HK1165743A - Process for the conversion of organic material to methane rich fuel gas - Google Patents

Description

Process for converting organic matter into methane-rich fuel gas

Technical Field

The present disclosure relates to the conversion of organic matter into methane-rich complete combustion fuel gas. In particular, the present disclosure relates to a method for treating organic matter comprising vaporizing organic matter in the presence of excess hydrogen and superheated steam.

Background

The worldwide demand for electricity is expected to increase by 60% by 2030 (world energy situation, paris IEA, 2004-10-26, page 31). The International Energy Agency (IEA) estimates that fossil fuels will account for 85% of the energy market by the year 2030. In fossil fuel power plants, chemical energy stored in fossil fuels (e.g., coal, fuel oil, natural gas, and oil shale) and oxygen in the air are sequentially converted into thermal energy, mechanical energy, and ultimately into electrical energy for continuous use and distribution. Most thermal power stations in the world use fossil fuels, which are more than nuclear power stations, geothermal power stations, biomass power stations and solar thermal power stations.

Natural gas, primarily methane, is widely used in many plants as a feedstock for chemical synthesis and a primary source of electricity generated through the use of gas and steam turbines. Natural gas is more completely burned than other fossil fuels such as oil and coal and produces less greenhouse gases per unit of energy released. Therefore, power generation using natural gas is the most complete fossil fuel energy source available for combustion and wherever this technology is used competitively. Compressed natural gas is also used as a clean alternative to automotive fuels.

Natural gas can be used to produce hydrogen by carbon dioxide reforming and water gas shift reactions. Hydrogen has a variety of applications, for example, it is a primary feedstock for the chemical industry, a hydrogenating agent, and a fuel source in hydrogen fuel cells such as hydrogen-powered automobiles.

With diminishing domestic supply, the price of natural gas is increasing, which creates an incentive to seek additional sources of this fuel. Gasification of fossil fuels such as coal is an option, however, most commercially available coal gasifiers are mostly designed to produce syngas with high carbon monoxide and hydrogen and minimal methane content.

Existing methods of destroying organic waste materials are typically accomplished using high temperature incineration. These incinerators are very capital intensive and therefore require large equipment, which raises public concerns. They are expensive to operate and have been shown to cause a detonation or detonation during the addition of the hazardous material.

The following are a group of patents related to commercial attempts at gasification and steam reforming:

TSANGARIS, Andreas, and Marc BACON, PCT patent application No. WO 2008/138118;

TSANGARIS, Andreas, and Marc BACON, PCT patent application No. WO 2008/138117;

TSANGARIS, Andrea, and Margaret SWAIN, PCT patent application No. WO/2008/117119;

TSANGARIS, Andreas, and Marc BACON, PCT patent application No. WO 2008/104088;

TSANGARIS, Andreas, and Marc BACON, PCT patent application No. WO 2008/104058;

TSANGARIS, Andrea, Margaret SWAIN, Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Thomas Edward WAGLER, Scott Douglas B Ash AM, Mao Pei CUI, Zhiyuan SHEN, Ashish CHOTALIYA, Nipun SONI, Alisdair AlanMCLEAN, Geoffrey DOBBS, Pascal Bonnie MARCEAU, and Xiaoying ZOU.PCT patent application No. WO/2008/011213;

TSANGARIS, Andreas, and Margaret SWAIN, PCT patent application No. WO 2007/143673;

TSANGARIS, Andrea, Margaret SWAIN, Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Thomas Edward WAGLER, Scott, Douglas B Ash AM, Zhiyuan SHEN, Geofrey DOBBS, Mao Pei CUI, and Alisdair Alan MCLEAN, PCT patent application No. WO/2007/131241;

TSANGARIS, Andrea, Margaret SWAIN, Douglas Michael FEASBY, ScottDouglas B Ash AM, Ash ish CHOTALIYA, and Pascal Bonnie MARCEAU, PCT patent application No. WO 2007/131240;

TSANGARIS, Andrea, Margaret SWAIN, Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Thomas Edward WAGLER, Xiaoying ZOU, Alisdair Alan MCLEAN, and Pascal Bonnie MARCEAU, PCT patent application No. WO 2007/131239;

TSANGARIS, Andrea, Margaret SWAIN, Douglas Michael FEASBY, ScottDouglas B Ash AM, Nipun SONI, and Pascale Bonnie MARCEAU, PCT patent application No. WO 2007/131236;

TSANGARIS, Andrea, Margaret SWAIN, Kenneth Craig CAMPBELL, Douglas Michael FEASBY, Scott Douglas B Ash AM, Alisdair Alan McLEAN, and Pascal Bonnie MARCEAU, PCT patent application No. WO 2007/131235;

TSANGARIS, Andreas and Margaret swain pct patent application No. WO 2007/131234;

TSANGARIS, Andreas, Kenneth c.campbell, and Michael d.feasby and Ke LI, PCT patent application No. WO 2006/128286;

TSANGARIS, Andreas, Kenneth c.campbell, Michael d.feasby, and Ke LI, PCT patent application No. WO 2006/128285;

TSANGARIS, Andreas v, and Kenneth c.campbell; PCT patent application nos. WO 2006/081661;

TSANGARIS, Andreas v., George w.cart, Jesse z., SHEN, michael d.feasby, and Kenneth c.campbell, PCT patent application No. WO 2004/072547;

ZWIERSCHKE, Jayson, and Ernest George DUECK, PCT patent application No. WO/2006/076801;

SHETH, Atul C.PCT patent application No. WO/2007/143376.

The following are other patents relating to hazardous waste destruction:

abdullah, shahid, a method for degrading polychlorobiphenyl in soil us patent 5932472;

almeida, Fernando caravalho. us patent 6767163;

anderson, Perry d., Bhuvan c.pant, Zhendi Wang, et al, U.S. patent 5118429;

baghel, Sunita s., and Deborah a.haitko. us patent 5382736;

balko, Edward n., Jeffrey b.hoke, and Gary a.graphite. U.S. patent 5177268;

batchelor, Bill, Alison Marie Hapka, Godwin Joseph Igwe, et al, U.S. Pat. No. 5789649;

bender, jim. U.S. patent 6117335;

boles, Jeffrey l., Johnny r. gamble, and Laura lackey. us patent 6599423.

Bolsing, Friedrich, and Achim habekost. methods for the reductive dehalogenation of halogenated hydrocarbons U.S. patent 6649044;

cutshall, Eule r., Gregory tilling, Sheila d.scott, et al, U.S. patent 5197823;

dellinger, hard Barrett, and John l.graham. us patent 5650549;

driemel, Klaus, Joachim Wolf, and Wolfgang Schwarz. Process for non-polluting destruction of polychlorinated waste materials U.S. Pat. No. 5191155;

farcasiu, Malvina, and Steven c.petrosius. us patent 5369214;

friedman, Arthur j, and Yuval halpern, U.S. patent 5290432;

ginosar, Daniel m., Robert v.fox, and Stuart k.janikowski. us patent 6984768;

gonzalez, Luciano a., Henry e.kowalyk, and Blair f.sim. us patent 6414212;

gonzalez, lucianno a., Dennis f.mullins, w.john Janis, et al, U.S. patent 6380454;

greenberg, Richard s., and Thomas andrews. U.S. patent 6319328;

levin, George b. U.S. patent 5602298;

us patent 5100638;

newman, Gerard k., Jeffrey h.hartwell, and lancet lobban, U.S. patent 6241856;

potter, Raleigh Wayne, and Michael fitzgerald. us patent 6213029;

us patent 6112675;

quimby, Jay m. U.S. statutory invention registration H2198H;

reagen, William Kevin, and Stuart Kevin janikowski. us patent 5994604;

rickard, Robert s. us 5103578;

ruddick, John n.r., and Futong cui. U.S. patent 5698829;

schulz, Helmut w. us patent 5245113;

sparks, Kevin a, and James e.johnston. U.S. patent 5695732; and

zachariah, Michael r, and Douglas p.dufaux. us 593613.

U.S. patent No. 5,050,511 to Hallett describes the treatment of organic materials using a process that combines gas phase chemical reduction at elevated temperatures above about 600 ℃, preferably above 875 ℃, under a reducing atmosphere and thereafter chemical oxidation of the material with a gaseous oxidant at temperatures above about 1000 ℃. However, this process results in the production of a tarry material, which can lead to process shut down to remove the tarry material.

Disclosure of Invention

It has now been found that heating the organic material to vaporize it in the presence of excess hydrogen and optionally superheated steam to dehalogenate and/or desulfurize the organic material, followed by further heating the mixture in the presence of excess hydrogen and superheated steam to reduce the organic compounds, results in the conversion of the organic material to methane-rich gas and a reduction in the amount of tarry material produced.

Accordingly, the present disclosure includes a process for converting organic matter to methane-rich gas comprising:

a) vaporizing the organic material in a substantially oxygen-free closed chamber and mixing the vaporized organic material with excess hydrogen gas and optionally superheated steam at a temperature of about 450 ℃ to about 650 ℃ to form a first mixture;

b) heating the first mixture in the presence of excess hydrogen and superheated steam to a temperature of about 600 ℃ to about 900 ℃ to form a gas mixture comprising methane, hydrogen, and acid; and

c) the gas mixture is neutralized with a base.

In another embodiment of the present disclosure, the first mixture is mixed thoroughly to reduce the formation of tarry material.

In an embodiment of the present disclosure, the vaporized organic material in a) is mixed with excess hydrogen and optionally superheated steam at a temperature of about 475 ℃ to about 600 ℃.

In yet another embodiment, the first mixture is heated in b) to a temperature of about 700 ℃ to about 900 ℃. In another embodiment, the first mixture is heated in b) to a temperature of about 800 ℃ to about 875 ℃.

In another embodiment of the present disclosure, hydrogen is produced in b) by steam-methane reforming and water-gas shift reactions. The hydrogen produced in this manner reduces the total demand of hydrogen that must be added to form the first mixture.

In another embodiment of the present disclosure, the process for converting organic matter to methane is carried out in the presence of a catalyst. In yet another embodiment, the catalyst is a metal catalyst, wherein the metal is selected from one or more of nickel, copper, iron, nickel alloys, tin, powdered tin, chromium, and noble metals. In another embodiment, the noble metal is selected from the group consisting of platinum, silver, palladium, gold, ruthenium, rhodium, osmium, and iridium.

In another embodiment of the present disclosure, the gas mixture is neutralized in c) at a temperature of about 70 ℃ to about 100 ℃, in yet another embodiment, the gas mixture is neutralized in c) at a temperature of about 85 ℃.

In one embodiment, the base comprises an alkali metal hydroxide or an alkali metal carbonate. In yet another embodiment, the alkali metal hydroxide is sodium hydroxide. In another embodiment, the alkali metal carbonate is calcium carbonate.

In another embodiment of the present disclosure, the method further comprises exposing the gas mixture from b) to ultraviolet light in the presence of excess hydrogen under conditions effective to reduce residual organic compounds in the gas mixture. In another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise heating to a temperature of from about 600 ℃ to about 800 ℃. In yet another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise heating to a temperature of from about 650 ℃ to about 750 ℃. In another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise ultraviolet light at a wavelength of about 200nm to about 300 nm. In another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise ultraviolet light at a wavelength of about 220nm to about 254 nm.

In yet another embodiment of the present disclosure, heating the first mixture in b) is carried out in a second closed chamber that is substantially free of oxygen.

In another embodiment of the present disclosure, the process further comprises cooling the neutralized gas mixture in c). In another embodiment, the gas mixture is cooled to a temperature of about 5 ℃ to about 35 ℃.

In another embodiment of the present disclosure, the method further comprises exposing the neutralized and cooled gaseous mixture to conditions effective to reduce residual organic compounds in the presence of excess hydrogen. In another embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture comprise ultraviolet light at a wavelength of about 200nm to about 300 nm. In yet another embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture comprise ultraviolet light at a wavelength of about 220nm to about 254 nm. In another embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture further comprise heating to a temperature of from about 300 ℃ to about 500 ℃. In one embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture further comprise heating to a temperature of about 400 ℃.

In another embodiment of the present disclosure, the process further comprises separating excess hydrogen from methane after neutralizing the gas mixture in c). In one embodiment, the hydrogen is recycled for use in a).

In another embodiment, the methane comprises from about 10% to about 20% hydrogen by volume.

In another embodiment, a), b), and c) of the disclosed process are carried out at a pressure of greater than 0 atmosphere to about 2 atmospheres, suitably greater than 0 atmosphere to about 0.5 atmosphere.

In another embodiment of the present disclosure, the organic material further comprises an inorganic material that is not vaporized and removed from the enclosed chamber.

In another embodiment of the present disclosure, the organic matter comprises organic waste matter. In yet another embodiment, the organic waste material comprises chlorinated or organophosphorus chemical warfare agents; biological warfare agents; sewage; municipal and industrial solid waste or refuse; agricultural waste materials; an organic solvent; a halogenated organic solvent; halogenated organic compounds, such as polychlorobiphenyl, hexachlorobenzene, chlorinated pesticides, brominated flame retardants, fluorinated propellants or fluorinated refrigerants; organic phosphorus compounds such as pesticides; explosives such as trinitrotoluene; a rocket fuel; a tire; plastics such as polyethylene; hydrazines; refinery and chemical manufacturing/processing waste, such as pot bottom residue; coal; or oil and/or bitumen processing waste, for example from tar sands. In another embodiment, the chlorinated or organophosphorous chemical warfare agent comprises mustard gas or VX nerve agent. In one embodiment, the biological warfare agent comprises anthrax. In yet another embodiment, the agricultural waste material comprises poultry, cattle, swine or other livestock waste material. In another embodiment, the organic matter comprises biomass, such as wood waste or pulp waste. In another embodiment, the biomass comprises wood chips. In another embodiment of the present disclosure, the organic material comprises fossil fuels, such as all types of coal, oil, or peat.

In yet another embodiment of the present disclosure, the methane gas produced in the process is converted to electricity using a conventional energy production system. The gases are thus fed into, for example, a gas turbine, a steam turbine or a fuel cell. In one embodiment, the capacity system is in close proximity to or associated with the apparatus for performing the disclosed method.

In another embodiment of the present disclosure, the methane gas produced in the process is used for chemical synthesis.

Further, the present disclosure includes a reaction, mixing, or milling device. The apparatus may be used as a Continuous Reducing Vaporizer (CRV). In an embodiment of the disclosure, an apparatus comprises a vessel rotatable about an axis, the vessel comprising a first end having a coaxial inlet or outlet for introducing or discharging material, respectively, from the vessel, the first end comprising a flange section having a first face extending generally radially. The device also includes a closure disposed proximate the first end, the closure including a second generally radially extending face generally opposite the first face. The device further comprises an inner sealing element and an outer sealing element arranged between the first face and the second face, the inner sealing element and the outer sealing element defining a substantially annular space, wherein the annular space containing the sealing liquid forms a seal between the container and the closure.

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 the specific examples, while indicating preferred embodiments of the disclosure, are given by way of illustration only, since various changes and modifications within the spirit and scope of the disclosure will become apparent to those skilled in the art from this detailed description.

Drawings

Embodiments of the present disclosure will be described with reference to the accompanying drawings, in which:

FIG. 1 is a schematic diagram of an embodiment of the process of the present disclosure;

FIG. 2 is a schematic view of an organic waste pretreatment system in an embodiment of the present disclosure;

FIG. 3 is a schematic illustration of an apparatus according to an embodiment of the disclosure;

FIG. 3a is a detailed view of the device shown in FIG. 3;

FIG. 3b is a cross-sectional view of the device shown in FIG. 3;

FIG. 4 is a schematic diagram of a mixer in an embodiment of the disclosure;

FIG. 5 is a schematic view of an enclosed chamber in an embodiment of the present disclosure;

FIG. 6 is a schematic view of an enclosed chamber with ultraviolet light in an embodiment of the present disclosure;

FIG. 7 is a schematic diagram of a chiller and primary scrubber system in an embodiment of the disclosure;

FIG. 8 is a schematic diagram of a secondary scrubber in an embodiment of the disclosure;

FIG. 9 is a schematic diagram of a hydrogen separator and recovery system in an embodiment of the disclosure; and

fig. 10 is a schematic diagram of a process embodiment of the disclosure.

Detailed Description

(I) Definition of

Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to apply to all embodiments and aspects described herein to which they are applicable, as understood by those of skill in the art.

The term "organic matter," as used herein, refers to any one or more organic compounds, biomass, one or more microorganisms, toxic mixtures, or any other carbon-based compound or mixture that can be converted to methane gas. The term "organic waste material" refers to material that requires treatment prior to treatment. The disposal of organic waste material may be necessary because the material is toxic, infectious, environmental pollutants, etc. Examples of organic waste materials include, but are not limited to, chlorinated or organophosphorus chemical warfare agents, such as mustard gas or VX; biological warfare agents such as anthrax; sewage, municipal or industrial solid waste or garbage; agricultural waste material such as from poultry, cattle, swine or other livestock; an organic solvent; a halogenated organic solvent; halogenated organic compounds such as polychlorobiphenyl, hexachlorobenzene, chlorinated pesticides, brominated flame retardants, fluorinated propellants or fluorinated refrigerants; organic phosphorus compounds such as pesticides; explosives such as trinitrotoluene; a rocket fuel; hydrazines; a tire; plastics such as polyethylene; refining and chemical manufacturing/processing waste such as bottom of a pot residue; coal; or oil and/or bitumen processing waste, for example from tar sands. Organic matter that can be converted to methane gas includes any type of fossil fuel, such as coal or peat, or any type of renewable fuel biomass, such as wood chips, that can be converted to methane gas because they are based on carbon. Further, biomass includes waste biomass, such as wood waste or pulping waste.

The term "coal" as used herein includes any form of readily combustible black or brown sedimentary rock, such as lignite (or brown coal), sub-bituminous coal, boiler coal, anthracite and graphite.

The term "substantially oxygen-free" as used herein refers to a process of dehalogenation, desulfurization and reduction of an organic compound in the absence of oxygen. The purpose of conducting the reaction in the absence of oxygen is to avoid oxidation of the organic compound to produce unwanted by-products. Thus, the oxygen content in the enclosed chamber is less than about 0.10%, optionally less than about 0.08%, and suitably less than about 0.04% by volume.

The term "excess" as used herein refers to an amount of hydrogen in excess of the stoichiometrically required amount mixed with the organic substance. The excess hydrogen remaining after completion of the reduction reaction is from about 10% to about 80% (mol%), suitably from about 20% to about 60%, more suitably from about 25% to about 50%.

The terms "mixing" and "intimately mixing" as used herein mean that the vaporized organic material is intimately mixed with excess hydrogen and superheated steam in such a way that the organic material is fully dehalogenated and reduced with hydrogen. Thorough mixing allows the hydrogen to bombard the organic compounds in the organic matter from all directions and helps the dehalogenation, desulfurization and reduction reactions to be nearly complete. If the vaporized organic material is not thoroughly mixed with excess hydrogen and superheated steam, the compounds in the organic material will not be fully dehalogenated and reduced, resulting in the formation and condensation of tar-like material. Mixing is achieved using any known method, such as a static mixer or conditions that create turbulence.

The term "tarry" as used herein refers to condensed polycyclic aromatic hydrocarbons derived from organic matter insufficiently mixed with excess hydrogen and superheated steam. When the organic matter is insufficiently mixed with excess hydrogen and superheated steam, the organic compounds in the organic matter are incompletely dehalogenated and/or desulfurized and then incompletely reduced. As a result, aromatics in the organic material condense and form a tar-like material that accumulates in the process reactor, causing the process to stop. In addition, the tarry material must be disposed of at the time.

The term "dehalogenation" as used herein 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 of the organic compound and replacement with a hydrogen atom. The reaction also produces an acid.

The term "desulfurization" as used herein refers to a process in which an organic compound containing a sulfur atom reacts with hydrogen, resulting in the loss of the sulfur atom of the organic compound and replacement with hydrogen. The reaction also produces hydrogen sulfide (H)₂S)。

The term "reduced organic compound" as used herein means the reduction of an organic compound to methane or other small aliphatic hydrocarbons such as, but not limited to, ethane, ethylene or propane.

The term "neutralizing" as used herein means adjusting the pH of a solution to a pH that is approximately neutral (pH 7) or not harmful to the environment or organisms. For example, neutralizing the acidic solution to a pH of about 7 can be achieved by adding a base to the acidic solution.

The term "superheated steam" as used herein refers to water that has been heated to a temperature of about 600 ℃ to 900 ℃ at a pressure of greater than 0 atmospheres to about 2 atmospheres.

The term "vaporized" as used herein refers to a liquid that has been converted to its gaseous form by heating.

The term "base" as used herein refers to any compound that is capable of accepting a proton and thereby neutralizing an acidic solution. Examples of the base include, but are not limited to, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkali metal carbonates such as calcium carbonate.

Unless otherwise indicated, the terms "a," "an," or "the" as used herein include aspects having one member, as well as aspects having more than one member. For example, embodiments that include "a catalyst" should be understood to present certain aspects having one catalyst or two or more additional different catalysts.

In understanding the scope of the present disclosure, the term "comprising" and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps. The foregoing also applies to words having similar meanings such as the terms, "including", "having" and their derivatives. Finally, terms of degree such as "substantially", "about" and "approximately" as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. To the extent that such terms are not intended to negate the meaning of the word they modify, they are to be construed as to include a deviation of at least 5% of the modified term.

(II) methods and apparatus of the present disclosure

The present disclosure includes a process for converting organic matter to methane-rich gas comprising:

a) vaporizing the organic material in a substantially oxygen-free closed chamber and mixing the vaporized organic material with excess hydrogen gas and optionally superheated steam at a temperature of about 450 ℃ to about 650 ℃ to form a first mixture;

b) heating the first mixture in the presence of excess hydrogen and superheated steam to a temperature of about 600 ℃ to about 900 ℃ to form a gas mixture comprising methane, hydrogen, and acid; and

c) the gas mixture is neutralized with a base.

In another embodiment of the present disclosure, the first mixture is mixed sufficiently to reduce, if appropriate, avoid the formation of tarry material. The vaporized organic material is intimately mixed with hydrogen gas and optionally superheated steam to intimately contact the organic compound with the hydrogen and reduce or avoid the formation of tarry material.

In embodiments of the present disclosure, the vaporized organic material is mixed with excess hydrogen and optionally superheated steam to form a first mixture at a temperature of about 475 ℃ to about 600 ℃.

At temperatures of about 450 ℃ to about 650 ℃ in a), most of the aromatic and aliphatic hydrocarbons present in the organic matter lose halogen atoms in the dehalogenation reaction, as shown in scheme 1. The reaction also produces an acid. Thus, more than about 50%, optionally more than about 70%, suitably more than about 80%, more suitably more than about 90% and most suitably more than about 95% of the organic compounds in the organic material have been dehalogenated when the first mixture enters b). Similarly, organic compounds containing sulfur atoms are desulfurized in the presence of excess hydrogen.

Scheme 1

a) The presence of superheated steam is optional. Superheated steam is not required if the organic matter already contains water, as heating such a mixture will generate steam. In one embodiment, superheated steam is added at some point in the process prior to b).

In yet another embodiment, the first mixture in b) is heated to a temperature of about 700 ℃ to about 900 ℃. In another embodiment, the first mixture in b) is heated to a temperature of about 800 ℃ to about 875 ℃.

At a temperature of about 600 ℃ to about 900 ℃ in b), a substantial portion of the dehalogenated and desulfurized aromatic and aliphatic hydrocarbon compounds in the first mixture will be reduced to methane or other smaller aliphatic hydrocarbons, as shown in scheme 2. Thorough mixing of the organic matter with excess hydrogen and superheated steam ensures that the organic compounds are substantially reduced and thus the formation of tarry matter is reduced or avoided.

Scheme 2

In another embodiment of the present disclosure, hydrogen is produced in b) by steam methane reforming and water gas shift reactions. The steam in the first mixture is combined with the methane produced in scheme 2 to produce hydrogen and carbon monoxide. The carbon monoxide is further combined with steam to produce hydrogen and carbon dioxide. The hydrogen produced in this manner reduces the total required amount of hydrogen that must be added to form the first mixture.

In another embodiment of the present disclosure, the process for converting organic matter to methane, the steam-methane reforming reaction and the water-gas shift reaction are carried out in the presence of a catalyst. In yet another embodiment, the catalyst is a metal catalyst, wherein the metal is selected from one or more of nickel, copper, iron, nickel alloys, tin, powdered tin, chromium, noble metals. In another embodiment, the noble metal is selected from one or more of platinum, silver, palladium, gold, ruthenium, rhodium, osmium, and iridium.

In another embodiment of the present disclosure, the gas mixture is neutralized in c) at a temperature of about 70 ℃ to about 100 ℃. In yet another embodiment, the gas mixture is neutralized in c) at a temperature of about 85 ℃. As a result of the dehalogenation and/or desulfurization reactions, the acidic by-product (HCl in scheme 1) is neutralized prior to separation and purification of hydrogen and methane.

In one embodiment, the base includes any compound that neutralizes an acid. In another embodiment, the base is an alkali metal hydroxide or an alkali metal carbonate. In yet another embodiment, the alkali metal hydroxide is sodium hydroxide. In another embodiment, the alkali metal carbonate is calcium carbonate.

In another embodiment of the present disclosure, the method further comprises exposing the gas mixture from b) to ultraviolet light in the presence of an excess of hydrogen gas under conditions effective to reduce residual organic compounds in the gas mixture. In another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise heating to a temperature of from about 600 ℃ to about 800 ℃. In yet another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise heating to a temperature of from about 650 ℃ to about 750 ℃. In another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise ultraviolet light at a wavelength of about 200nm to about 300 nm. In another embodiment, the conditions effective to reduce residual organic compounds in the gas mixture comprise ultraviolet light at a wavelength of about 220nm to about 254 nm. The exposure of the gas mixture to uv light reduces any residual organic compounds that are not reduced by the temperature in b). The ultraviolet light helps to reduce any residual aromatic or partially aromatic structures at lower temperatures than those required in b). The ultraviolet light possesses a wavelength of 254nm, 248nm or 220nm, which helps to reduce the residual compounds to form saturated or fully reduced non-double bond aliphatic organic compounds, preferably methane, as shown in scheme 3.

Scheme 3

In yet another embodiment of the present disclosure, heating the first mixture in b) is performed in a second closed chamber that is substantially free of oxygen.

In another embodiment of the present disclosure, the process further comprises cooling the neutralized gas mixture in c). In another embodiment, the gas mixture is cooled to a temperature of about 5 ℃ to about 35 ℃.

In another embodiment of the present disclosure, the method further comprises exposing the neutralized and cooled gas mixture to conditions effective to reduce residual organic compounds. In another embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture comprise ultraviolet light at a wavelength of about 200nm to about 300nm in the presence of excess hydrogen. In yet another embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture comprise ultraviolet light at a wavelength of about 220nm to about 254 nm. In another embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture further comprise heating to a temperature of from about 300 ℃ to about 500 ℃. In one embodiment, the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture further comprise heating to a temperature of about 400 ℃. At this point in the process, if unacceptable levels of aromatics, such as benzene, remain, the gas mixture is reheated and exposed to ultraviolet light in the presence of excess hydrogen to reduce the residual levels of unsaturated organic compounds, as shown in scheme 4.

Scheme 4

In another embodiment of the present disclosure, the process further comprises separating hydrogen and methane after neutralizing the gas mixture in c). In one embodiment, the hydrogen is recycled for use in a). In one embodiment, the process of separating hydrogen and methane is accomplished using a hydrogen separator known to those skilled in the art.

In another embodiment of the present disclosure, methane gas is compressed and can be used as a complete combustion fuel. In one embodiment, the methane gas has from about 0% to about 30% hydrogen by volume, optionally from about 5% to about 25% hydrogen by volume, and in the case of hydrogen, from about 10% to about 20% hydrogen by volume.

In another embodiment of the present disclosure, the organic material further comprises inorganic material that does not vaporize and is removed from the process. Since the inorganic matter cannot be vaporized, the inorganic matter is separated from the vaporized organic waste matter. In one embodiment, the inorganic material is allowed to settle at the bottom of the closed chamber and is subsequently removed by draining from the bottom of the chamber.

In another embodiment of the present disclosure, the organic waste material comprises chlorinated or organophosphorus chemical warfare agents; biological warfare agents; sewage; municipal or industrial solid waste or refuse; agricultural waste materials; an organic solvent; halogenated organic solvents, halogenated organic compounds such as polychlorobiphenyl, hexachlorobenzene, chlorinated pesticides, brominated flame retardants, fluorinated propellants or fluorinated refrigerants; organic phosphorus compounds such as pesticides; explosives such as trinitrotoluene; a rocket fuel; hydrazines; a tire; plastics such as polyethylene; refining and chemical manufacturing/processing waste such as bottom of a pot residue; coal; or oil and/or bitumen processing waste, for example from tar sands. In another embodiment, the chlorinated or organophosphorous chemical warfare agent comprises mustard gas or VX nerve agent. In one embodiment, the biological warfare agent comprises anthrax. In yet another embodiment, the agricultural waste material includes poultry, cattle, swine or other livestock waste material such as manure and render waste. In another embodiment, the organic matter comprises biomass, such as wood waste or pulp waste. In another embodiment, the biomass comprises wood chips.

In embodiments of the present disclosure, the organic material used in the methods of the present disclosure includes fossil fuels such as all types of coal, oil, or peat. In this embodiment, the process represents a method for the vaporization of fossil fuels and for converting these fuel sources into completely combusted methane and hydrogen.

In one embodiment, the organic material is pre-treated to form a uniform and easily transportable feed. In yet another embodiment, when the organic substance comprises water, the method further comprises treating the substance to remove water prior to vaporization of the organic substance in (a).

With respect to fig. 1, an overview of the process is illustrated. In embodiments of the present disclosure, prior to treatment and depending on the nature of the organic material, the material is pre-treated in the crusher/pulverizer apparatus 2 to form a uniform and easily transportable feed. In one embodiment, when the organic matter is soil, sediment, sewage, sludge, municipal solid waste, or any other solid type of matter, the crusher/crusher device 2 crushes the matter to a uniform size and is able to transfer the matter through the process. In yet another embodiment, when the organic substance comprises water, a pretreatment is optionally performed to remove the water prior to treatment.

In another embodiment, the organic material is sent to a device capable of vaporizing the organic material, for example, a Continuous Reduction Vaporizer (CRV) 3. In one embodiment, the material is transported to CRV3 using a auger. In yet another embodiment, when the material is flowable, it is transported to the CRV using a slurry pump.

In embodiments of the present disclosure, the CRV3 is a rotatable reaction, mixing, and/or milling device (described further below) that is heated and thus vaporizes organic material that has been transported to the CRV 3. In embodiments of the present disclosure, the organic matter comprises non-vaporizable inorganic waste material in addition to the vaporizable organic compound. In one embodiment, the inorganic waste material that is not vaporized in the CRV3 is withdrawn from the CRV3 as treated solids 10. The treated inorganic waste material free of organic material is suitably recycled or disposed of to waste. Examples of inorganic waste materials include any type of material that does not vaporize in heating the CRV3 and include, but are not limited to, metals, minerals, stone, sand, or silica.

In yet another embodiment, vaporized organic material is passed from the CRV3 to a mixer, such as a static mixer 4, where the vaporized organic material is thoroughly mixed with excess hydrogen and superheated steam. The intimate mixing of vaporized organic material with excess hydrogen and superheated steam allows the components of the mixture to be thoroughly mixed and reduces the formation of tarry material. Mixing can also be performed using any other known means.

In another embodiment of the present disclosure, the well-mixed and heated vaporized organic material, hydrogen gas, and superheated steam are delivered to a substantially oxygen-free enclosed chamber, e.g., process reactor 5. In yet another embodiment, the mixture is further heated in the process reactor 5 to produce methane gas.

In yet another embodiment, the gas mixture is discharged from the process reactor 5 and enters the secondary reaction chamber 6, and the secondary reaction chamber 6 employs ultraviolet light in the presence of excess hydrogen to reduce residual organic compounds in the gas mixture.

In another embodiment, the gas mixture then enters a cooler and primary scrubber 7, where the mixture is cooled and the acid, water and any particulate matter are removed from the mixture. In yet another embodiment, the mixture enters a secondary scrubber 8 to remove residual acid and water.

In another embodiment, the gas mixture now comprises primarily hydrogen and methane. In another embodiment, the mixture then enters a separator 9, such as a hydrogen separator, which compresses and cools the mixture before entering the membrane-type separator. The separator 9 separates hydrogen from the gas mixture with an efficiency of about 85% to form two separate gas streams. Stream 11 is a methane-rich gas stream containing 10% to 20% hydrogen which can then be used, for example, as a complete combustion fuel, for the generation of heat or electricity or for any other known use of methane. In yet another embodiment, the methane-rich gas stream is further reformed to produce hydrogen and used as a fuel, for example in a fuel cell, or for any other known use for hydrogen. Stream 12 is essentially hydrogen recovered from the gas mixture, which is recycled for reuse in the project and returned to the CRV3 or mixer 4. Water is a by-product of the reaction occurring in the process reactor and is removed from the process as stream 79 from the primary scrubber 7 and as stream 89 from the secondary scrubber 8. Streams 79 and 89 are mixed prior to discharge as effluent from the process, then treated and tested.

Fig. 2 illustrates an apparatus for pretreatment of organic matter according to one embodiment of the present disclosure. In this embodiment, organic material 1 enters primary feed hopper 20. In yet another embodiment, the organic material enters a crusher/pulverizer apparatus 2, which grinds the material into a uniform feedstock that is easily transported in the process. Crushers/mills are known to those skilled in the art and are commercially available. In one embodiment, the organic material is fed through a crusher/pulverizer 21, the crusher/pulverizer 21 also being a product known to those skilled in the art and commercially available. In yet another embodiment, the pulverized homogeneous mass falls into a secondary hopper 22 where the mass is metered into the process through a valve 23, such as a rotary valve. The organic matter then enters a tertiary hopper 24 and is then transported by a transport device 25, such as a screw conveyor or a slurry pump, to an inlet 26 of the continuous reduction vaporizer 3.

In one embodiment, tertiary hopper 24 is charged with an inert gas, such as nitrogen, argon or carbon dioxide, through inlet 27 to remove oxygen from the system. This charging places the process to be carried out in a substantially oxygen-free environment.

In another embodiment, the tertiary hopper 24 is heated and charged with steam.

In another embodiment, the volume of organic material in secondary hopper 22 is controlled by valve 23, which meters organic material into tertiary hopper 24. In another embodiment, secondary hopper 22 also provides a back pressure to the inert environment of tertiary hopper 24, thus providing a positive pressure seal for the process and allowing the reaction to proceed in a substantially oxygen-free environment. In yet another embodiment, the conveyance device 25 also provides a back pressure to the inert environment between the conveyance device 25 and the tertiary hopper 24.

In an embodiment of the present disclosure, the conveyor 25 is a screw conveyor comprising two counter-rotating screws, which convey the organic waste material to the inlet 26 of the CRV 3. The design of the auger is such that the auger is fully filled and the counter-rotation provides positive feed without packing.

In another embodiment, when the organic matter is flowable, such as sewage sludge, the matter is metered and transported to the CRV using a slurry pump. Slurry pumps are known to those skilled in the art and are commercially available.

With respect to fig. 3, the apparatus is shown generally at 64. In some embodiments, the apparatus 64 may be implemented as a CRV 3. Apparatus 64 is an example of a suitable apparatus that may be implemented as a CRV3 and is not to be construed as limiting the various embodiments provided by the present disclosure. Furthermore, the apparatus 64 should not be limited to being a particular tool for the CRV3, and may be implemented in other organic vaporization applications. The apparatus 64 may be used more broadly, for example, but not limited to, as a reaction apparatus, a mixer apparatus, or as a milling apparatus (e.g., as a ball mill, rod mill, or pebble mill).

The apparatus 64 includes a container 30 rotatable about an axis 28. The shaft 28 is generally horizontal. The container 30 may include a first end having an inlet 68 and a second end having an outlet 69, the inlet 68 and outlet 69 for introducing a substance into the container 30 or discharging a substance out of the container 30, respectively. The inlet 68 and outlet 69 are generally coaxial with the shaft 28. A helical scraper 32 may be provided in the container 30 adjacent the outlet 69 to assist in discharging the solids through the outlet 69 (see figure 3 b). In some embodiments, the container 30 may include a main barrel portion 30a, a tapered portion 30b on either side of the barrel portion 30a, and a flange section 30c on either side of the tapered portion 30 b. Depending on the particular embodiment, vessel 30 may be constructed from a variety of materials including, for example, but not limited to, inert materials, stainless steel, and superalloys.

With respect to fig. 3a, the flange segment 30c may include inner and outer flange walls 46a, 46 b. The flange walls 46a, 46b are generally cylindrical and coaxial with the shaft 28. A radial web wall 47 may connect the flange walls 46a, 46 b. The web wall 47 may include a first face 73 that extends generally radially. The flange walls 46a, 46b and web wall 47 may form a relatively rigid I-column-type structure. The device 64 may include a support bearing 54 for rotatably supporting the outer flange wall 46b of the flange section 30c, the flange section 30c thus supporting the entire weight of the vessel 30 and its contents. The device 64 may also include a drive mechanism (not shown) for rotating the container 30.

The device 64 includes a closure member 66 disposed adjacent an inlet 68 and an outlet 69. The closure 66 may include a generally radially extending second face 74 generally opposite the first face 73 of the web wall 47. The closure 66 adjacent the inlet 68 may include at least one inlet for introducing a substance into the container 30. As illustrated, closure 66 proximate inlet 68 includes screw conveyor feed 26 and gas feed 12 for delivering material to container 30. The closure 66 adjacent the outlet 69 may include at least one outlet for discharging the substance from the container 30. As illustrated, the closure 66 near the outlet 69 is directly connected to the cyclone chamber 33 of the separating apparatus 65.

The device 64 also includes a sealing device 29 at least one end of the container 30 to provide a seal between the rotating container 30 and the non-rotating closure 66. The sealing device 29 may include an inner sealing element 48a and an outer sealing element 48b disposed between the first face 73 and the second face 74. The inner seal member 48a and the outer seal member 48b define a generally annular space 49. Annular space 49 contains a sealing fluid that forms a seal between container 30 and closure 66. The sealing elements 48a, 48b are generally annular and arranged concentrically. The sealing elements 48a, 48b may be fixed to either of the first and second faces 73, 74 and slide relative to each other. As illustrated, the sealing elements 48a, 48b may each be mounted on the second face 74 using a base member 78 and remain slidable relative to the first face 73. As illustrated, the radial length of the first face 73 between the inner flange wall 46a and the outer flange wall 46b allows the second face 74 to be radially displaced relative to the first face 73 to resist radial thermal expansion and contraction of the vessel 30. The inner and outer sealing members 48a, 48b may be formed from a non-stick material, such as a fluoropolymer (e.g., TEFLON)^TM) And (4) forming.

Closure member 66 may include fluid feed stream 38 and exit stream 39 connected to annulus 49 for circulation of a sealing fluid in annulus 49. The discharge 39 is generally above the feed 38 so that the circulating flow opposes gravity. The flow of the sealing liquid may be controlled between feed stream 38 and discharge stream 39 so as to maintain annular space 49 substantially filled with sealing liquid. Leakage of the sealing fluid from the sealing means 29 is tolerable if the sealing fluid is not detrimental to any reactions taking place in the container 30. The sealing liquid can cool the sealing device 29 and the container 30. In some embodiments, the containment fluid may include water. In some embodiments, the sealing liquid may be recycled after being returned via outlet 39.

Closure 66 may also include a first wall portion 66a and a second wall portion 66b separated by an expansion section 67. The first wall portion 66a includes a second face 74. The second wall portion 66b may be secured to the screw conveyor feed 26 and the gas feed 12. The expansion section 67 may allow axial displacement of the first wall portion 66a relative to the second wall portion 66b to resist axial thermal expansion and contraction of the container 30. To prevent gaps from forming between the sealing elements 48a, 48b and the first face 73, the expansion section 67 may bias the second face 74 against the first face 73 to maintain a good seal between the sealing elements 48a, 48b and the first face 73. Alternatively, external clamps or other means of applying force may be used to bias the second face 74 against the first face 73 in order to maintain a good seal between the sealing elements 48a, 48b and the first face 73.

The apparatus 64 may also include a shield 31 surrounding at least a portion of the container 30. The enclosure 31 may include a heat source (or a heat sink, neither shown) such that the temperature within the enclosure 31 is controllable. In one embodiment, hood 31 may be heated using, for example, but not limited to, indirect gas heating, indirect or direct electronic heating, microwave energy, ultraviolet energy, or superheated steam. Heat is transferred to the vessel 30 by radiative heat transfer, convective heat transfer, or conductive heat transfer, such as a hot oil bath. As shown in FIG. 3, the shroud 31 generally surrounds the barrel portion 30a and terminates at a tapered portion 30b, leaving the flange section 30c exposed outside of the shroud 31 and accessible for maintenance or other purposes.

The device 64 may be connected in combination with a separation device 65. The separation device 65 may include a swirl chamber 33 fluidly connected to and tangentially aligned with the outlet 69 of the vessel 30 for receiving the discharged material. An outlet conduit 40 is positioned above the cyclone chamber 33 for collecting gaseous material from the cyclone chamber 33. A hopper 35 is located below the cyclone chamber 33 and is in flow communication with the cyclone chamber 33 for collecting liquid and solid matter from the cyclone chamber 33. Valves 34a, 34b may be provided to separate the cyclone chamber 33 from the hopper 35. A steam purge stream 37 may be provided between valves 34a, 34 b. A fluid source 36 may be provided in the hopper 35 for cooling the liquid and solid matter.

In some embodiments of apparatus 64 implemented as CRV3, organic material is fed into CRV3 from transport apparatus 25 via inlet 26. The container 30 is rotated within the shielding 31 and the organic substance is vaporized in the container 30.

In some embodiments of apparatus 64 implemented as CRV3, enclosure 31 may be heated using, for example, but not limited to, indirect gas heating, indirect or direct electronic heating, microwave energy, ultraviolet energy, or superheated steam. Heat is transferred to the vessel 30 by radiative heat transfer, convective heat transfer, or conductive heat transfer, such as a hot oil bath. In embodiments of the present disclosure, the organic material in vessel 30 may be directly heated by allowing a controlled amount of oxygen to be introduced. Vessel 30 ensures uniform vaporization of the organic material and helps to thoroughly mix the material with the hydrogen entering the CRV3 via stream 12. The temperature within the vessel 30 may be controlled between about 300 c and about 650 c depending on the boiling or sublimation temperature of the organic matter. The person skilled in the art will be able to determine the temperature necessary for the vaporization of the organic material and the start of the dehalogenation and desulfurization reactions, which will depend on the nature of the material.

In some embodiments of apparatus 64 implemented as CRV3, vessel 30 facilitates intimate mixing of vaporized organic material with excess hydrogen gas. Thorough mixing of the vaporized organic material with excess hydrogen gas produces a homogeneous mixture and facilitates dehalogenation and desulfurization of the organic compounds and thus reduces or avoids the formation of tar-like material.

In some embodiments, the halogen-containing organic compounds in the waste material begin to lose attached halogen atoms in the dehalogenation reaction as shown in scheme 1 as the temperature in the CRV3 increases. Similarly, the organic compounds in the organic matter also lose sulfur atoms in the desulfurization reaction.

In some embodiments, the CRV3 is operated continuously so that a steady stream of organic material is converted to methane gas without interrupting the process.

In some embodiments of the plant 64 implemented as CRV3, the organic matter comprises inorganic waste matter that does not vaporize. The inorganic solid waste material may be removed from the container 30 using, for example, a helical scraper 32. The scraper 32 can lift the solids from the vessel 30 and transport them to the cyclone chamber 33 of the separating device 65. Inorganic solid waste material may be discharged from the cyclone chamber 33 substrate through valve 34 which may include a steam purge stream 37. The steam wash 37 may provide initial cooling of the inorganic solid waste matter to the high temperature from the hood 31. The inorganic solid waste material falls into a process solids hopper 35 where it can be further cooled by a water spray 36. The inorganic material is then discharged from hopper 35 by conveyor 10, such as a screw conveyor. In some embodiments, the water spray 36 and steam purge stream 37 on the hot inorganic substances create a positive pressure within the system, thus helping to maintain a substantially oxygen-free environment.

In some embodiments of the apparatus 64 implemented as CRV3, the recycled hydrogen stream 12 is introduced into the apparatus 64 and a positive raffinate stream is provided through the rotary vessel 30. Stream 12 may assist in transporting vaporized organic waste material through vessel 30 and out of apparatus 64 through swirl outlet 40 into mixer 44, such as a static mixer.

In some embodiments of apparatus 64 implemented as CRV3, vessel 30 may be designed for a high temperature reducing environment. The container 30 may be exposed to harsh chemicals such as halogenated compounds, sulfur, phosphorus and heavy metals, and hydrogen gas at elevated temperaturesStream 12 in a reducing environment. Thus, in some embodiments of the present disclosure, materials used to construct rotating vessel 30 include high temperature and corrosion resistant chromium nickel superalloys such asOr

In some embodiments, the methods of the present disclosure are carried out in the presence of a catalyst. In yet another embodiment, the catalyst is a metal catalyst, wherein the metal is selected from one or more of nickel, copper, iron, nickel alloys, tin, powdered tin, chromium, noble metals. In another embodiment, the noble metal is selected from one or more of platinum, silver, palladium, gold, ruthenium, rhodium, osmium, and iridium. In one embodiment, the mechanical components of the process, such as the rotating vessel 30, are comprised of a metal that catalyzes the process of the present disclosure.

In another embodiment of the invention, the CRV3 is replaced with an autoclave-type vessel for batch-based processing of organic material. In one embodiment, one or more continuous batch vaporizers (SBVs) are charged with organic material and then the vessel is sealed and filled with air containing an inert gas such as nitrogen, argon, or carbon dioxide. In one embodiment, the vessel is heated and the vaporized organic material is conveyed by the sweep gas to a mixer 44, such as a static mixer.

In another embodiment of the present disclosure, when the organic material is in liquid form, such as a waste organic solvent or pesticide, the organic material is simply boiled to form vaporized organic material. In one embodiment, the operation is carried out in a specially designed Liquid Waste Vaporizer (LWV), which is similar in design to an SBV and smaller. The spray nozzles spray the organic material onto a hot plate of an autoclave type vessel. Some of the liquid droplets vaporize directly or flash upon impact with the hot plate. The LWV is periodically closed in order to clean the hot plate, as inorganic matter will collect thereon. In another embodiment of the present disclosure, one or more of any combination of CRV, SBV or LWV are used, for example as shown in fig. 10.

Once the organic material has been vaporized in the CRV3, the vaporized organic material is further mixed with a hydrogen stream 41 and a superheated steam stream 42, as shown in fig. 4. In one embodiment, the mixed gas stream 43 then enters a mixer 44, such as a static mixer, which contains insulated tubing to maintain the temperature of the mixed gas stream 43 and a static mixer element 45. In yet another embodiment, mixer 44 thoroughly mixes mixed gas stream 43 to produce a mixed gas for reaction in process reactor 5. The mixer 44 is commercially available and its operation is well known to those skilled in the art.

In embodiments of the present disclosure, once the organic matter is heated to the temperature in the CRV3, the organic matter continues to be dehalogenated and desulfurized as it proceeds along the CRV3, through the swirl chamber 33 and into the mixer 44. Thus, in embodiments of the present disclosure, greater than about 50%, optionally greater than about 70%, suitably about 80%, more suitably about 90% and most suitably about 95% of the organic compounds in the organic material are dehalogenated and desulfurized prior to entering process reactor 5.

In yet another embodiment of the present disclosure, the mixed gas stream 43 is well mixed in view of the reaction in the process reactor 5. In another embodiment, the mixed gas stream 43 exits the mixer 44 and is conveyed to the inlet 50 of the process reactor 5. In another embodiment, the temperature of the mixed gas stream 43 at the inlet 50 is maintained by controlling the temperature of the hydrogen stream 41 and the superheated steam stream 42. Maintaining the temperature of mixed gas stream 43 and ensuring that said stream 43 is thoroughly mixed in mixer 44 increases the efficiency of the subsequent reactions and reduces the formation of unwanted by-products, such as tarry substances (condensed polycyclic aromatic hydrocarbons), which reduce the working efficiency of the overall process.

Figure 5 illustrates an enclosed chamber or process reactor 5 in one embodiment of the present disclosure. In one embodiment, the mixed gas stream 43 enters the inlet 50 of the process reactor 5. In one embodiment, the process reactor 5 is designed such that the gas flow is turbulent and may also be designed to function as a plug flow process reactor. Those skilled in the art will appreciate that turbulent flow is characterized by exhibiting eddies and vortices throughout the flow region. Plug flow process reactors means that the flow is well mixed at any given cross section and not mixed in the axial direction. In one embodiment, the turbulent gas flow helps to thoroughly mix the organic compounds in the organic matter with the excess hydrogen. As mentioned, thorough mixing of the organic compound with excess hydrogen reduces the formation of tarry substances.

In the embodiments of the present disclosure, the dehalogenation reaction is mainly performed in the CRV3, the swirl chamber 33 and the mixer 44, while the reduction reaction of the organic compounds is mainly performed in the process reactor 5. In another embodiment, the dehalogenation and desulfurization reactions and the reduction reaction are carried out in the same process reactor. In this embodiment, after completion of the dehalogenation reaction, the reduction reaction is carried out with increasing temperature.

In an embodiment of the present disclosure, the process reactor 5 includes a heating zone 51 and a residence time zone 52. Heating zone 51 is defined as the volume required to heat mixed gas stream 43 to a temperature effective to cause dehalogenation and reduction reactions at 90% efficiency, optionally 95% efficiency, optionally 99% efficiency, optionally 99.9% efficiency, and suitably 99.9999% efficiency. The efficiency of the reaction is the percentage of any particular organic compound that is destroyed or chemically converted by the reduction process. Mathematically, the Destruction Efficiency (DE) is defined as:

DE＝(W_in-W_out)x100

wherein W_inMass entry rate of the target compound; and is

W_outMass discharge rate of target compound

In one embodiment, the temperature at which this efficient dehalogenation and desulfurization reaction is achieved is from about 450 ℃ to about 650 ℃, suitably from about 475 ℃ to about 600 ℃. In another embodiment, the temperature at which the efficient reduction reaction is achieved is from about 600 ℃ to about 900 ℃, suitably from about 700 ℃ to about 900 ℃, suitably from about 800 ℃ to about 875 ℃. Those skilled in the art will recognize that the exact temperature will depend on the organic material being processed by the process.

In another embodiment of the present disclosure, the residence time zone 52 is defined as the volume in which the temperature of the gas has reached a temperature at which the organic compounds in the vaporized organic substance (first mixture) are reduced. In one embodiment, the residence time in residence time zone 53 is from about 1 to about 10 seconds, optionally from about 1 to about 5 seconds, suitably from about 2 to about 4 seconds. In another embodiment of the present disclosure, the gas mixture produced from the reduction reaction travels up the central tube 53 of the process reactor 5.

In another embodiment, the process reactor 5 is heated using one or more radiant tube type heaters 55 located in the annular heating zone 51 of the process reactor. In one embodiment, the radiant tube heater is a gas furnace or electronic. In another embodiment, one or more radiant heaters 55 are coupled to process reactor 5 in the region of the top end 58 of process reactor 5 that is filled with an inert gas, such as nitrogen, argon, or carbon dioxide. This design ensures that outside air cannot penetrate into the process reactor 5 if the radiant tubes 55 leak.

In another embodiment of the present disclosure, the process reactor 5 comprises an insulated vessel consisting of an outer shell 57 made of, for example, carbon steel with a floating liner 56 made of, for example, a nickel alloy. Floating liner 56 allows for movement during thermal expansion due to the high temperatures in process reactor 5. In yet another embodiment, the process reactor 5 also has an insulating material, such as ceramic fibers, to help maintain the high temperature in the process reactor 5. In another embodiment, the floating liner 56 and one or more radiant tube heaters 55 are fabricated from materials that can withstand the high temperature reducing environment in the process reactor in addition to chemicals such as halogenated compounds, sulfur, phosphorus, and heavy metals. In one embodiment, floating liner 56 and oneThe one or more radiant tube heaters 55 are made of a high temperature and corrosion resistant chromium-nickel alloy, such as KanthalOrAnd (4) manufacturing. In another embodiment, the process reactor 5 includes a removable bottom plug 59 to enable access to the process reactor vessel during shutdowns for inspection, repair and cleaning.

In another embodiment of the present disclosure, the process reactor 5 comprises a tubular process reactor design comprising several tubes arranged in parallel and heated from the outside, rather than a large vessel with internal heating elements.

In one embodiment, as shown in fig. 6, a secondary reaction chamber 61 is used to ensure complete destruction of double bonds and aromatics that may remain in the gas mixture. In this embodiment, the gas mixture 60 enters a secondary reaction chamber 61 where it is exposed to ultraviolet light generated by one or more ultraviolet lamps 62 in the presence of excess hydrogen. The gas mixture then exits the secondary reaction chamber 61 as an ultraviolet treated gas mixture 70. In another embodiment, the secondary reaction chamber 61 comprises a carbon steel shell with a floating liner 63 made of, for example, a nickel alloy. In another embodiment, the secondary reaction chamber 61 is insulated using, for example, ceramic fibers.

In yet another embodiment and as illustrated in fig. 7, the optionally uv treated gas mixture 70 enters the cooler 71 from the secondary reaction chamber 61. In one embodiment, the cooler 71 includes a water spray 72 that rapidly cools the gas mixture to a temperature of about 100 ℃ to about 300 ℃. In yet another embodiment, the cooled gas mixture passes through a pipe 75 to a scrubber 77. In the embodiment of the present disclosure, scrubber 77 is a venturi scrubber having a narrow section 76, with water added to narrow section 76. The narrow portion forces the gas flow to accelerate as the conduit narrows and then expands. The water is atomized into small droplets by the turbulent flow within the narrow section, which greatly improves the contact between the gas mixture and the water. The cooler 71 and the scrubber 77 remove heat, water, particularly substances and acid gas generated as byproducts from dehalogenation and reduction reactions of halogenated compounds (particularly chlorine compounds, fluorine compounds, or bromine compounds).

In embodiments of the present disclosure, the acid gas in the gas mixture is neutralized and removed by adding a base, such as sodium hydroxide. The addition of base results in the production of water and salt.

In another embodiment, water added in the narrow portion 76 of the scrubber 77 collects at the bottom of the scrubber and is discharged as a water stream 79. In yet another embodiment, water from cooler 71 is added to water stream 79. In yet another embodiment, the water stream 79 comprising scrubber effluent enters a water treatment system for filtration and testing prior to discharge. In another embodiment, the scrubber treated gas stream 80 exits the scrubber vessel 77 and is conveyed to the secondary scrubber 81 by a pipe.

In another embodiment of the present disclosure, the cooler and venturi scrubber are replaced with a dry lime type scrubber. When the organic material being treated is highly halogenated, for example hexachlorobenzene, a dry lime scrubber is used. The dry lime scrubber for this type of organic matter greatly reduces the water effluent from the process.

In another embodiment of the present disclosure, as shown in fig. 8, the scrubber treated gas stream 80 enters a secondary scrubber 81, where the treated gas 80 is scrubbed again to further reduce the temperature of the treated gas 80 and remove as much water from the treated gas 80 as possible. In another embodiment, the treated gas 80 is cooled by a cold water spray 82 to a temperature of about 5 ℃ to about 35 ℃. In another embodiment, the secondary scrubber 81 includes a demister member 83, which eliminates the possibility of entrained water droplets in the secondary scrubber treated gas stream 90. In yet another embodiment, the secondary scrubber treated gas stream 90 is vented through a pipe near the top of the secondary scrubber 81. In this embodiment, the water 85 collected in the secondary scrubber 81 passes as a water stream 89 through a pipe bank located at the bottom of the secondary scrubber 81, and the water stream 89 comprising the scrubber effluent enters the water treatment system for filtration and testing prior to discharge.

In another embodiment of the present disclosure, the secondary scrubber 81 is also used to remove unwanted compounds, for example, phosphorus-containing compounds, such as phosphine gas. In this embodiment, the phosphine gas is removed in the secondary scrubber 81 using a permanganate solution.

In another embodiment of the present disclosure, as illustrated in fig. 9, the secondary scrubber treated gas stream 90 enters a separator 9, such as a hydrogen separation system. In another embodiment, stream 90 enters a compressor 91, such as a screw compressor, where the gas is compressed to a pressure greater than about 100psig (about 690kPa), which is the pressure required for the hydrogen separation membrane to separate hydrogen from methane gas. In one embodiment, compressed treated gas is delivered from compressor 91 to hydrogen separator assembly 93 via process conduit 92. In one embodiment, several hydrogen separation modules 93 are used in parallel. In yet another embodiment, each hydrogen separation assembly comprises a membrane member 94 that filters hydrogen gas. In an embodiment of the present disclosure, the membrane section 94 is provided by, for example, Air ProductsA membrane system. Membrane systems for hydrogen separation are known to those skilled in the art and are commercially available. In one embodiment, stream 90 enters a hydrogen separation assembly 93 comprising a tube comprising a cylindrical membrane component 94. In this embodiment, hydrogen under pressure passes through the membrane at about 85% recovery, while the membrane rejects methane at about 90% efficiency (rejection of carbon monoxide is about 85%). In one embodiment, the hydrogen-rich permeate exits the hydrogen separation assembly as stream 12 and is recycled in the process as described above (calculations show, by using this techniqueThe hydrogen is recycled, the total hydrogen demand in the gas phase reduction process is reduced by 67%), and the methane-rich and reduced hydrogen amount of the non-passed gas exits the hydrogen separation assembly as stream 11. In yet another embodiment, the methane-rich gas 11 enters the gas storage area for testing before it can be used as a fully combusted fuel or for other uses. In one embodiment, the methane comprises from about 10% to about 20% hydrogen by volume.

In another embodiment of the present disclosure, the methane-rich gas undergoes a further methanation reaction to convert the available carbon monoxide and hydrogen in the gas to methane and water. This does not increase the total fuel heating value of the gas, but higher methane to hydrogen and carbon monoxide ratios are desirable for certain applications, such as automotive use.

In another embodiment of the invention, carbon dioxide is removed and separated from the methane-rich stream 11. This increases the heating value of the produced gas and minimizes the release of greenhouse gases from the process.

In embodiments of the present disclosure, the gas produced in the process is used as a fuel for complete combustion. For example, the methane-rich fuel gas may be used as a fuel source for any known energy generation system, such as, but not limited to, gas turbines, steam turbines, and other engines. The operation and construction of such energy generating systems is well known in the art. Methane can also be converted to hydrogen using known carbon dioxide reforming and water gas shift processes, and the hydrogen is subsequently used as a fuel for known hydrogen power generation systems, such as fuel cells. The operation and construction of hydrogen Fuel cells is well known in the art and includes Fuel cells for automobiles or larger power generation systems, such as those developed by Fuel Cell Energy of Danbury connectivity. Either methane and/or hydrogen is collected and transported to an energy generation system or can be delivered directly into such a system, which in one embodiment of the disclosure is in close proximity to the process plant or integrated.

Three embodiments of the present disclosure are described below to provide for the conversion of a rich from three specific organic speciesExamples of methane fuel gas. This information is generated using a computer model that takes the chemical composition of the organic matter as input and calculates the composition of the fuel gas using standard engineering principles known to those skilled in the art. Calculations assume that methane is added as a reactant to produce hydrogen by steam methane reforming and water gas shift reactions. The efficiency of the hydrogen separation and recovery system assuming the following was calculated: 85% hydrogen recovery, 92% methane rejection, 100% CO rejection, 50% CO₂Repulsion, and 100% water repellency.

In one embodiment, digested sewage sludge is converted. Sewage sludge has the following dry basis chemical composition (mol%): 4.7% nitrogen, 34% carbon, 20% oxygen, 4.9% hydrogen, 1.3% sulfur, 0.1% chlorine, and 35% ash. The process was run such that the excess hydrogen remaining after completion of the reduction reaction was 40 mol%. The fuel gas produced contained the following chemical composition (mol%): 19% hydrogen, 40% methane, 29% CO and 12% CO₂.1 tonne of sewage sludge converted to produce a methane-rich complete combustion fuel gas having a higher heating value of 18,500 MJ.

In one embodiment, municipal solid waste is converted. The municipal solid waste has the following chemical composition on a dry basis (mol%): 3.5% nitrogen, 39% carbon, 26% oxygen, 6.4% hydrogen, 0.3% sulfur, 1.2% chlorine, 0.2% phosphorus, and 23.4% ash. The process was run such that the excess hydrogen remaining after completion of the reduction reaction was 35 mol%. The fuel gas produced contained the following chemical composition (mol%): 16% hydrogen, 40% methane, 31% CO and 13% CO₂. The 1 tonne dry municipal solid waste conversion produces a methane-rich complete combustion fuel gas having a higher heating value of 19,400 MJ.

In one embodiment, the brown coal is converted. The brown coal had the following dry basis chemical composition (mol%): 2.0% nitrogen, 77% carbon, 10.6% oxygen, 5.5% hydrogen, 4.5% sulfur, 0.1% chlorine, and 0.3% ash. The process was run such that the excess hydrogen remaining after completion of the reduction reaction was 30 mol%. The fuel gas produced contained the following chemical composition (mol%): 12% hydrogen, 42% methane, 32% CO and 14% CO₂. The 1 dry metric ton brown coal conversion produced a methane-rich completely combusted fuel gas having a higher heating value of 39,600 MJ.

Claims (65)

1. A process for converting organic matter to methane-rich gas comprising:

a) vaporizing the organic material in a substantially oxygen-free closed chamber and mixing the vaporized organic material with excess hydrogen gas and optionally superheated steam at a temperature of about 450 ℃ to about 650 ℃ to form a first mixture;

b) heating the first mixture in the presence of excess hydrogen and superheated steam to a temperature of about 600 ℃ to about 900 ℃ to form a gas mixture comprising methane, hydrogen, and acid; and

c) the gas mixture is neutralized with a base.

2. The method of claim 1, wherein the first mixture is mixed sufficiently to reduce the formation of tarry material.

3. The process according to claim 1 or 2, wherein the vaporized organic material is mixed with excess hydrogen and superheated steam at a temperature of about 475 ℃ to about 600 ℃.

4. A process according to any one of claims 1 to 3, wherein the first mixture is heated in b) to a temperature of from about 700 ℃ to about 900 ℃.

5. The method of claim 4, wherein the first mixture is heated in b) to a temperature of about 800 ℃ to about 875 ℃.

6. A process according to any one of claims 1 to 5 wherein the process is carried out in the presence of a catalyst.

7. The process according to claim 6, wherein the catalyst is a metal catalyst, wherein the metal is selected from one or more of nickel, copper, iron, nickel alloys, tin, powdered tin, chromium and noble metals.

8. The method according to claim 7, wherein the noble metal is selected from one or more of the group consisting of platinum, silver, palladium, gold, ruthenium, rhodium, osmium, and iridium.

9. The process according to any one of claims 1 to 8, wherein the gas mixture is neutralized in c) at a temperature of about 70 ℃ to about 100 ℃.

10. The method according to claim 9, wherein the gas mixture is neutralized in c) at a temperature of about 85 ℃.

11. A process according to any one of claims 1 to 10 wherein the base comprises an alkali metal hydroxide or an alkali metal carbonate.

12. The process according to claim 11, wherein the alkali metal hydroxide is sodium hydroxide.

13. The process according to claim 11, wherein the alkali metal carbonate is calcium carbonate.

14. The process according to any one of claims 1 to 13, further comprising exposing the gas mixture from b) to ultraviolet light in the presence of an excess of hydrogen gas under conditions effective to reduce residual organic compounds in the gas mixture.

15. The method of claim 14, wherein the conditions effective to reduce residual organic compounds in the gas mixture comprise heating to a temperature of about 600 ℃ to about 800 ℃.

16. The method of claim 15 wherein the conditions effective to reduce residual organic compounds in the gaseous mixture comprise heating to a temperature of from about 650 ℃ to about 750 ℃.

17. The method according to any one of claims 14 to 16, wherein the conditions effective to reduce residual organic compounds in the gas mixture comprise ultraviolet light at a wavelength of about 200nm to about 300 nm.

18. The method of claim 17, wherein the conditions effective to reduce residual organic compounds in the gas mixture comprise ultraviolet light having a wavelength of about 220nm to about 254 nm.

19. A process according to any one of claims 1 to 18, wherein the heating of the first mixture in b) is carried out in a second closed chamber substantially free of oxygen.

20. The method according to any one of claims 1 to 19, further comprising cooling the neutralized gas mixture in c).

21. The method of claim 20, wherein the gas mixture is cooled to a temperature of about 5 ℃ to about 35 ℃.

22. The method of claim 20 or 21, further comprising exposing the neutralized and cooled gaseous mixture to conditions effective to reduce residual organic compounds in the presence of excess hydrogen.

23. The method of claim 22, wherein the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture comprise ultraviolet light at a wavelength of about 200nm to about 300 nm.

24. The method of claim 23, wherein the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture comprise ultraviolet light having a wavelength of about 220nm to about 254 nm.

25. The method according to any one of claims 22 to 24, wherein the conditions for reducing residual organic compounds in the neutralized and cooled gas mixture further comprise heating to a temperature of about 300 ℃ to about 500 ℃.

26. The method according to any one of claims 1-25, carried out at a pressure greater than 0 atmosphere and less than 2 atmospheres.

27. The process according to any one of claims 1 to 26, further comprising separating hydrogen and methane after neutralizing the gas mixture in c).

28. The process according to claim 27, wherein hydrogen gas is recycled for use in a) and/or b).

29. The method of claim 27, wherein the methane comprises from about 10% to about 20% hydrogen by volume.

30. The method according to claim 29, further comprising transferring methane to an energy production system.

31. The method according to claim 30, wherein the energy producing system is a gas turbine or an engine.

32. The method according to claim 30, wherein the energy producing system is a fuel cell.

33. The method according to any one of claims 1 to 32, wherein the organic material further comprises an inorganic material that cannot be vaporized and removed from the closed chamber.

34. The method of any one of claims 1 to 33, wherein the organic matter comprises chlorinated or organophosphorus chemical warfare agents, biological warfare agents, sewage, municipal or industrial solid waste or refuse, agricultural waste, organic solvents, halogenated organic compounds, organophosphorus compounds, explosives, rocket fuels, hydrazines, tires, plastics, coal, oil, peat, biomass, refinery or chemical manufacturing/processing waste such as bottom of a boiler residue, or oil and/or bitumen processing waste.

35. The method according to claim 34, wherein the chlorinated or organophosphate chemical warfare agent comprises mustard gas or VX nerve agent.

36. The method of claim 34, wherein the biological warfare agent comprises anthrax.

37. A method according to claim 34, wherein the agricultural waste material comprises poultry, cattle, swine or other livestock waste material such as manure and processing waste.

38. The method of claim 34, wherein the halogenated organic compound is a polychlorinated biphenyl, a hexachlorobenzene, a chlorinated pesticide, a brominated flame retardant, a fluorinated propellant, or a fluorinated refrigerant.

39. The method of claim 34 wherein the organophosphorus compound is a pesticide.

40. The method of claim 34, wherein the oil and/or bitumen processing waste is oil and/or bitumen processing waste from tar sands.

41. The method of claim 34, wherein the organic material is a fossil fuel.

42. The method of claim 41, wherein the fossil fuel is coal, oil, or peat.

43. The method of claim 34, wherein the biomass is wood waste, pulp waste, or wood chips.

44. A reaction, mixing or milling apparatus comprising:

a) a container rotatable about an axis, the container comprising a first end having a coaxial inlet or outlet for respectively introducing or discharging material into or from the container, the first end comprising a flange section having a first face extending generally radially;

b) a closure member disposed proximate the first end, the closure member including a second generally radially extending face generally opposite the first face; and

c) an inner sealing element and an outer sealing element disposed between the first face and the second face, the inner sealing element and the outer sealing element defining a generally annular space, the annular space containing a sealing liquid forming a seal between the container and the closure.

45. The device of claim 44, wherein the sealing member is generally annular and coaxially disposed.

46. An apparatus according to claim 44 or 45, wherein the sealing element is fixed to one of the first and second faces and slides relative to the other of the first and second faces.

47. Apparatus according to any one of claims 44 to 46, wherein the closure member comprises an inlet member and an outlet member in fluid communication with the annular space for circulation of the confining liquid in the annular space.

48. The apparatus according to claim 47 wherein the outfeed member is positioned above the infeed member.

49. Apparatus according to any one of claims 44 to 48, wherein the flange section comprises coaxial, substantially cylindrical inner and outer flange walls, and a radial web wall connecting the inner and outer flange walls, the web wall comprising the first face.

50. The apparatus of claim 49, further comprising a support bearing for rotatably supporting the outer flange wall of the vessel flange section.

51. The device according to any one of claims 44 to 51, wherein the closure member comprises first and second wall portions separated by an expansion section, the expansion section allowing axial displacement of the first wall portion relative to the second wall portion, and the first wall portion comprising the second face.

52. The device of claim 51, wherein the expansion section biases the second face against the first face.

53. Apparatus according to any of claims 44 to 52, further comprising a shield substantially surrounding at least a portion of the vessel.

54. An apparatus as defined in claim 53, wherein the container includes a main barrel portion and a tapered portion between the barrel and the flange section, and the shroud substantially surrounds the barrel portion and terminates at the tapered portion.

55. Apparatus according to claim 53 or claim 54, wherein the enclosure comprises a heat source.

56. Apparatus according to any of claims 44 to 55, wherein the first end has a coaxial inlet for introducing the substance into the container and the closure member comprises at least one inlet conduit for introducing the substance into the container through the first end.

57. The apparatus of claim 56, wherein the at least one inlet conduit comprises a screw conveyor feed and a gas feed for delivering the substance to the vessel.

58. Apparatus according to any one of claims 44 to 55, wherein the first end has a coaxial outlet for discharging material from the vessel, and further comprising a helical flight within the vessel adjacent the first end for discharging solid material.

59. Apparatus according to any one of claims 44 to 58, wherein the axis is substantially horizontal.

60. A device according to any one of claims 44 to 59, wherein the inner and outer sealing members comprise a non-stick material.

61. An apparatus according to any one of claims 44 to 60, wherein the vessel comprises an inert material.

62. An apparatus according to any one of claims 44 to 61, wherein the vessel comprises stainless steel.

63. An apparatus according to any one of claims 44 to 62, wherein the vessel comprises a superalloy.

64. A combination of the following devices:

a) apparatus according to any one of claims 44 to 63; and

b) a separation device, comprising:

i) a cyclone chamber in fluid communication with and tangentially aligned with the vessel outlet for receiving the discharged material;

ii) an outlet conduit disposed above the cyclone chamber for collecting gaseous material from the cyclone chamber; and

iii) a hopper disposed below and in fluid communication with the cyclone chamber for collecting liquid and solid matter from the cyclone chamber.

65. The combination of claim 64 wherein the separator means further comprises:

a) at least two valves separating the cyclone chamber from the hopper;

b) a steam purge stream connected between the two valves; and

c) a fluid source in the hopper for cooling the liquid and solid matter.