to the environment or living organisms. For example, neutralization of an acidic solution to a pH of about 7 can be accomplished by adding a base to the acidic solution.

[0038] As used herein, the term "vaporized" refers to a liquid that has been converted to vapor or gas form by the application of heat and hydrogen.

[0039] As used herein, the term "volatilized" refers to the conversion of large solid or liquid compounds by hydrogen reduction into smaller, lighter molecules that form the gas phase.

[0040] As used herein, the term "base" refers to any compound capable of neutralizing an acidic solution. Examples of bases include, but are not limited to, alkali metal hydroxides (such as sodium hydroxide or potassium hydroxide), alkaline earth metal hydroxides, alkali metal carbonates, or alkaline earth metal carbonates (such as calcium carbonate).

[0041] Process Description Described herein is a process for the reduction of organic material to produce methane, which was developed by the inventors to address challenges encountered during the use of other processes for the reduction of organic material known in the art.

[0042] The processes described herein for the reduction of organic material to produce methane, which may then be converted to hydrogen, as discussed in more detail herein, may be carried out on a wide variety of feed types, ranging from agricultural materials to sewage waste, automotive shredding residues, and munitions.

[0043] The inventors have surprisingly found that the initial reduction reaction in the processes described herein for reducing organic materials can occur under positive pressure (i.e., above ambient pressure) at temperatures up to 425° C. This provides the advantage of being able to operate the initial reduction process at lower temperatures than other processes known in the art, thereby improving the overall efficiency of the process.

[0044] Additionally, the inventors have noted that, in practice, personnel implementing processes for reducing organic material to produce methane may be motivated to rapidly ramp up the systems / equipment used to run such processes to operating temperature in order to begin achieving methane production as soon as possible and to increase process throughput. The inventors have observed that this can have the unintended effect of causing rapid pressure excursions, such as when the organic material is rapidly heated to temperatures of 450° C. or higher. The effects of such rapid pressure excursions may be two-fold. First, such rapid reactions may rapidly consume hydrogen available to the process, resulting in incomplete reduction of the organic molecules. Second, large pulses of volatilized organic material may rapidly transport unreduced organic molecules through the systems / equipment used to run the process, contaminating the desired products of the reduction reaction. In either of these scenarios, consistent production of vaporized organics may be prevented, and tar formation may occur (resulting in the need to shut down the systems / equipment for periodic cleaning, resulting in efficiency losses in the process). However, the inventors have discovered that such rapid pressure excursions can be reduced or avoided by careful control of temperature, including a gradual increase in temperature to the operating temperature of the reduction process, and preferably by monitoring and carefully controlling the pressure at which such process is carried out.

[0045] The process described herein is preferably carried out as a batch process, which is particularly suitable for incorporating the careful temperature control and temperature ramping process developed by the present inventors. Operating the process in a batch, as opposed to continuous, mode not only simplifies the equipment required to carry out the process, but also avoids pretreatment steps that may be required for a continuously operating process (which may require continuous feeding of organic material to the process).

[0046] Thus, the ability to operate the reduction process described herein at lower temperatures, combined with a carefully controlled temperature ramp up to operating conditions, results in processes and systems that can operate efficiently and cleanly across a wide variety of starting organic materials. The process described herein can further take into account the range of operator experience, taking into account the personnel who perform the reduction process and control the equipment used to perform the process steps, in that the process can be reliably reproduced by various process operators in an efficient and safe manner. Finally, the inventors have found that the process described herein can further reduce the formation of tarry materials compared to processes that operate at higher temperatures and / or lack such temperature control / ramp up built into the process.

[0047] Thus, in one embodiment, there is provided a process for reducing organic material to produce methane and / or hydrogen, the process comprising: (a) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, the reduction chamber being substantially free of oxygen, and heating the reduction chamber to effect a temperature increase from ambient to up to about 425° C. under positive pressure at a rate of up to about 8° C. per minute within the organic material to form a first gaseous mixture comprising methane, hydrogen, an acid, and partially reduced volatile organic molecules; (b) heating the first gaseous mixture in the presence of an excess of hydrogen gas to a temperature of about 675° C. to about 875° C. to form a second gaseous mixture comprising methane, and / or hydrogen, and an acid; and (c) neutralizing the second gaseous mixture with a base.

[0048] For the reduction reaction to occur, excess hydrogen must be present. If not enough hydrogen is present, only the most volatile hydrocarbons will be partially reduced and released from the solid and liquid phase materials. It has been found that by using an initial reduction chamber (IRC), also referred to herein as the reduction chamber, with excess hydrogen flow always present, all organic hydrocarbons are reduced and transferred from the solid and liquid phase materials in gaseous state, leaving behind clean solid metals or minerals, elemental carbon, and silica. This reduction reaction can be temperature controlled, providing optimization of gaseous hydrocarbon production in the form of a controllable continuous flow of partially reduced gaseous hydrocarbons to the reactor, leaving little or no organic residue. Preferably, a continuous flow of heated hydrogen gas is provided to the reduction chamber. In one embodiment, a pipe or tube for supplying hydrogen can extend into the reduction chamber to allow heating of the hydrogen contained in the reduction chamber prior to its release and reaction with the organic material.

[0049] It has been found that the reduction of organic materials from a variety of sources in solid, liquid, and gaseous states in step (a) can occur in the presence of an excess of flowing hydrogen gas. This can be accomplished in a simple low pressure chamber that can handle pressures up to 10 atmospheres and can be loaded using a bin that can be lifted into the chamber with a standard loader or bobcat device.

[0050] In step (a), when the flowing hydrogen attacks or causes reduction, hydrogen penetrates the organic material and directly reduces the molecules in the solid, liquid, and gaseous states, allowing the breaking of bonds, especially carbon-carbon bonds, carbon-halogen bonds, and any sulfhydryl bonds. Preferably, a continuous input of fresh hydrogen is provided. This is known collectively as hydrogen reduction. The organic material should be oriented to allow immediate exposure to hydrogen and to allow the reduced gaseous organic molecules to be swept away. The volatilized or gaseous organic molecules eventually react with excess hydrogen gas to cause further reduction. In addition to methane, hydrogen, acid, and partially reduced volatile organic molecules, the first gaseous mixture may also include CO and CO2.

[0051] In one embodiment, step (a) is carried out as a batch process.

[0052] In yet another embodiment, the process is carried out at a pressure greater than 1 atmosphere and less than about 5 atmospheres. In one embodiment, the process is carried out at a pressure of at least about 2 atmospheres and less than about 5 atmospheres. In another embodiment, the process is carried out at a pressure of about 2 atmospheres to about 3 atmospheres.

[0053] Although a pressure increase of up to 10 atmospheres can be tolerated by the reduction chamber and other equipment used to carry out the process, in one embodiment, if a rapid pressure increase occurs and / or the pressure in the reduction chamber approaches about 5 atmospheres, the rate of temperature increase in the organic material is reduced, i.e., heating of the reduction chamber is reduced. When the pressure in the reduction chamber stabilizes and / or is less than about 5 atmospheres, or about 2 atmospheres to about 3 atmospheres, heating of the reduction chamber is resumed to cause a temperature increase in the organic material from ambient to up to 425°C at a rate of up to about 8°C per minute. In one embodiment, the rapid increase in pressure can be a pressure increase of about 1 atmosphere / 30 seconds. In a preferred embodiment, the process is carried out under positive pressure (i.e., at a pressure higher than ambient pressure).

[0054] When the temperature of step (a) is increased to a temperature of 425° C., preferably at a pressure of at least about 2 atmospheres and less than about 5 atmospheres, or from about 2 atmospheres to about 3 atmospheres, most of the halogenated aromatic and aliphatic hydrocarbons present in the organic material have been dehalogenated by reduction and hydrogen displacement. Similarly, organic compounds containing sulfur atoms, such as asphaltenes in bitumen, are desulfurized in the presence of excess hydrogen gas.

[0055] In another embodiment, the organic material includes water (e.g., sewage sludge), and in step (a), the process further includes heating the reduction chamber to create a temperature increase in the organic material to about 100°C to about 105°C, and holding the temperature of the organic material at about 100°C to about 105°C to evaporate water from the organic material and form steam, and removing the steam from the reduction chamber before further increasing the temperature of the organic material. In one embodiment, the steam is removed, such as through a reactor bypass tube, and the organic material is dried before the temperature of step (a) is further increased and before step (b) and further steps are performed. By evaporating and removing the water (e.g., through a reactor bypass tube leading to a quencher / primary scrubber), a more efficient process is created by eliminating the need to pass the water through the reactor, heating the water to 875°C, and then cooling the water. This will produce a final product gas with high methane content and low CO and CO2 content. If additional hydrogen can be economically added, maximum methane yields can be obtained and either CO and CO2 content can be minimized or eliminated. In another embodiment, the process further includes cooling the steam removed from the reduction chamber (e.g., to a temperature of about 70°C) to reform water, neutralizing the water to neutralize any acids present (such as via an acid scrubber), and treating the water to remove any organic molecules and / or metals present. In one embodiment, a basic solution is added to neutralize any acids formed, such as sulfuric or hydrochloric acid. In another embodiment, treating the water includes filtering the water through an activated carbon filter.

[0056] In another embodiment, step (b) is carried out in a substantially oxygen-free, sealed reaction vessel. In yet another embodiment, step (b) is carried out under continuous mixing conditions. In yet another embodiment, step (b) comprises heating the first gaseous mixture to a temperature of about 750°C to about 850°C. In yet another embodiment, step (b) comprises heating the first gaseous mixture to a temperature of about 800°C to about 850°C.

[0057] The first gaseous mixture is transferred via positive pressure to a sealed reaction vessel, where the first gaseous mixture is rapidly heated to a temperature of about 675°C, and, if necessary, to a high temperature of about 875°C, while again thoroughly mixing the gaseous mixture with an excess of hydrogen gas. The complete reduction of the organic material is carried out in step (b) and can be carried out in a sealed reaction vessel (also referred to herein as a hydrogen reduction reactor, reaction vessel, or reactor) designed to generate a turbulent flow of gas at high temperature, where all the organic material is in a gaseous state and is continuously mixed with an excess of hydrogen as a reducing agent. The sealed reaction vessel is maintained under controlled temperature and pressure, resulting in the production of methane. The excess hydrogen reduces the remaining organic molecules to form more methane. The resulting product gas (i.e., the second gaseous mixture) should be substantially free of other aromatic molecules and especially larger organic molecules, such as siloxanes, naphthalenes, and benzene. The resulting CO and CO2 produced can be reacted with excess hydrogen in the presence of a nickel catalyst at a lower temperature of about 400°C to form more methane and water. The resulting hydrogen and methane can then be separated and used commercially. The formation of CO and CO2 depends on the amount of water or steam present, which reacts with the methane formed. If the presence of these gases is problematic for any reason, the amount of moisture in the organic material or the amount of water or steam added should be limited or eliminated. This would limit or eliminate the source of CO and CO2 formation. Additional hydrogen can be added from an external source if necessary.

[0058] Optionally, as further described below, additional water or steam can be added to the reactor to promote the formation of hydrogen and CO via a steam-methane reforming reaction in the presence of a catalyst, whereby all of the methane present can be reformed into hydrogen, CO, and CO2, which can then be separated using commercially available membranes and sold.

[0059] The reaction vessel should be designed so that the gas flow is turbulent throughout the vessel, providing continuous mixing. There should be no stagnant areas that allow unreacted hydrocarbons to accumulate and undergo condensation reactions that lead to the formation of tars. The vessel can be made as a longer tubular structure or in a shape similar to that shown by Hallett and Campbell in U.S. Patent No. 5,050,511.

[0060] The steam will further react with the CO to form CO2 and more hydrogen via the water gas shift reaction at these temperatures. Ultimately, this will form a second gaseous mixture that contains primarily hydrogen with low concentrations of acid, CO, CO2, and methane. This reduces the need for additional hydrogen. Alternatively, additional hydrogen may be added to the reaction from an external source to maximize the production of methane and reduce the production of CO and CO2, which are greenhouse gases (GHGs) and undesirable. In such an embodiment, no steam or water would be added to the reactor to minimize any possibility of CO2 formation.

[0061] This second gaseous mixture may contain trace amounts of ionic metals such as mercury, lead, cadmium, and arsenic, and halides such as chlorides, fluorides, and bromides, as well as sulfur, nitrogen, and ammonium.

[0062] This second gaseous mixture is thoroughly mixed with excess hydrogen and thoroughly heated, thereby accelerating the interaction of hydrogen with other molecules and promoting hydrogen reduction, which is intended to substantially eliminate all aromatic or partially aromatic compounds.

[0063] In another embodiment, step (b) of the process is carried out in the presence of a catalyst, as described above. In yet another embodiment, the catalyst is a metal catalyst, the metal being selected from one of nickel, copper, iron, nickel alloys, tin (such as powdered tin), chromium, and more of the precious metals. In another embodiment, the precious metal is selected from platinum, silver, palladium, gold, ruthenium, rhodium, osmium, and iridium. In yet another embodiment, the catalyst is embedded in one or more walls of the closed reaction vessel. In yet another embodiment, the closed reaction vessel is constructed of a steel alloy containing nickel. In a preferred embodiment, the nickel catalyst is provided to the gaseous organic molecules by constructing a high temperature reactor (vessel or tubular reactor) with a steel alloy containing a high concentration of nickel. These metals are commonly known as Hastelloy. In another embodiment, step (b) further comprises heating the first gaseous mixture in the presence of superheated steam to reform hydrogen from the methane being produced from the reduction reaction.

[0064] In another embodiment, the reduction chamber and the sealed reaction vessel are first purged with an inert gas, such as nitrogen, to make them substantially oxygen-free. In another embodiment, the level of excess hydrogen is monitored so that the excess hydrogen is preferably greater than 10%. In one embodiment, 10% excess hydrogen means that there is at least 10% hydrogen in the gas measured downstream of the reactor in the process. The hydrogen concentration, along with methane, CO, and CO2, may be measured by a continuous gas analyzer. In one embodiment, the gas may be continuously analyzed as it exits the scrubber system before the hydrogen is separated for recycling. As the skilled worker will appreciate, if the relative concentration of hydrogen in the total gas exiting the scrubber system is 10% or more, there should be at least this concentration of excess hydrogen early in the process (such as the reactor) where hydrogen is being consumed.

[0065] At a temperature of about 675°C to about 875°C in step (b), the dehalogenated and desulfurized aromatic and aliphatic hydrocarbon compounds in the first mixture are reduced to methane or other small aliphatic hydrocarbons, for example, as shown in hydrogen reduction. By thoroughly mixing the organic material with an excess amount of hydrogen gas, and optionally mixing the generated methane with water or steam to generate more hydrogen therein and increase the concentration, it is ensured that the organic compounds are substantially reduced, thus reducing or avoiding the formation of tar-like substances.

[0066] Hydrogen reduction [ka] [ka] [ka]

[0067] As stated above, the presence of water or steam in step (b) is optional. If there is a sufficient external hydrogen source available, the presence of water or steam is not required. The addition of water or steam to step (b) reduces the demand for hydrogen as this water or steam reacts with methane to form hydrogen and CO, first via steam-methane reforming (hydrogen generation). The water or steam will then react further to produce more hydrogen and CO2 via the water-gas shift reaction (hydrogen generation). Typically, these reactions are carried out at an optimum temperature of 700°C to 1100°C. Ultimately, four new hydrogen molecules are produced from these reactions at the expense of just one molecule of methane. However, CO and CO2 may be undesirable products, so depending on their desired levels in the mixture, external hydrogen may be used to minimize the production of CO and CO2.

[0068] Hydrogen Generation CH4+H2O⇔CO+3H2 (steam methane reforming) CO+H2O⇔CO2+H2(water gas shift) In another embodiment, step (c) includes neutralizing the second gas mixture with a base at a temperature of about 70° C. to about 100° C., or about 85° C. to form a neutralized second gaseous mixture. In yet another embodiment, the base is selected from an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, or an alkaline earth metal carbonate. In yet another embodiment, the base is selected from sodium hydroxide or calcium carbonate. A quencher and a primary scrubber can be used to neutralize the second gaseous mixture. As a result of the dehalogenation and / or desulfurization reactions, acidic by-products are neutralized before the hydrogen gas and methane are separated and purified. It is particularly important to accomplish this before the hydrogen gas and methane are separated, since the membranes made of precious metals used to accomplish this are sensitive to sulfur and other acidic products.

[0069] In another embodiment, the process further comprises cooling the neutralized second gaseous mixture. In another embodiment, the neutralized second gaseous mixture is cooled to a temperature of about 5° C. to about 35° C. In yet another embodiment, the neutralized second gaseous mixture is contacted with a solution containing potassium permanganate to remove phosphorus-containing molecules (as well as ions including phosphine gas) from the neutralized second gaseous mixture; for this purpose, a secondary scrubber may be used. The potassium permanganate solution removes phosphorus-containing molecules and ions by forming potassium phosphate, which is removed as a salt.

[0070] In one embodiment, cooling and / or neutralizing the second gaseous mixture may be carried out in a third vessel with an aqueous solution containing a base, such as sodium hydroxide, which allows for the formation of sodium halides, including sodium chloride. Sulfur is also removed to form sodium sulfide and sodium sulfate. Volatile metals, such as mercury, lead, arsenic, and cadmium, will also form halides, such as mercuric chloride. In another embodiment, the third vessel is first purged with an inert gas, such as nitrogen, to render the vessel substantially free of oxygen.

[0071] In another embodiment, steps a), b), and c) of the above process are carried out at a pressure of greater than 1 atmosphere to about 10 atmospheres, preferably greater than 1 atmosphere to about 5 atmospheres, with a positive pressure being maintained in the system at all times.

[0072] In another embodiment, the process further comprises separating excess hydrogen from the methane after neutralizing the second gaseous mixture. In yet another embodiment, the process further comprises recycling the excess hydrogen to step (a) and / or step (b). The recycled hydrogen may include amounts of methane, CO, and CO2. In another embodiment, the process of separating hydrogen from methane is accomplished by first compressing the neutralized gaseous mixture of c) and sending the compressed gas to a hydrogen separator. In one embodiment, the hydrogen separator is a membrane made of a precious metal, such as palladium, which separates gases based on their molecular size, with hydrogen being the smallest. In another embodiment, the hydrogen separator is a pressure swing absorber. In another embodiment of the present disclosure, the separated hydrogen gas is transferred for use in an energy generation system, including a fuel cell.

[0073] The amount of CO and CO2 produced varies with the moisture content of the organic material and / or water added to the high temperature reactor. To minimize the formation of CO and CO2 in the product gas, the organic material can be pre-dried or the amount of water present or added should be kept to a minimum. If the organic material does not contain water, pure hydrogen can be added and the formation of CO or CO2 is insignificant. By adding hydrogen at lower temperatures in the presence of a nickel catalyst, small amounts of CO and CO2 can be converted to methane, but the cost of this process becomes prohibitive to convert larger amounts of CO and CO2 to methane. In this case, removal of these gases from the product gas is necessary to obtain pure methane or hydrogen.

[0074] In another embodiment of the present disclosure, when the desired product is methane, the hydrogen is substantially separated and the remaining gas contains primarily methane.

[0075] In another embodiment of the present disclosure, the remaining gas, which contains primarily methane, is transported for use in an energy generation system.

[0076] In another embodiment of the present disclosure, the remaining gas, which contains primarily methane, may be compressed and used as a clean-burning fuel. In another embodiment of the present disclosure, the methane gas has about 0% to about 30% by volume hydrogen, optionally about 5% to about 25% by volume hydrogen, and preferably about 10% to about 20% by volume hydrogen.

[0077] In another embodiment of the present disclosure, methane is separated from other gases using commercially available technologies such as membrane or pressure swing absorption. Methane can be separated from the remaining gases (hydrogen, CO, and CO2) to form a gas that is 95%-98% methane.

[0078] In further embodiments of the present disclosure, the methane gas produced from the process can be used to generate electricity using gas-powered and steam turbines. In further embodiments of the present disclosure, the methane gas produced can be upgraded by separating the methane from the hydrogen, CO, and CO2 to produce and distribute pipeline-grade synthetic natural gas (SNG) or renewable natural gas (RNG). These alternative and renewable fuel sources can offset fossil fuels and reduce overall GHG emissions.

[0079] In a further embodiment of the present disclosure, the process may be used to produce hydrogen, CO, and CO2, which may be used in chemical syntheses such as the Fischer-Tropsch process.

[0080] In another embodiment, the organic material is organic waste, biomass, chemical warfare agents, pathogens, or munitions. In another embodiment, the organic waste includes sewage sludge, municipal and industrial solid waste or garbage, landfill gas, agricultural waste, corn and other crops contaminated with mold and associated toxins, organic solvents, halogenated organic compounds, organophosphorus compounds, tires, plastics, automobile shredding residue (ASR), refinery and chemical manufacturing / processing waste, or fossil fuels. In yet another embodiment, the biomass includes wood waste, paper waste, cardboard waste, wood chips, pulp waste, or agricultural biomass. In yet another embodiment, the chemical warfare agents include halogenated or organophosphorus chemical warfare agents such as Sarin or VX. In another embodiment, the pathogen includes a virus or bacteria. In yet another embodiment, the munitions include rockets or shells containing explosive organic materials and / or propellants such as TNT or RDX (note that such materials should be treated with careful attention to temperature so that the molecules are reduced below the temperature of spontaneous cascade that causes deflagration or explosion). In another embodiment, the organic materials are as defined in the definition section above.

[0081] Considering the processing of munitions such as rockets or shells containing explosive organic materials, one skilled in the art would understand that hydrogen reduction of TNT itself and the products of activated molecular rearrangement can occur without approaching TNT's explosion temperature of 502.22°C (936°F), since TNT has a melting point of 80.35°C and a boiling point of only 295°C. However, once TNT has been melted and is in the liquid state used to fill shells, it can be destroyed at low temperatures while being reduced by gaseous hydrogen. RDX and HMX are preferred explosives over TNT in that they are much less sensitive to impact or friction. RDX has a melting point of 205°C and an explosion temperature of 260°C. Thus, one skilled in the art would understand that RDX reduces at temperatures above 205°C, but must be kept well below 260°C to prevent explosion. HMX has a melting point of 276°C, which is above the explosion point of RDX. Those skilled in the art will appreciate that for these reasons, co-flowing high concentrations of HMX with RDX should generally be avoided, although HMX has a much higher detonation temperature of 375°C.

[0082] In another embodiment of the present disclosure, the organic material also contains inorganic materials such as fixed carbon, elemental carbon, silica, glass, and precious and non-precious metals such as tin, zinc, and lead that do not volatilize and are retained in either reduced or natural form. In one embodiment of the present disclosure, the inorganic materials are removed from the reduction chamber as particles after cooling the material before exposing it to air. In one embodiment of the present disclosure, the temperature of this inorganic material after cooling must be lower than the ignition points of all of the metals present or the metals will ignite when exposed to oxygen in the ambient air.

[0083] In another embodiment, a process for reducing organic material to produce methane is provided, comprising: (a1) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, the reduction chamber being substantially oxygen-free, and heating the reduction chamber to provide a temperature increase from ambient to up to about 425° C. under positive pressure in the organic material at a rate of up to about 8° C. per minute to form a first gaseous mixture comprising methane, hydrogen, acid, and partially reduced volatile organic molecules; and (b1) neutralizing the first gaseous mixture with a base. In one embodiment, the organic material is bitumen. In yet another embodiment, step (a1) is carried out as a batch process. In yet another embodiment, the process is carried out at a pressure greater than about 1 atmosphere and less than about 5 atmospheres. In one embodiment, the process is carried out at a pressure of at least about 2 atmospheres and less than about 5 atmospheres. In another embodiment, the process is carried out at a pressure of about 2 atmospheres to about 3 atmospheres.

[0084] As described above for step (a), a pressure increase of up to 10 atmospheres can be tolerated by the reduction chamber and other equipment used to carry out the process, but in one embodiment of step (a1), if a rapid pressure increase occurs and / or the pressure in the reduction chamber approaches about 5 atmospheres, the rate of temperature increase in the organic material is reduced, i.e., heating of the reduction chamber is reduced. When the pressure in the reduction chamber stabilizes and / or is less than about 5 atmospheres, or about 2 atmospheres to about 3 atmospheres, heating of the reduction chamber is resumed to cause a temperature increase from ambient temperature to up to 425°C in the organic material at a rate of up to about 8°C per minute. In one embodiment, the rapid increase in pressure can be a pressure increase of about 1 atmosphere / 30 seconds. In one embodiment, the process is carried out under positive pressure (i.e., at a pressure higher than atmospheric pressure). As described above for step (a), preferably a continuous flow of heated hydrogen gas is provided to the reduction chamber. In one embodiment, a pipe or tube for supplying hydrogen may extend into the reduction chamber to allow heating of the hydrogen contained in the reduction chamber prior to release of hydrogen and reaction with the organic material.

[0085] In yet another embodiment, step (b1) comprises neutralizing the first gaseous mixture with a base at a temperature of about 70° C. to about 100° C., or about 85° C. to form a neutralized first gaseous mixture. In another embodiment, the base is as defined above. In another embodiment, the process further comprises cooling the neutralized first gaseous mixture. In yet another embodiment, the neutralized first gaseous mixture is cooled to a temperature of about 5° C. to about 35° C. In yet another embodiment, the neutralized first gaseous mixture is contacted with a solution comprising potassium permanganate to remove phosphorus-containing molecules from the neutralized first gaseous mixture. In another embodiment, the organic material is bitumen and the temperature increase within the organic material is from ambient temperature to a maximum of about 400° C. In another embodiment, the organic material is bitumen and the first gaseous mixture comprises a lighter fraction of synthetic crude oil and step (a1) produces a non-volatile product comprising synthetic crude oil. In yet another embodiment, the process further comprises separating excess hydrogen from the methane and lighter fractions of the synthetic crude oil after neutralizing the first gaseous mixture. In yet another embodiment, the process further comprises recycling the excess hydrogen to step (a1) and / or step (b1).

[0086] In another embodiment, the organic material is only partially reduced to form smaller organic molecules. As an example, the organic material may be Alberta bitumen, which may be treated with hydrogen reduction to form a less viscous synthetic crude type product (i.e., a fluid oil type product). Bitumen found in the Alberta oil sands may be treated with hydrogen reduction to break down the large asphaltene sulfur-containing molecules that make the material viscous and slow to move in pipelines. Thus, the large sulfur-containing asphaltene molecules will be reduced and most of the sulfur removed. What distinguishes bitumen from conventional crude oil is the low concentration of low molecular weight hydrocarbons present and the abundance of high molecular weight polymeric materials. The latter are amorphous solids that dissolve in colloidal form in the low molecular weight liquid components, giving bitumen a viscous, syrupy consistency. The higher molecular weight solids are soluble in liquid aromatics such as benzene or toluene, but insoluble in lower molecular weight paraffins, and so can be separated from the bitumen by n-pentane precipitation from a benzene solution of the bitumen. The solids thus precipitated are called asphaltenes.

[0087] Most asphaltenes are rich in the heteroatoms oxygen, nitrogen, and especially sulfur. The asphaltene content of Alberta oil sands bitumen (AOSB) ranges from 16-25%, with asphaltenes containing approximately 80% carbon, 8.0% hydrogen, 8-9% sulfur, 2.5% oxygen, and 1.0% nitrogen. The main problems associated with underground recovery of AOSB are a result of the very high viscosity of the bitumen, which is primarily responsible for the asphaltenes.

[0088] In the case of Alberta bitumen, hydrogen reduction can be used as a soft cracker to produce a relatively small amount of methane from the bitumen. This methane can be reformed to hydrogen to produce more process gas. This hydrogen can be used to react with the primarily larger molecules in the asphaltene of the bitumen. The asphaltene is bound with sulfur and hydrogen bonds and simple cyclic molecules that are susceptible to hydrogen reduction. Essentially, the large molecules of the asphaltene are made into small aromatic molecules, which will reduce the viscosity of the bitumen and produce a free-flowing liquid oil. The larger molecules cannot be reformed. High sulfur can also be removed at this stage.

[0089] The bitumen is heated in the IRC in the presence of hydrogen. As the IRC heats up to 400°C, the evolved gaseous hydrocarbons and acid gases, especially H2S, are transferred directly to the quencher to avoid further reaction with excess hydrogen at high temperatures. This can be accomplished, for example, by using a reactor bypass tube. The quencher / primary scrubber can condense the lighter fractions of the synthetic crude and remove the large amount of sulfur that was removed from the bitumen by cracking the asphaltene molecules. The liquid remaining in the IRC bin will be removed as synthetic crude and the viscosity of this product will be reduced compared to the feedstock and defined by the peak temperature and pressure in the IRC. As mentioned above, the liquid material condensed in the scrubber will be a lighter fraction of the synthetic crude, more similar to C heavy oil or diesel. This liquid can be separated from the scrubber aqueous and caustic solutions using a standard oil-water separator. The pipeline would transport only the hydrocarbons derived from the original bitumen without the dilution currently required for transportation. This should add significant value and be very cost effective.

[0090] In some embodiments, step (a) of the above process may include heating the reduction chamber to optionally effect a temperature increase in the organic material from ambient temperature up to about 600° C. at a rate of up to about 8° C. per minute, although it is noted that, as noted above, it has been found by the inventors that it is not necessary to operate at such high temperatures as the process may operate more efficiently at lower temperatures.

[0091] Furthermore, it has been found that the process described herein can be successfully carried out using two or more IRCs to provide a continuous stream of gaseous organic molecules (i.e., the first gaseous mixture described herein) to a single reactor for further reduction. The IRCs can be sequenced in such a manner that a new load of gaseous organic molecules begins to be introduced from the IRC once the previous load has been processed to completion. The sequencing time is indicated by the pressure drop in the reactor as a result of the reduction in gaseous organic molecules entering the reactor. In order to use multiple IRCs, it is still necessary to increase the temperature during the initial reduction and volatilization of the organic material in step (a) / (a1) of the process. As previously mentioned, this allows for control of the pressure in the IRC and the reaction vessel to ensure that complete reduction occurs to minimize tar formation in the process. The use of IRCs allows for a simple means of not only loading the organic material, but also unloading the residual inorganic material for reuse. The use of an IRC for hydrogen reduction is practical and eliminates the need for moving parts in a hydrogen atmosphere, the need to continuously introduce organic materials to a single vessel, and / or the need to seal hydrogen in a moving vessel.

[0092] Exemplary Process and System for the Reduction of Organic Material to Produce Methane Gas With reference to FIG. 1, a block flow diagram of the overall process is shown. In one embodiment, before being processed and depending on the nature of the organic material, the organic material is pretreated. In FIG. 1, an exemplary organic material is shown as being organic waste. In one embodiment, the organic material is pretreated (preprocessed) to form a homogenous feedstock with a high surface area. This pretreatment may include chipping, grinding, or shredding the organic material, or any other method known to those skilled in the art. In a further embodiment, if the organic material contains water, the organic material is optionally pretreated to remove water before being processed.

[0093] In another embodiment, the organic material is placed in an open vessel inserted into an initial reduction chamber or IRC. In another embodiment where pretreatment of the waste is not desired, the moisture content of the material can be reduced by first increasing the temperature in the IRC from ambient to about 105° C. (at a rate of up to about 8° C. per minute). In another embodiment, the water in the organic material is steamed and sent directly to a scrubber via a reactor bypass tube, eliminating the need for pre-drying of the organic material. In another embodiment, the organic material is placed on a long tray inserted into the IRC, so that the waste on the tray can be uniformly exposed to both heat and excess hydrogen gas. In a further embodiment, when the organic material is relatively uniform and flowable, such as, for example, sewage sludge with a low solids content, the material is metered and pumped into the trays in the IRC using a sludge pump.

[0094] In one embodiment, one or more IRCs (three are shown in FIG. 1) are loaded with organic material, then the vessel is sealed and purged of air with an inert gas such as nitrogen or argon through an inlet. Purging allows the process to be carried out in a substantially oxygen-free environment. In one embodiment, excess hydrogen is added to the IRCs as the temperature is increased from ambient to 425° C. at a rate of up to 8° C. per minute under positive pressure. Those skilled in the art will be able to determine the temperature required to vaporize the organic material and initiate the dehalogenation, desulfurization, and reduction reactions, which will depend in part on the nature of the material. An excess of hydrogen is added to the vessel and maintained at an outlet such that excess hydrogen leaves the vessel. Hydrogen is continually added during this process as it is consumed as the molecules are reduced. Organic molecules that exist in a solid, liquid, or gaseous state are directly reduced, producing a gaseous organic mixture as the molecules become smaller. These gaseous organic molecules are continually reduced, dehalogenated, and desulfurized as they pass through the IRCs.

[0095] It has been found that this process can be successfully operated using an IRC to feed a continuous stream of gaseous organic molecules to a single reactor to be further reduced. The use of an IRC also allows for the temperature to be increased during the initial reduction and volatilization of the organic material. This also allows for control of the pressure in the IRC and reaction vessel to ensure that complete reduction occurs to minimize tar formation in the process. The use of an IRC allows for a simple means of loading the organic material. The use of an IRC also allows for a simple means of unloading the residual inorganic material that is not reduced and volatilized. The inorganic materials are primarily elemental carbon, silica, metals, and glass that are suitable for recycling. The use of an IRC for hydrogen reduction is practical and eliminates the need to continuously introduce organic material to a single vessel. The IRC allows for control of pressure spikes by monitoring and controlling the temperature increase. The temperature increase (at a rate of up to about 8°C per minute) is essential for efficiency and the prevention of pressure spikes that can cause tar formation in the reactor and scrubber.

[0096] In a further embodiment, the reduced and volatilized organic molecules are transported from the IRC to a second vessel called the hydrogen reduction reactor. In one embodiment, the combined process gas and hydrogen gas enter the inlet of the reactor where they are further mixed with additional excess hydrogen, which is added using various injectors and nozzles. In one embodiment, the reactor is designed such that the gas flow is turbulent, characterized by eddies and vortices present throughout the flow field. In one embodiment, the turbulent gas flow helps to thoroughly mix the organic compounds in the organic material with the excess hydrogen gas. As explained, thorough mixing of the organic compounds with the excess hydrogen gas reduces all the molecules that form methane and completely removes any aromatic molecules.

[0097] In another embodiment, the reaction vessel is also exposed to high temperatures, corrosive chemicals such as halide compounds, halogens, sulfur, phosphorus, and heavy metals, and a reducing environment as a result of the hydrogen gas stream. Thus, in some embodiments of the present disclosure, the materials used to construct the reaction vessel are made of high temperature and corrosion resistant chromium nickel superalloys such as 253MA®, Hastelloy® X, or Haynes® 188.

[0098] In a further embodiment, the mixture is further heated in the presence of a catalyst such as nickel present in the metal vessel walls of the reactor and mixed with water or steam to convert the methane being produced to hydrogen and CO gas via steam methane reforming. The CO reacts further to produce more hydrogen and CO2 via the water gas shift reaction. This is particularly desirable when the end product is to be hydrogen.

[0099] In some embodiments, the process of the present disclosure is carried out in the presence of a catalyst. In a further embodiment, the catalyst is a metal catalyst, and the metal is selected from one or more of nickel, copper, iron, nickel alloys, tin (such as powdered tin), chromium, and precious metals. In another embodiment, the precious metal is selected from one or more of platinum, silver, palladium, gold, ruthenium, rhodium, osmium, and iridium. In one embodiment, the reaction vessel is constructed with a metal, such as nickel, that catalyzes the process, as described above.

[0100] In one embodiment of the present disclosure, the reactor includes a heating zone and a reduction zone. The heating zone is defined as the volume required to heat the mixed gas to a temperature effective for complete reduction reaction to occur within the reduction zone. The reduction zone is defined as the volume that, as a result of sufficient heating and mixing with excess hydrogen, has sufficient residence time for complete reduction of the gaseous organic molecules to occur.

[0101] In one embodiment, the residence time in the reduction zone is from about 1 to about 10 seconds, optionally from about 1 to about 5 seconds, and preferably from about 2 to about 4 seconds. In another embodiment of the present disclosure, the gaseous mixture produced from the reduction reaction travels up the central tube of the process reactor.

[0102] In another embodiment, the process reactor is heated using one or more radiant tube heaters located in an annular heating zone. In one embodiment, the radiant tube heaters are gas-fired or electric. In another embodiment, the radiant heaters are connected to the process reactor in a zone above the process reactor that is filled with an inert gas, such as nitrogen, argon, or carbon dioxide. This design ensures that if a leak occurs in the radiant tube, outside air cannot leak into the process reactor.

[0103] In another embodiment of the present disclosure, the process reactor comprises an insulated vessel consisting of an outer shell made of, for example, carbon steel with a floating liner made of, for example, a nickel alloy. The floating liner allows for movement due to thermal expansion as a result of high temperatures within the process reactor. In a further embodiment, the process reactor also has insulation, such as ceramic fiber, that helps maintain high temperatures within the process reactor. In another embodiment, the floating liner and radiant tube heater are constructed of materials that can withstand chemicals such as halogens, halogen compounds, sulfur, phosphorus, and heavy metals, including chlorine and fluorine, as well as the high temperature reducing environment within the process reactor. In one embodiment, the floating liner and radiant tube heater are constructed of high temperature and corrosion resistant chromium nickel superalloys, such as Kanthal APM®, 253MA®, Hastelloy® X, or Haynes® 188. In another embodiment, the process reactor includes a removable bottom plug to allow access into the process reactor vessel during shutdown for inspection, maintenance, and cleaning.

[0104] In another embodiment of the present disclosure, the process reactor comprises a tubular process reactor design consisting of several tubes that are heated externally, rather than a large vessel with internal heating elements. These tubes may be made from the above-mentioned chromium-nickel alloys, such as Hastelloy.

[0105] In another embodiment, the gaseous mixture then enters a quencher and a primary scrubber. In one embodiment, the initial quencher includes a water spray that rapidly cools the gaseous mixture from 875°C to a temperature of about 100°C to about 300°C. In a further embodiment, the cooled gaseous mixture travels through a tube to a venturi scrubber. In the venturi scrubber, the water is atomized into small droplets by turbulent flow in the throat to greatly improve contact between the gaseous mixture and the water. The quencher and scrubber remove heat, water, particulate matter, and acid gases from the gaseous mixture that are generated as by-products from the dehalogenation and reduction reactions of halogenated compounds (especially chlorinated, fluorinated, or brominated compounds) and sulfur compounds.

[0106] In one embodiment of the present disclosure, acid gases such as halogens and sulfur as ions or as hydrides are neutralized by adding a base such as sodium hydroxide or calcium hydroxide, which results in the production of water and salts of the halogens and sulfur, such as sodium chloride or sodium bromide or calcium sulfate.

[0107] In another embodiment, the water added to the venturi scrubber is collected at the bottom of the scrubber and exits as a water stream. In a further embodiment, water from the quencher also joins the water stream. In a further embodiment, the water stream containing the scrubber effluent goes to a water treatment system for filtration with activated carbon and testing before collection.

[0108] In another embodiment, the gas stream exits the scrubber vessel and enters a secondary scrubber. In another embodiment of the present disclosure, the gas stream enters a secondary scrubber where the process gas is scrubbed again to further reduce the temperature of the process gas and remove as much water as possible from the process gas. In another embodiment, the process gas is cooled by cold water sprays to a temperature of about 5°C to about 35°C. In another embodiment, the secondary scrubber includes a demister element that eliminates the possibility of carryover of water droplets in the secondary scrubber process gas stream. In a further embodiment, the secondary scrubber process gas stream exits through a tube near the top of the secondary scrubber. In this embodiment, the water collected in the secondary scrubber discharges as a water stream through a tube located at the bottom of the secondary scrubber, and the water stream containing the scrubber effluent goes to a water treatment system for filtration with activated carbon and testing before collection.

[0109] In another embodiment of the present disclosure, a secondary scrubber is further used to remove undesirable compounds, such as ions including phosphorus-containing molecules and phosphine gas. In a further embodiment, a potassium permanganate solution is used in the secondary scrubber to remove phosphorus-containing molecules and ions that form potassium phosphate, which is removed as a salt.

[0110] In one embodiment of the disclosure, water is a by-product of the reactions occurring in the process reactor and exits the process from the primary scrubber and from the secondary scrubber. This water is combined and tested before being collected and distributed as a clarified water source. If the water does not meet the discharge standards, it is treated with activated carbon. The carbon may be reactivated with a hydrogen reduction process.

[0111] In a further embodiment, the gaseous mixture, now containing primarily hydrogen and methane, exits the scrubber system and is compressed. In another embodiment, the compressed mixture then enters a separator, such as a hydrogen separator. In one embodiment, the hydrogen separator is a membrane separator made of precious metals that separates gases based on the molecular size of the gases, with hydrogen being the smallest. The separator separates the hydrogen gas from the gaseous mixture with about 85% efficiency to form two separate gas streams. In one embodiment, the recovered hydrogen gas stream, which may contain methane, CO, and CO2, is recycled back to either the IRC or hydrogen reduction reactor in the process. In another embodiment, the recovered hydrogen gas stream is used as a fuel or in an energy generation system, such as a fuel cell. In another embodiment, the hydrogen separator is a pressure swing absorption unit.

[0112] In another embodiment, the remaining gas stream consists primarily of methane, which may be further separated to produce a gas consisting of about 95% or more methane. The remaining gas stream may contain amounts of hydrogen, CO, and CO2. In one embodiment, the further separation is performed using membrane or pressure swing absorption. In one embodiment, the product gas containing primarily methane may be used as a clean-burning fuel. In another embodiment, the product gas containing primarily methane may be injected into a natural gas pipeline for distribution as synthetic natural gas (SNG) or renewable natural gas (RNG), depending on the supply type. In another embodiment, if the desired product is hydrogen, the gas exiting the hydrogen separator consists primarily of CO2 with some methane and CO.

[0113] In one embodiment, the organic material is processed using hydrogen reduction as described to form a product gas composed primarily of hydrogen that can be used to power a hydrogen fuel cell or as a hydrogen fuel source. In another embodiment, the organic material is processed using hydrogen reduction as described to form a product gas composed primarily of methane that can be used as a fuel or injected into a distribution pipeline as synthetic natural gas (SNG) or renewable natural gas (RNG). EXAMPLES

[0114] In order to better understand the invention described herein, the following examples are set forth. It should be understood that these examples are for illustrative purposes only. As such, they should not be construed as limiting the scope of the invention in any way.

[0115] Example 1 – Process Modeling Two embodiments of the present disclosure are described below to provide examples of the production of methane from the conversion of two specific organic materials. The following examples are based on the known chemical composition of these materials. This information is combined with standard engineering calculations, as well as process modeling of the chemical reactions. The chemical reactions have been described above. The calculations assume that hydrogen is added as a reactant. For hydrogen separation, the following efficiencies are used: hydrogen recovery 85%, methane rejection 92%, CO rejection 100%, CO2 rejection 50%, and water rejection 100%.

[0116] In one embodiment, polyethylene-based plastic waste, such as Automotive Shredding Residue (ASR), is converted to methane or synthetic natural gas (SNG). The material is placed in a bin that is fed directly into the Initial Reduction Chamber (IRC). The ASR has the following chemical composition (mol %) on a dry basis: 2.2% nitrogen, 53.6% carbon, 16.4% oxygen, 6.6% hydrogen, and 21.2% ash. The process was modeled using 10 mol % excess hydrogen after completion of the hydrogen reduction reaction. The operating conditions used in the model were that the reduction chamber was operated from ambient to 425°C, as measured on the substrate, at a ramp rate of 8°C / min, and the vessel was held within a pressure range of 1 atm to 5 atm (with positive pressure maintained). According to the model, the produced gas is transferred to a reactor at 425°C where a continuous supply of hydrogen is added to maintain a measured excess concentration of hydrogen of 10% (this concentration can be determined by ensuring that at least 10% hydrogen is present in the gas exiting the scrubber system before the hydrogen is separated for recycle, as described above), and the reactor is operated at 850°C. The moisture content of the ASR is typically 5%-25%. In addition to polyethylene, the ASR may contain DEHP (diethylhexyl phthalate) and brominated flame retardants. The predicted output gas had the following chemical composition: methane 51.7%, CO2 38.5%, CO 8.2%, and hydrogen 1.6%. Conversion of one dry ton of ASR produces a higher heating value output gas of 28.7 GJ. According to the model, the remaining solid residue is expected to contain elemental carbon, silica, glass debris, and metals including zinc. DEHP and brominated flame retardants, as well as any traces of PCBs, are expected to be destroyed. Tar formation throughout the process is expected to be virtually nonexistent. The methane in this output gas can be separated from other components to produce a gas that is greater than 95% methane and suitable for distribution in natural gas pipelines as SNG.

[0117] In another modeled process, digested sewage sludge is converted to methane or renewable natural gas (RNG). The material is placed in trays that are fed directly into the Initial Reduction Chamber (IRC). The digested sewage sludge has the following chemical composition (mol %) on a dry basis: 4.7% nitrogen, 34.0% carbon, 20.0% oxygen, 4.9% hydrogen, 1.3% sulfur, 0.1% chlorine, and 35.0% ash. The process was modeled using 10 mol % excess hydrogen after completion of the hydrogen reduction reaction (this concentration can be determined by ensuring that at least 10% hydrogen is present in the gas exiting the scrubber system before the hydrogen is separated for recycle, as described above). The moisture content of digested sewage sludge is typically 70%-80%. According to the model, the sewage sludge was first ramped from ambient to 105°C at 8°C / min, and the reactor bypass valve was opened to allow water from the sludge in the form of steam to be captured in a scrubber and quenched to 30°C to form water again. According to the model, once the sludge was substantially water-free and evaporation was no longer consuming energy from heating, the temperature was ramped at 8°C / min until a maximum temperature of 425°C was reached in the sludge, and the vessel was held at a pressure of 1-5 atmospheres (with positive pressure maintained). The gas produced was transferred at 425°C to the reactor operated at 850°C. As above, additional hydrogen can be added to the reactor to maintain a 10% excess concentration of hydrogen in the reactor gas. The expected output gas had the following chemical composition: methane 45.2%, CO2 43.3%, CO 9.2%, and hydrogen 2.4%. Conversion of one dry tonne of digested sewage sludge is expected to produce 20.4 GJ of higher heating value output gas. The methane in this output gas can be separated from other components to produce gas that is greater than 95% methane and suitable for distribution in natural gas pipelines as RNG.

[0118] Example 2 - Comparative Example - PCB Destruction A bottle of electrolytic capacitors was placed in the reduction chamber and operated as follows.

[0119] The chamber was purged with nitrogen to remove oxygen-containing air, and then hydrogen was introduced. Once hydrogen was introduced, the chamber was heated externally with natural gas-fired heating tubes so that the temperature of the vessel reached 600°C as quickly as possible. When the temperature, measured with a thermocouple placed on the inside wall within the vessel, reached 550°C, the chamber quickly filled with gaseous hydrocarbons, resulting in a rapid pressure surge in both the reduction chamber, the reactor (850°C), and the scrubber. The burners were immediately turned down and the pressure surge subsided within one minute. The chamber was then heated again to maintain a constant but manageable production of gases flowing into and through the reactor into the scrubber system. This resulted in visible tar formation throughout the scrubber system, requiring thorough cleaning at least every 28 days. Increasing the reactor temperature to 875°C and 900°C had little or no effect on this tar formation.

[0120] Example 3 - Methane production from dried wood chips An example of dried wood chips is carried out after the temperature of the reduction chamber was increased from ambient to 450°C at 8°C / min. A container made of steel mesh was filled with dried wood chips and placed in the sealed chamber. The chamber was purged with nitrogen and placed in an electrically heated furnace apparatus. Hydrogen was added at a constant rate and the temperature was increased to 450°C at a constant rate of 8°C / min at a pressure of 1 atmosphere. Methane gas began to be detected after the scrubber when the temperature reached 80°C. The concentration of methane gradually increased as the temperature increased and the concentration of hydrogen decreased corresponding to the production of methane, reaching a maximum concentration at 400-420°C. When 450°C was reached, the heating rate was stopped as no further methane was being produced. No tar was formed in the scrubber or any other part of the reactor system.

[0121] All publications, patents, and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains, and are hereby incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.

[0122] Although the present invention has been described with reference to preferred embodiments, it should be understood that modifications and variations may be made therein without departing from the spirit and scope of the invention, as would be readily understood by one skilled in the art, and such modifications and variations are deemed to be within the spirit and scope of the invention and the appended claims.

Claims

1. 1. A process for reducing organic material to produce methane and / or hydrogen, comprising: (a) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, the reduction chamber being substantially free of oxygen, and heating the reduction chamber to effect a temperature increase within the organic material from ambient temperature to up to 425° C. at a pressure greater than about 1 atmosphere and less than about 5 atmospheres at a rate of up to about 8° C. per minute to form a first gaseous mixture comprising methane, hydrogen, acids, and partially reduced volatile organic molecules; (b) heating the first gaseous mixture to a temperature of about 675° C. to about 875° C. in the presence of an excess of hydrogen gas; methane and / or hydrogen, and forming a second gaseous mixture comprising an acid; (c) neutralizing the second gaseous mixture with a base.

2. 10. The process of claim 1, wherein step (a) is carried out as a batch process.

3. 3. The process of claim 1 or 2, wherein the process is carried out at a pressure of at least about 2 atmospheres and less than about 5 atmospheres.

4. The process of any one of claims 1 to 3, wherein the process is carried out at a pressure of from about 2 atmospheres to about 3 atmospheres.

5. In step (a), the process comprises:

3. The process of claim 1 or 2, further comprising decreasing the heating of the reduction chamber if a sudden pressure increase occurs and / or if the pressure in the reduction chamber approaches about 5 atmospheres.

6. The organic material comprises water, and in step (a) the process comprises: heating the reduction chamber to effect the temperature increase in the organic material to about 100° C. to about 105° C. and maintaining the temperature of the organic material at about 100° C. to about 105° C. to evaporate water from the organic material and form steam; The process of any one of claims 1 to 5, further comprising removing the steam from the reduction chamber before further increasing the temperature of the organic material.

7. 7. The process of claim 6, wherein the process further comprises cooling the steam removed from the reduction chamber to reform water, neutralizing the water to neutralize any acids present, and treating the water to remove any organic molecules and / or metals present.

8. 8. The process of claim 7, wherein treating the water comprises filtering the water through an activated carbon filter.

9. The process of any one of claims 1 to 8, wherein step (b) is carried out in a substantially oxygen-free, closed reaction vessel.

10. 10. The process of claim 9, wherein step (b) is carried out under continuous mixing conditions.

11. The process of any one of claims 1 to 10, wherein step (b) comprises heating the first gaseous mixture to a temperature of from about 750°C to about 850°C.

12. The process of claim 11, wherein step (b) comprises heating the first gaseous mixture to a temperature of about 800°C to about 850°C.

13. The process according to any one of claims 9 to 12, wherein step (b) of the process is carried out in the presence of a catalyst.

14. 14. The process of claim 13, wherein the catalyst is a metal catalyst and the metal is selected from one of more of nickel, copper, iron, nickel alloys, tin (such as powdered tin), chromium, and precious metals.

15. 15. The process of claim 14, wherein the catalyst is embedded in one or more walls of the closed reaction vessel.

16. 16. The process of claim 15, wherein the closed reaction vessel is constructed of a nickel-containing steel alloy.

17. The process of any one of claims 13 to 16, wherein step (b) further comprises heating the first gaseous mixture in the presence of superheated steam.

18. 18. The process of any one of claims 1 to 17, wherein step (c) comprises neutralizing the second gaseous mixture with a base at a temperature of from about 70°C to about 100°C, or about 85°C, to form a neutralized second gaseous mixture.

19. 20. The process of claim 18, wherein the base is selected from an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, or an alkaline earth metal carbonate.

20. 20. The process of claim 19, wherein the base is selected from sodium hydroxide or calcium carbonate.

21. The process of any one of claims 18 to 20, further comprising cooling the neutralized second gaseous mixture.

22. 22. The process of claim 21, wherein the neutralized second gaseous mixture is cooled to a temperature of from about 5°C to about 35°C.

23. 23. The process of claim 21 or 22, wherein the neutralized second gaseous mixture is contacted with a solution comprising potassium permanganate to remove phosphorus-containing molecules from the neutralized second gaseous mixture.

24. 24. The process of any one of claims 1 to 23, further comprising separating the excess hydrogen from the methane after neutralizing the second gaseous mixture.

25. 25. The process of claim 24, further comprising recycling the excess hydrogen to step (a) and / or step (b).

26. The process of any one of claims 1 to 25, wherein the organic material is organic waste, biomass, a chemical warfare agent, a pathogen, or a munitions.

27. 27. The process of claim 26, wherein the organic waste comprises sewage sludge, municipal and industrial solid waste or garbage, landfill gas, agricultural waste, corn and other crops contaminated with mold and associated toxins, organic solvents, halogenated organic compounds, organophosphorus compounds, tires, plastics, automobile shredder residue (ASR), refinery and chemical manufacturing / processing waste, or fossil fuels.

28. 27. The process of claim 26, wherein the biomass comprises wood waste, paper waste, cardboard waste, wood chips, pulp waste, or agricultural biomass.

29. 27. The process of claim 26, wherein the chemical warfare agent comprises a halogenated or organophosphorus chemical warfare agent, such as sarin or VX.

30. 27. The process of claim 26, wherein the pathogen comprises a virus or a bacterium.

31. 27. The process of claim 26, wherein the munitions include rockets or shells containing explosive organic materials and / or propellants such as trinitrotoluene (TNT) or cyclotrimethylenetrinitramine (RDX).

32. 1. A process for reducing organic material to produce methane, comprising: (a1) contacting the organic material with an excess of hydrogen gas in a sealed reduction chamber at ambient temperature, the reduction chamber being substantially free of oxygen, and heating the reduction chamber to effect a temperature increase from ambient temperature to up to 425° C. within the organic material at a pressure greater than about 1 atmosphere and less than about 5 atmospheres at a rate of up to about 8° C. per minute to form a first gaseous mixture comprising methane, hydrogen, acids, and partially reduced volatile organic molecules; (b1) neutralizing the first gaseous mixture with a base.

33. 33. The process of claim 32, wherein step (a1) is carried out as a batch process.

34. 34. The process of claim 32 or 33, wherein the process is carried out at a pressure of at least about 2 atmospheres and less than about 5 atmospheres, or from about 2 atmospheres to about 3 atmospheres.

35. In step (a1), the process comprises:

34. The process of claim 32 or 33, further comprising reducing the heating of the reduction chamber if a sudden pressure increase occurs and / or if the pressure in the reduction chamber approaches about 5 atmospheres.

36. 36. The process of any one of claims 32 to 35, wherein step (b1) comprises neutralizing the first gaseous mixture with a base at a temperature of from about 70°C to about 100°C, or about 85°C to form a neutralized first gaseous mixture.

37. 37. The process of claim 36, wherein the base is selected from an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, or an alkaline earth metal carbonate.

38. 38. The process of claim 37, wherein the base is selected from sodium hydroxide or calcium carbonate.

39. The process of any one of claims 36 to 38, further comprising cooling the neutralized first gaseous mixture.

40. 40. The process of claim 39, wherein the neutralized first gaseous mixture is cooled to a temperature of from about 5°C to about 35°C.

41. 41. The process of claim 39 or 40, wherein the neutralized first gaseous mixture is contacted with a solution comprising potassium permanganate to remove phosphorus-containing molecules from the neutralized first gaseous mixture.

42. The process of any one of claims 32 to 41, wherein the temperature increase within the organic material is from ambient temperature up to about 400°C.

43. 43. The process of claim 42, wherein the organic material is bitumen and the first gaseous mixture comprises a lighter fraction of syncrude oil, and step (a1) produces a non-volatile product comprising syncrude oil.

44. 44. The process of claim 43, further comprising separating said excess hydrogen from said methane and lighter fractions of said syncrude after neutralizing said first gaseous mixture.

45. 45. The process of claim 44, further comprising recycling the excess hydrogen to step (a1) and / or step (b1).

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