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WO2012174284A1 - Réacteurs contenant un métal liquide - Google Patents

Réacteurs contenant un métal liquide Download PDF

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Publication number
WO2012174284A1
WO2012174284A1 PCT/US2012/042521 US2012042521W WO2012174284A1 WO 2012174284 A1 WO2012174284 A1 WO 2012174284A1 US 2012042521 W US2012042521 W US 2012042521W WO 2012174284 A1 WO2012174284 A1 WO 2012174284A1
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WO
WIPO (PCT)
Prior art keywords
reactor
metal
materials
oxygen
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2012/042521
Other languages
English (en)
Inventor
Irving B. Morrow, Jr.
Mark Wilkinson
David STECKLER
Shawn ROY
William H. Davis
Roderick SIDWELL
Frank MEDROS
Terumi OKANO
Jonathan LEBEAUX
Alejandro RIVERA
Shawn CAHILL
David Robertson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZE-GEN Inc
Ze Gen Inc
Original Assignee
ZE-GEN Inc
Ze Gen Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZE-GEN Inc, Ze Gen Inc filed Critical ZE-GEN Inc
Publication of WO2012174284A1 publication Critical patent/WO2012174284A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/57—Gasification using molten salts or metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C10J2300/0923—Sludge, e.g. from water treatment plant
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air

Definitions

  • the present invention generally relates to reactors containing one or more metals in a liquid state for at least partially oxidizing feed materials, e.g., to produce syngas or other products, for example, gases such as fuel gases.
  • Feed materials such as organic materials can be reacted to produce synthesis gas (typically a mixture of CO and H 2 , sometimes referred to as syngas) by various techniques.
  • the feed materials desired to be converted into syngas may include bulk feed materials such as municipal solid waste, construction and demolition waste, wastewater sludge, or the like.
  • suitable known production techniques include plasma technologies, reactions involving steam, or reactors containing liquid iron.
  • reactors containing liquid iron many challenges remain before such reactors can be reliably used commercially, especially with bulk feed materials.
  • reactors may produce relatively large amounts of carbon dioxide (which often cannot be further processed into useful products and/or energy), irreversibly create iron oxides (with a reduction in the amount of liquid iron available for continued reaction), and/or heterogeneously or non-uniformly react with the feed materials (e.g., due to poor mixing and/or reaction within the liquid iron), resulting in the formation of carbon boils (a sudden, violent production of carbon monoxide and/or carbon dioxide from within the liquid iron). Accordingly, improvements in systems and methods for reacting feed materials to produce syngas or other gases are needed.
  • the present invention generally relates to reactors containing one or more metals in a liquid state for at least partially oxidizing feed materials, e.g., to produce syngas or other products, for example, gases such as fuel gases.
  • feed materials e.g., to produce syngas or other products, for example, gases such as fuel gases.
  • gases such as fuel gases.
  • the subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
  • the present invention is generally directed to a method of producing a synthesis gas from a carbonaceous material in a liquid metal gasifier reactor.
  • the method includes acts of providing a reactor containing a liquid metal comprising copper, feeding one or more materials to the reactor such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1, and reacting the one or more materials within the reactor to produce synthesis gas comprising carbon monoxide.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen.
  • reaction occurs within the reactor such that substantially no copper oxide accumulates within the reactor over a period of at least one day.
  • the method includes acts of providing a reactor containing a liquid metal comprising copper, feeding one or more materials to the reactor such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1, and reacting the one or more materials within the reactor to produce synthesis gas.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen.
  • at least about 80% of the oxygen in the one or more materials fed to the reactor is reacted within the reactor.
  • the method includes acts of providing a reactor containing a metal in a liquid state, feeding one or more materials to the reactor, and reacting the one or more materials within the reactor to produce carbon monoxide under conditions selected such that substantially no oxide of the metal accumulates within the reactor.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen, such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1.
  • the method comprises acts of providing a reactor containing a metal in a liquid state, feeding one or more materials to the reactor, and reacting the one or more materials within the reactor such that at least about 80% of the oxygen in the one or more materials is reacted within the reactor.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen, such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1.
  • the method includes acts of providing a reactor containing at least 10 tons of metal in a liquid state, feeding one or more materials containing carbon and oxygen to the reactor, and reacting the one or more materials within the reactor to produce a synthesis gas comprising carbon monoxide under conditions without active stirring of the metal in the liquid state in the reactor. In certain instances, essentially all stirring of the metal in the liquid state within the reactor is driven by heat convection.
  • the method includes acts of providing a reactor containing one or more liquid metals having an overall standard oxidation potential of at least 0 V, feeding one or more materials to the reactor such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1, and reacting the one or more materials within the reactor to produce synthesis gas comprising carbon monoxide.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen.
  • reaction occurs within the reactor such that substantially no metal oxide accumulates within the reactor over a period of at least one day.
  • the method includes acts of providing a reactor containing one or more liquid metals having an overall standard oxidation potential of at least 0 V, feeding one or more materials to the reactor such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1, and reacting the one or more materials within the reactor to produce synthesis gas.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen.
  • at least about 80% of the oxygen in the one or more materials fed to the reactor is reacted within the reactor.
  • the method includes acts of providing a reactor containing one or more liquid metals having an overall standard oxidation potential of at least 0 V, feeding one or more materials to the reactor, and reacting the one or more materials within the reactor to produce carbon monoxide under conditions selected such that substantially no oxide of the metal accumulates within the reactor.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen, such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1.
  • the method comprises acts of providing a reactor containing one or more liquid metals having an overall standard oxidation potential of at least 0 V, feeding one or more materials to the reactor, and reacting the one or more materials within the reactor such that at least about 80% of the oxygen in the one or more materials is reacted within the reactor.
  • at least one of the materials fed to the reactor is a carbonaceous material and at least one of the materials comprises oxygen, such that an overall molar ratio of carbon to oxygen in the one or more materials is between about 0.8: 1 and about 1.2: 1.
  • the method includes acts of providing a reactor containing at least 10 tons of one or more liquid metals having an overall standard oxidation potential of at least 0 V, feeding one or more materials containing carbon and oxygen to the reactor, and reacting the one or more materials within the reactor to produce a synthesis gas comprising carbon monoxide under conditions without active stirring of the metal in the liquid state in the reactor. In certain instances, essentially all stirring of the metal in the liquid state within the reactor is driven by heat convection.
  • the present invention in another aspect, is generally directed to a method of operating a liquid metal gasifier reactor.
  • the method includes acts of providing a reactor containing (a) a liquid metal comprising copper and (b) copper oxide, and feeding a carbon-containing material to the reactor under conditions selected to chemically reduce the copper oxide to form copper.
  • the method includes acts of providing a reactor containing: (a) a metal in a liquid state and (b) an oxide of the metal, and feeding a carbon-containing material to the reactor under conditions selected to chemically reduce the oxide of the metal.
  • the method includes acts of providing a reactor containing a metal in a liquid state, feeding one or more materials containing carbon and oxygen to the reactor, and reacting the one or more materials within the reactor to produce heat at least sufficient to maintain the metal in the liquid state within the reactor over a period of at least one day.
  • the method in still another set of embodiments, includes acts of providing a reactor containing a metal in a liquid state; at a first time, feeding a carbon-containing material to the reactor under conditions selected to facilitate reacting the material with oxygen or an oxygen containing material to produce carbon monoxide, where some of the metal is oxidized to produce a metal oxide; and at a second time, feeding a carbon-containing material to the reactor under conditions selected to facilitate reacting the material with the metal oxide to chemically reduce the metal oxide within the reactor to the metal.
  • the present invention encompasses methods of making one or more of the embodiments described herein, for example, a reactor containing a metal in a liquid state. In still another aspect, the present invention encompasses methods of using one or more of the embodiments described herein, for example, a reactor containing a metal in a liquid state.
  • Fig. 1 is a process flow diagram illustrating a reactor containing a liquid metal, according to certain embodiments of the invention
  • Fig. 2 is a schematic cross-sectional diagram that illustrates a reactor in accordance with one embodiment of the invention
  • Figs. 3A-3C illustrate additional views of the reactor shown in Fig. 2;
  • Figs. 4A-4B are graphs that show data illustrating the production of syngas from a reactor as is shown in Fig. 2;
  • Fig. 5 shows experiments using various C:0 ratios in a reactor in certain embodiments of the invention.
  • Figs. 6A-6B show various experiments illustrating autothermal operation of a reactor, in accordance with certain embodiments of the invention.
  • the present invention generally relates to reactors containing one or more metals in a liquid state for at least partially oxidizing feed materials, e.g., to produce syngas or other products, for example, gases such as fuel gases.
  • the metals within the reactor may include, for example, one or more of copper, iron, tin, zinc, silver, palladium, gold, and/or other metals and alloys thereof.
  • the reactor may be operated such that substantially no oxide of the metals accumulate within the reactor, and/or such that substantially all of the oxygen entering the reactor is utilized by the feed material or char within the reactor.
  • a carbon-containing material may be fed to the reactor to chemically reduce any metal oxides that are present.
  • the reactor may also be operated such that substantially no carbon boils occur within the reactor.
  • the reactor can be operated autothermally in some cases, i.e., essentially all of the heat necessary to keep the metal within the reactor in a liquid state comes exclusively from exothermic partial oxidation of one or more feed materials supplied to the reactor.
  • the present invention is generally directed to reactors containing at least one metal in a liquid or molten state.
  • reactor 10 contains at least one metal 15 in a liquid state.
  • the liquid metal may include, for example, copper or iron, or other metals as discussed below.
  • Feed materials are fed into the reactor, e.g., into the liquid metal and/or into the "headspace" or gas space above the liquid metal.
  • feed materials are illustrated as entering headspace 18 above liquid metal 15 through inlet 20 from conduit 22.
  • the feed materials are oxidized (or pyrolyzed), e.g., reacted with oxygen to produce products such as syngas.
  • a carbon-containing material may be oxidized to produce carbon oxides, typically carbon monoxide (CO) and/or carbon dioxide (C0 2 ).
  • the amount of carbon monoxide and/or carbon dioxide produced is a function of various factors, including the amount of oxygen (0 2 ) present within the reactor, which may be supplied to the reactor as, e.g., air, enriched air (i.e., enriched in oxygen over atmospheric levels), a purified oxygen stream, or as another oxygen-containing material.
  • Other materials present within one or more of the feed materials may be oxidized as well.
  • a feed material also contains hydrogen (as would be the case, for instance, with organic or hydrocarbon feed materials)
  • such materials may be oxidized or pyrolyzed to produce hydrogen gas (H 2 ) and/or water (H 2 0).
  • the amount of hydrogen gas and/or water that is produced may be a function of various factors, including the amount of oxygen present within the reactor.
  • feed materials may also be at least partially oxidized, depending on the partial pressure of oxygen within the reactor; for example, sulfur may be partially or fully oxidized or otherwise reacted to produce sulfur oxides (SO x ) or H 2 S, nitrogen may be partially or fully oxidized to produce nitrogen oxides (NO x ), calcium may be partially or fully oxidized to produce calcium oxide (CaO), silicon may be partially or fully oxidized to produce silicon dioxide (Si0 2 ), etc.
  • SO x sulfur oxides
  • H 2 S nitrogen may be partially or fully oxidized to produce nitrogen oxides (NO x )
  • calcium may be partially or fully oxidized to produce calcium oxide (CaO)
  • silicon may be partially or fully oxidized to produce silicon dioxide (Si0 2 ), etc.
  • it may be possible to produce oxides within a reducing atmosphere e.g., within an atmosphere having a relatively low oxygen partial pressure
  • syngas produced within the reactor may then be captured from the reactor, and subsequently used as a fuel and/or as a reactant for further chemical reactions.
  • some of the gas within headspace 18, e.g., syngas may exit reactor 10 through outlet 30 into conduit 33, e.g., for purification, separation, collection, further reaction, etc.
  • Metal 15 within reactor 10 may be heated to cause the metal to melt or liquefy using one or more sources of heat; for example, electrical or resistive heating may be used, or other sources of heat as discussed below.
  • the metal may be heated within the reactor and/or prior to entering the reactor.
  • the reactor may be operated, at least at certain times, under "autothermal" conditions, i.e., such that essentially all of the heat necessary to keep the metal within the reactor in a liquid state comes exclusively from the reaction of one or more feed materials supplied to the reactor.
  • the oxidation reaction to convert one or more of the feed materials to produce syngas is an exothermic reaction, i.e., some heat is produced in the process, which may be harnessed under certain conditions to control the temperature of the reactor, e.g., such that the metal within the reactor remains liquid.
  • certain aspects of the present invention are generally directed to reactors containing one or more metals in a liquid state for oxidizing feed materials, e.g., to produce syngas or other products, such as gases or liquids.
  • feed materials e.g., to produce syngas or other products, such as gases or liquids.
  • Any material fed into the reactor may be considered a "feed material," including solid materials, liquid materials, gaseous materials (e.g., gaseous hydrocarbons such as methane, air, oxygen, etc.), and the like, as well as any combinations thereof.
  • the feed materials may be added to the reactor using any suitable technique. For instance, feed materials may be actively fed into the reactor, e.g., using conveyor belts, bucket elevators, hopper tubes, pipes, tubes, lances, tuyeres, etc.
  • feed materials may be physically "pushed” or pressurized to flow into the reactor.
  • gravity or passive techniques may be used to deliver feed materials into the reactor, alone or in combination with other delivery techniques. If more than one feed material is fed to the reactor, the feed materials may enter the reactor as one stream (e.g., through a single inlet) or as multiple streams (e.g., through multiple inlets), for example, using any suitable combination of these and/or other techniques as described herein.
  • the feed material includes a carbon-containing material.
  • a carbon-containing material may be any material containing carbon, e.g., in a relatively pure or carbon-rich form (for example, coal, coke, etc.), and/or as compounds that include carbon atoms (for example, organic compounds, hydrocarbons, etc.).
  • Examples of carbon-containing materials include, but are not limited to, biomass (e.g., produced from plants such as switchgrass, corn, sugar cane, sugar beets, trees, straw, rice, cotton, etc.), wood, polymers such as rubber or plastics, hydrocarbons such as gasoline, diesel, kerosene, methane, propane, butane, petroleum oil, or the like.
  • feed materials include, but are not limited to, waste materials such as garbage, municipal solid waste (MSW), refuse derived fuels (RDF), including RDF based upon MSW, construction and demolition wastes (C&D), wastewater sludge, scrap tires, plastic wastes, medical waste, waste oils, or the like.
  • the carbon-containing materials can include solid feed materials and/or non-solid materials (e.g., semi-solid mixtures, liquid materials, gas materials, etc.).
  • the feed material may not be precisely known, and/or the feed material may be one that is compositionally heterogeneous.
  • various types of bulk feed materials may be used, such as garbage, MSW, RDF, C&D, waste oil, or the like.
  • Such materials are typically collected "in bulk” (for instance, from different sources) and may not be typically sorted to produce a homogenous feed composition, e.g., due to the mass and/or difficulty in sorting such materials. Accordingly, such materials can be fed into a reactor as an unsorted or heterogeneous bulk feed.
  • C&D waste may include wood, nails, wallboard, cardboard, carpet remnants, metal fragments, plastic fragments, pipe, dried glue, plastic, etc., and such C&D waste may not be presorted compositionally prior to being fed into a reactor.
  • waste oil from different cars, other vehicles, and/or other sources e.g., having different grades of oil, additives, contaminants, etc.
  • MSW and waste oil may be mixed together as a feed material.
  • a solid feed material may be processed (e.g., cut, chopped, shredded, etc.) to produce particles (e.g., forming "chips" or "pellets") of a certain size before being fed into the reactor. In some cases, this may be performed without any sorting of the feed material, although in other cases, some sorting of the feed material may occur.
  • a solid feed material may be processed to produce particles having a maximum size of less than about 5 inches (about 12.7 cm), less than about 4 inches (about 10.2 cm), less than about 3 inches (7.6 cm), less than about 2 inches (about 5.1 cm), less than about 1.5 inches (about 3.8 cm), or less than about 1 inch (about 2.5 cm).
  • a feed material comprising wood may be broken down or chopped into wood pellets, although there may be no attempt to separate different types of wood and/or contaminants that are present within the wood.
  • the wood may include fresh wood (e.g., from cut trees, bushes, etc.), and/or "waste wood" (e.g., railroad ties, utility poles, wooden pallets or skids, wood panels, etc. which have been previously used for other applications). Other examples may be seen, for instance, in U.S. Pat. Apl. Pub. No. 2009/0188844.
  • a feed material can include moisture (i.e., water).
  • the moisture within a feed material may be at least about 5% by weight, and in some instances, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50% by weight of moisture.
  • the liquid metal within the reactor may be chosen to be one that does not react, or does not irreversibly react, with water, e.g., to produce oxides.
  • a liquid metal including copper does not typically react irreversibly with water to produce copper oxides. Non-limiting examples of such liquid metals are discussed below.
  • the moisture may be no more than about 60%, no more than about 50%, no more than about 40%, no more than about 30%, no more than about 20%, or no more than about 10% by weight in certain embodiments.
  • a feed material is treated, physically and/or chemically, to at least partially remove water (for example, through drying) before being fed to the reactor.
  • the feed materials can be fed into a reactor containing one or more metals in a liquid state.
  • references herein to a "metal" in a reactor is for ease of convenience and presentation only, and in other embodiments of the invention, there may be more than one metal present within the reactor, e.g., in a liquid state.
  • a "metal" within a reactor as discussed herein may include a mixture or an alloy of two, three, four, or more metals.
  • the metal within the reactor may be brass (e.g., an alloy of copper or zinc), bronze (an alloy of copper and tin), or the like. In other embodiments, however, the reactor may consist essentially of a single metal that is in a liquid state.
  • a reactor as discussed herein may comprise or consist essentially of a liquid metal such as copper, iron, nickel, chromium, tin, nickel, zinc, lead, silver, palladium, and/or gold, and/or a combination of any of these and/or other metals or materials, e.g., as in a liquid metal alloy.
  • the liquid metal within a reactor may be copper, iron, or an alloy such as brass or bronze.
  • the alloy may be eutectic in some embodiments.
  • the reactor may include a noble metal in a liquid state, such as copper, silver, gold, palladium, platinum, or the like.
  • a reactor may include a liquid metal comprising or consisting essentially of copper.
  • the reactor may contain a liquid metal comprising at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% copper, with the remainder of liquid metal being other materials, e.g., other metals and/or other materials.
  • the liquid metal may include one or more gases (e.g., air, oxygen, syngas, feed gases, inert gases, etc.), carbon-containing materials, other solids, other liquids, etc.
  • gases e.g., air, oxygen, syngas, feed gases, inert gases, etc.
  • one or more fluxes may be present within the liquid metal (for example, AI 2 O 3 , lime, silica, CaO or quicklime, CaC0 3 , Ca(OH) 2 , CaS0 4 , etc.), or the liquid metal may contain slag materials (e.g., Fe 3 0 4 , Fe 2 0 3 , CaSi0 3 , A1 2 0 3 , PbO, Pb0 2 , Pb 0 4 , Pb 2 0 3 , ⁇ 2 0 5 , CuO, etc.), oxides (e.g., of one or more of the liquid metals within the reactor), or the like.
  • slag materials e.g., Fe 3 0 4 , Fe 2 0 3 , CaSi0 3 , A1 2 0 3 , PbO, Pb0 2 , Pb 0 4 , Pb 2 0 3 , ⁇ 2 0 5 , CuO, etc.
  • oxides e.g
  • any suitable method can be used to heat the metal within the reactor to a temperature greater than the melting point of the metal to melt some or all of the metal. If more than one metal is present, then the metal mixture or alloy may have a single melting point, e.g., as in a eutectic mixture, and/or the metal mixture may have two or more melting points when various components of the mixture reach their respective melting points.
  • Non-limiting examples of techniques for heating the metal include supplying heat to the reactor from an external source (e.g., to heat the reactor and/or the metal within the reactor), heating one or more materials entering the reactor, causing a chemical reaction within the reactor that produces heat, supplying electrical current to the reactor and/or to a metal within the reactor to cause resistive heating to occur, or the like. Combinations of these and/or other techniques may be used in certain cases.
  • the heat may arise from any suitable source.
  • a fuel can be oxidized or burned to produce heat energy
  • the heat may be produced using an electrical or induction heater
  • an external source of heat e.g., a municipal source or heat from another process or another factory
  • a reactant may be fed into the reactor that can be reacted (for instance, oxidized or pyrolyzed) to produce heat.
  • the reactant may also be reacted, e.g., to produce syngas and/or other products, for example, if the reactant is a feed material or contains a carbon-containing material.
  • syngas e.g.
  • the heat produced from such reactions can be used to at least partially maintain the temperature within the reactor, for instance, such that the reactor is running under autothermal conditions at least for certain periods of time, such that the heat necessary to keep the metal within the reactor in a liquid state comes essentially exclusively from one or more feed materials supplied to the reactor.
  • electric power for use in heating can be supplied in such a manner that causes electrical current to flow through the reactor and/or through the liquid metal, e.g., via one or more induction channels located at the bottom, top, and/or sides of the reactor.
  • the reactor may be electrically heated, for instance, by induction currents induced by alternating current flowing through coils or loops.
  • a high-frequency alternating current (AC) can be provided, e.g., using an electromagnet, and/or heat may be generated by magnetic hysteresis losses in materials that have significant relative permeability.
  • the frequency of AC used may depend on factors such as the reactor size, the composition of the reactor and/or materials within the reactor, coupling (e.g., between a coil and the reactor), the penetration depth, etc.
  • a standalone induction furnace can be used to heat a metal, which is then fed to the reactor.
  • Induction heaters can be readily obtained from various commercial sources, for example, from Ajax Tocco Magnetothemic, Inc., Warren, OH.
  • the metal within the reactor may be heated to a temperature at least sufficient to melt at least a portion of the metal within the reactor, i.e., to a temperature that is the same or greater than the melting point of the metal within the reactor.
  • relatively high temperatures are used within the reactor.
  • the metal within the reactor may be heated to at least the melting point of copper, the melting point of iron, the melting point of nickel, etc., or to the melting point of any other metals disclosed herein.
  • the metal within the reactor can be heated to a temperature of at least about 1000 °C, at least about 1200 °C, at least about 1500 °C, at least about 1700 °C, at least about 2000 °C, etc.
  • Metals may be added prior to operation of the reactor and/or during operation of the reactor, e.g., as a "make up" volume to replace metal that is lost during operation of the reactor.
  • the metal may be added in liquid form (e.g., heated separately prior to being added to the reactor) and/or in solid form (e.g., to be heated, at least partially, within the reactor).
  • the feed materials fed to the reactor can be reacted within the reactor to produce carbon monoxide (CO) and/or carbon dioxide (C0 2 ), and/or other products such as hydrogen (H 2 ) or water (H 2 0), in accordance with certain aspects of the invention.
  • a carbon- containing material can be at least partially oxidized upon reaction with oxygen (e.g., from air, oxygen, enriched air, etc.) to produce carbon oxides, typically carbon monoxide (CO) and/or carbon dioxide (C0 2 ).
  • oxygen e.g., from air, oxygen, enriched air, etc.
  • Many carbon-containing materials also contain hydrogen (for example, such as organic materials, biomaterials, hydrocarbons, etc.), which materials may be reacted to form hydrogen (H 2 ) or water (H 2 0).
  • the reaction is performed under partial oxidation conditions (as discussed below) to encourage the production of at least some carbon monoxide and hydrogen gas with respect to carbon dioxide and water.
  • a gas containing at least about 8% carbon monoxide and at least about 8% hydrogen gas by volume may be considered to be a syngas.
  • the syngas is mixed with other gases (e.g., nitrogen, water, carbon dioxide, etc.), although the syngas may also be purified from such gases using techniques such as those known to those of ordinary skill in the art, e.g., after exiting the reactor.
  • the feed materials may be fed to the liquid metal and/or the headspace above the liquid metal.
  • some reactions can occur within the headspace, especially when certain liquid metals such as copper or copper alloys are used within the reactor.
  • the heat generated using certain liquid metals within the reactor heats gases within the headspace above the liquid metal such that at least some of the reactions involving the feed material can occur in the headspace, e.g., due to exposure of those feed materials to relatively high temperatures and/or because there may be a large area of contact between the feed materials and reactive gases within the headspace.
  • carbon-containing materials entering the reactor may pass through the headspace (e.g., due to action of gravity), and such materials are exposed to such relatively high temperatures and/or are separated or dispersed as they pass through the headspace, thereby allowing such reactions to occur.
  • headspace e.g., due to action of gravity
  • a reactor is operated to have a suitable volume of headspace in which such reactions may at least partially occur.
  • a relatively large headspace volume may be desirable to facilitate such reactions within the reactor, although in other embodiments, the headspace volume is smaller, e.g., to encourage more reaction within the liquid metal within the reactor.
  • the volume of headspace may depend on whether feed materials (e.g., carbon-containing materials and/or oxygen-containing materials) are fed into the headspace above the liquid metal, and/or into the liquid metal itself).
  • the volume of the headspace may be at least about 10%, at least about 20%, at least about 30%, at least about 50%, at least about 75%, at least about 100%, at least about 150%, at least about 200%, at least about 300%, at least about 400%, at least about 500%, at least about 700%, or at least about 1000% of the volume of the liquid metal contained within the reactor. It should also be understood that there may be dozens or hundreds of reactions occurring within the headspace within the reactor, and in some cases, the reactions may not be completely understood.
  • Non-limiting examples of decomposition reactions that can occur within the reactor include oxidation and pyrolysis.
  • both types of reaction may be occurring simultaneously, and in certain instances, other reactions may also be occurring as well as, instead of or in addition to, oxidation and/or pyrolysis reactions.
  • the specific reactions occurring within the reactor may not be easy to determine or quantify.
  • a carbon-containing material reacts with oxygen (e.g., in air, enriched air, oxygen, etc.) to produce smaller compounds containing oxygen; if time and reaction conditions permit, the compounds can be oxidized fully to from carbon oxide products (carbon monoxide and/or carbon dioxide).
  • oxygen e.g., in air, enriched air, oxygen, etc.
  • a hydrocarbon-containing material is reacted to produce smaller or simpler compounds (e.g., H 2 ), but oxygen is not used as part of this reaction.
  • Partial oxidation and pyrolysis reactions may occur within the reactor at relatively elevated temperatures, e.g., at temperatures at least sufficient to cause at least a portion of the metal within the reactor to be in a liquid state, as previously discussed.
  • such reactions may not be particularly well- defined or well-characterized.
  • certain feed materials for example, complex or compositionally heterogeneous bulk feed materials, may be oxidized and/or pyrolyzed in a complex series of oxidation, pyrolysis, and/or other decomposition reactions to ultimately produce simpler compounds, such as lower-carbon compounds or carbon oxides, although not all of these reactions may be understood or defined within the context of the overall reaction scheme.
  • a combination of oxidation and pyrolysis occurs, for example, under partial oxidation conditions.
  • a carbon- containing material may be reacted with oxygen such that at least some carbon monoxide is produced, in addition to or instead of carbon dioxide.
  • At least about 10% by volume of the carbon oxides produced under partial oxidation conditions may be carbon monoxide, and in some cases, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% by volume may be carbon monoxide.
  • the creation of partial oxidation conditions within the reactor can be controlled, for example, by controlling the temperature of the reactor and/or by controlling one or more of the feed materials entering the reactor, for example, controlling the amount or rate at which one or more of the feed materials enters the reactor.
  • the entry of the feed materials may be controlled to control the overall molar ratio of carbon to oxygen entering the reactor, e.g., such that the reaction stoichiometry and heat generation in the reactor can be controlled.
  • a reactor can be operated under partial oxidation conditions by other methods.
  • one or more feed materials may be fed to the reactor such that an overall molar ratio of carbon to oxygen in the feed materials is between about 0.6: 1 and about 1.2: 1.
  • the overall molar ratio of carbon to oxygen in the feed materials that are fed to the reactor may be between about 0.7: 1 and about 1.2: 1, between about 0.8: 1 and about 1.2: 1, between about 0.9: 1 and about 1.1: 1, or between about 0.95: 1 and about 1.05: 1, etc.
  • the overall molar ratio of carbon to oxygen in the feed materials can be estimated, e.g., by determining or estimating the composition of the feed materials entering the reactor.
  • the overall molar ratio of a known hydrocarbon and air entering a reactor at a known flow rate may be determined using standard chemical engineering calculations and nothing more than routine skill in the art.
  • the overall molar ratio of carbon to oxygen in the feed materials is not precisely known, and/or in embodiments where compositionally heterogeneous feed materials may be used.
  • the overall molar ratio may still be estimated in certain cases with reasonable accuracy and without requiring undue experimentation by knowing the general composition of the incoming feed materials.
  • the overall molar ratio of carbon to oxygen may be controlled as discussed herein while the carbon-containing material is fed to the reactor at a high feed rate.
  • the feed material may be supplied to the reactor at a feed rate of at least about 0.001%/s, where the percentage is taken as the mass of feed material relative to the mass of liquid metal within the reactor.
  • the feed material can be measured as the carbon-containing material that is fed to the reactor.
  • feed rates of at least about 0.003%/s, at least about 0.005%/s, at least about 0.01%/s, at least about 0.03%/s, at least about 0.05%/s, at least about 0.07%/s, at least about 0.1%/s, at least about 0.2%/s, at least about 0.3%/s, at least about 0.5%/s, at least about 0.7%/s, or at least about 1%/s.
  • the overall molar ratio of carbon to oxygen is externally controlled, for example, by monitoring the amount of carbon monoxide and/or the ratio of carbon monoxide to carbon dioxide produced within the reactor, and adjusting the feed materials as necessary, e.g., by increasing or decreasing, as necessary, the feed rates of any carbon- containing materials and/or oxygen-containing materials, and/or by adding or removing streams of feed material to the reactor.
  • adjusting the feed materials as necessary, e.g., by increasing or decreasing, as necessary, the feed rates of any carbon- containing materials and/or oxygen-containing materials, and/or by adding or removing streams of feed material to the reactor.
  • a first stream may include a carbon-containing material (which may also include some oxygen in some cases) and a second stream may include an oxygen-containing gas such as air, oxygen, enriched air, or the like.
  • an oxygen-containing gas such as air, oxygen, enriched air, or the like.
  • the overall molar ratio of carbon to oxygen can be controlled, e.g., to produce ratios such as those described above.
  • the overall molar ratio of carbon to oxygen is controlled by feeding another feed material, for example, one that is oxygen-poor or oxygen-rich, and/or one that is carbon-poor or carbon-rich. See, for example, U.S. Patent Application Serial No.
  • reactors containing one or more metals in a liquid state conventionally primarily liquid iron, and not typically configured to convert feed materials into syngas while employing relatively high overall molar ratios of carbon to oxygen, e.g., such that the overall molar ratio of carbon to oxygen in the feed materials is between about 0.6: 1 and about 1.2: 1, as such conditions have been understood to result in the production of iron oxide or slag within the reactor due to the relatively high amounts of oxygen present under such conditions.
  • iron oxides or slag that are produced are produced irreversibly, and cannot be removed from the reactor without first shutting down the reactor; and if not removed, the production of iron oxide or slag within the reactor can cause the reactor to shut down as the iron oxide or slag accumulates and eventually blocks access to any liquid iron remaining within the reactor.
  • reactor can be prone to substantial breakdowns or loss of efficiency if operated under such conditions.
  • Reactors containing one or more metals in a liquid state to convert feed materials into syngas have therefore typically been operated such that there were very low levels of oxygen present so as to avoid the production of iron oxides or slag.
  • certain embodiments of the present invention involve reactors and reactor conditions, such that reactors containing one or more metals in a liquid state can be operated with relatively high levels of oxygen.
  • a reactor employs a metal with a relatively low oxidation potential, such as, e.g. copper.
  • the reactor may include any number of liquid metals (e.g., as in a mixture or an alloy), where the liquid metal(s) have an overall standard electrode (oxidation) potential of greater than 0 V, e.g., as measured against a standard hydrogen electrode.
  • the standard oxidation potential is measured under conditions of 25 °C and 1 atm with the metal in a pure state, and is defined relative to a standard hydrogen electrode, which is arbitrarily given a potential of 0 V.
  • the liquid metal may have a standard oxidation potential of greater than about 0.1 V, greater than about 0.2 V, greater than about 0.3 V, greater than about 0.4 V, or greater than about 0.5 V.
  • Copper does not produce copper oxides (e.g., CuO and/or Cu 2 0) as readily as iron is able to produce iron oxides (i.e., iron is more apt to be oxidized than is copper, as illustrated by their standard oxidation potentials of -0.04 V and +0.52 V respectively), and under certain inventive conditions, substantially no copper oxide may be produced while oxidizing feed materials to produce syngas or other gases. For instance, when the reactor is operated such that a relatively large amount of carbon-containing material is fed into the reactor, any copper oxides that are produced may be essentially immediately reduced back to copper; thus, under such conditions, there may be essentially no production or accumulation of copper oxide within the reactor.
  • circulation within the reactor of fluids and/or metal may be used to facilitate the reduction of metal oxides such as copper oxide to metals, e.g., by causing the metal oxides to enter regions within the reactor having relatively lower oxygen partial pressures.
  • any copper oxides that are produced are not produced irreversibly. Accordingly, even if the reactor is operated under conditions in which some copper oxide production occurs, the copper oxides can be readily reduced back to copper metal by feeding additional carbon-containing materials to the reactor and/or altering the reaction conditions within the reactor such that the copper oxides are exposed to reducing conditions. For example, circulation of metal in the bath, addition of a reducing gas such as hydrogen to the reactor, increasing the amount of feed material, and/or reduction in the amount of oxygen added to the reactor relative to the amount of feed material may be used to reduce any copper oxides that may be present.
  • a reducing gas such as hydrogen
  • the reactor can be run under a wide range of overall molar ratios of carbon to oxygen. Controll of the overall molar ratio of carbon to oxygen in the feed materials entering the reactor may be used to reduce or eliminate any metal oxides that are present or might be produced within the reactor. In other embodiments, however, the reactor can be operated under conditions in which some metal oxide is produced, but the metal oxide that is produced may be one that is not irreversibly produced and can be reduced to metal as discussed above.
  • the reactor is operated by controlling the overall molar ratio of carbon to oxygen in the one or more feed materials such that substantially no metal oxide (e.g. copper oxide) accumulates within the reactor, e.g., under normal operating conditions.
  • the reactor may be operated for a period of at least about an hour, at least about a day, at least about a week, at least about 4 weeks, at least about 30 days, etc., and substantially no metal oxide (e.g. copper oxide) accumulates within the reactor.
  • metal oxide e.g. copper oxide
  • copper oxide may be produced but is not sufficient to slow reaction within the reactor and/or block access to copper or other liquid metals within the reactor.
  • high overall molar ratios of carbon to oxygen may result in substantially all of the oxygen that is fed to the reactor being reacted within the reactor, e.g., producing carbon monoxide and/or carbon dioxide, or other oxidation products (e.g., metal oxides or incompletely oxidized carbon-containing materials).
  • at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% by volume of the oxygen fed into the reactor may be consumed or reacted within the reactor (including the headspace above the liquid metal).
  • metals such as gold, lead, zinc, silver, tin, palladium, platinum, or the like may be used, as such metals also may be used in a liquid state within a reactor to facilitate the oxidation of feed materials to produce syngas or other gases without producing the respective metal oxides, and/or such that any metal oxides that are produced can be reduced back to the metal state, for example, upon the addition of carbon-containing materials and/or by exposing such metal oxides to suitably reducing conditions, such as those described above.
  • mixtures or alloys of one or more of these metals and/or other metals are used.
  • oxides of metals such as these can be reduced and/or eliminated from the reactor, and/or substantially no metal oxides may be produced within the reactor.
  • the reactor can be operated such that any metal oxides that are produced are substantially balanced by the reaction of such metal oxides to a reduced, non-oxide metal state; thus, substantially no accumulation of any metal oxides within the reactor may occur.
  • the reactor may contain one or more liquid metals having an overall standard oxidation potential of at least about 0 V, or other potentials as described herein.
  • a metal oxide can be reduced by reacting the metal oxide with a carbon-containing material under suitable conditions.
  • the metal oxide is reduced to a non- oxidized state upon exposure to a carbon-containing material, as the metal oxide is reduced while the carbon-containing material is oxidized, e.g., to produce carbon monoxide and/or carbon dioxide, or other oxidation products as discussed herein.
  • any metal oxides that are produced within the reactor may be reduced, for example, upon exposure to carbon-containing material, and/or upon exposure to a reducing environment.
  • any metal can be used within the reactor, where the metal oxide of that metal can be reduced in a suitable reducing environment and/or upon exposure to a suitable carbon-containing material that is oxidized while the metal oxide is reduced to the metal.
  • a reactor may be operated such that substantially no carbon boils occur in the liquid metal during the oxidation of the carbon-containing materials.
  • a carbon boil there is a sudden, violent production of carbon monoxide and/or carbon dioxide from the liquid metal.
  • the carbon boil is disruptive and droplets of liquid metal may be violently splattered or expelled from the surface of the liquid metal within the reactor, potentially disrupting operation of the reactor or damaging the reactor itself.
  • a carbon boil occurs when a large mass of carbon-containing material contained within the bulk of the liquid metal is oxidized therein to produce carbon monoxide and/or carbon dioxide within the liquid metal.
  • the carbon monoxide and/or carbon dioxide gases are trapped below the surface of the liquid metal.
  • the trapped gases cannot escape the liquid metal, and instead are released after a large amount of such gases have accumulated within the liquid metal, thereby providing enough mass and/or buoyant force to be able to escape.
  • the gases are thus able to escape the surface of the liquid metal as a violent "carbon boil.”
  • Those of ordinary skill in the art will be familiar with carbon boils within a liquid metal, including techniques for identifying carbon boils.
  • carbon boils may be reduced or eliminated using various techniques as discussed herein.
  • a higher overall molar ratio of carbon to oxygen in the feed materials can be used to reduce or eliminate carbon boils.
  • the feed rate of carbon-containing material can be increased and/or the amount of oxygen fed to the reactor may be reduced.
  • Other techniques such as those described herein may also be used. For example, by increasing the amount of carbon that is present within the reactor, relative to oxygen, more pyrolysis and less oxidation may occur for any carbon-containing material that is present within the liquid metal, thereby reducing the amount of carbon monoxide and/or carbon dioxide that is produced within the liquid metal.
  • the carbon-containing material may be fed at a relatively high feed rate, for example, at a feed rate of at least about 0.001 /s, or other rates such as those discussed above.
  • a reactor can be operated to increase the amount of reaction that occurs in the headspace above the liquid metal, relative to the amount of reaction that occurs internally of the liquid metal, in order to decrease carbon boils within the reactor. Under such conditions, more reaction can occur in the headspace, which is of course not susceptible to carbon boils. Reaction in the headspace may be facilitated, for example, by feeding feed materials into the headspace above the liquid metal instead of into the liquid metal itself (for example, which would be the case for bottom-fed lances or tuyeres).
  • liquid metals within the reactor may be useful in heating the headspace above the liquid metal such that at least some reaction of the feed materials occurs in the headspace instead of within the liquid metal.
  • metals having relatively high thermal conductivities for example, copper, can be used to facilitate reaction within the headspace.
  • the metals may be chosen such that the metals within the reactor, when in a liquid state, have an overall thermal conductivity of at least about 60 W/m K, at least about 70 W/m K, at least about 80 W/m K, at least about 90 W/m K, at least about 100 W/m K, at least about 110 W/m K, at least about 120 W/m K, at least about 130 W/m K, at least about 140 W/m K, at least about 150 W/m K, or at least about 160 W/m K.
  • relatively high thermal conductivities can result in more even heating of the liquid metal, at least in some embodiments, which may be useful in reducing localized "hot spots" within the liquid metal and creating more uniform conditions to facilitate reaction, e.g., within or above the liquid metal, thereby reducing concentrations of localized reaction or carbon boil formation.
  • Certain metals such as copper or certain alloys (e.g., eutectic alloys), may also be useful, in some embodiments, because of their relatively low melting points.
  • eutectic alloys involving copper include alloys including manganese, germanium, magnesium, antimony, or silicon.
  • a reactor can be operated to have an operating temperature of less than about 2800 °F (1811 K), less than about 2600 °F (1700 K), less than about 2400 °F (1589 K), less than about 2200 °F (1478 K), less than about 2000 °F (1366 K), less than about 1800 °F (1255 K), less than about 1600 °F (1144 K), less than about 1400 °F (1033 K), less than about 1200 °F (922 K), less than about 1000 °F (811 K), etc.
  • a reactor having a smaller mass or volume of liquid metal than is conventional for typical liquid metal reactors of similar overall size or syngas production capacity can be used, e.g., such that more of the reaction occurs in the headspace above the liquid metal and/or such that there is not as much mass of liquid metal in which reactions involving the carbon-containing material can occur.
  • the volume of the headspace may be at least about 10%, at least about 20%, at least about 30%, at least about 50%, at least about 75%, at least about 100%, at least about 150%, at least about 200%, at least about 300%, at least about 400%, at least about 500%, at least about 700%, or at least about 1000% of the volume of the liquid metal contained within the reactor.
  • the reactor can be operated with a nominal height of liquid of less than about 24 inches (about 61 cm), less than about 18 inches (about 46 cm), less than about 16 inches (about 41 cm), less than about 12 inches (about 30 cm), less than about 10 inches (about 25 cm), less than about 8 inches (about 20 cm), less than about 6 inches (about 15 cm), or less than about 4 inches (about 10 cm).
  • the nominal height can be calculated using the volume and the geometry of the reactor and the volume of metal within the reactor (for example, determined by dividing the mass of metal within the reactor that will be liquid during operation of the reactor by the density of the metal at the operating temperature of the reactor).
  • a reactor can be used that contains liquid copper (and/or other metals as discussed herein) and a relatively large headspace, where a carbon-containing material is fed into the headspace at a relatively rapid rate, thereby promoting reaction within the headspace relative to the liquid copper itself, e.g., to reduce or eliminate the number of carbon boils that occur during oxidation of the carbon-containing materials.
  • the reactor can be operated under conditions where the liquid metal within the reactor is not actively stirred, e.g., by inductive heating, porous plugs, stirrers, mixing blades, baffles, impellers, etc. (although in other embodiments, one or more of these may be used, and many of these are readily available from commercial suppliers).
  • mixing of the liquid metal within the reactor may be driven by passive processes such as heat convection, e.g., where the heat and/or feed materials provided to the reactor may be used to heat and/or stir the liquid metal within the reactor, without requiring additional energy or material inputs to stir the liquid metal.
  • Examples of techniques which can be used to reduce and/or eliminate active stirring of the liquid metal within the reactor during operation of the reactor include any of those described above.
  • metals having relatively high thermal conductivities can be used, e.g., such that less stirring is required to substantially heat the liquid metal while avoiding localized "hot spots.”
  • a liquid metal may be used in which the metal has a thermal conductivity of at least about 60 W/m K, at least about 70 W/m K, etc., as discussed herein.
  • a reactor having a smaller mass or volume of liquid metal can be used, i.e., a reactor having a relatively large headspace.
  • Such reactors may have more exposed surface metal, relative to the bulk of the metal, and/or less stirring may be needed to bring portions of the bulk metal to the surface of the liquid.
  • stirring may happen passively, e.g., due to differences in temperature, volume, etc., that are created within the liquid metal due to differences in temperature, pressure, bubble creation, etc. Accordingly, such stirring may be sufficient for operation of the reactor as discussed herein, without the addition of active stirring mechanisms.
  • a lack of active stirring would typically cause regions of uneven temperature or heating (e.g., due to poor heat conduction within the metal), regions of uneven reaction (e.g., of feed materials), carbon boils, or the like.
  • a reactor may be operated, at least partially, such that the heat necessary to keep the metal within the reactor in a liquid state comes essentially from one or more feed materials supplied to the reactor, i.e., the reactor is operated under "autothermal" conditions.
  • the reactor may be operated to be autothermal, i.e., without the use of any additional sources of heat, for at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of the time when the reactor is operated such that a liquid metal is present within the reactor.
  • certain metals such as those described herein may be useful in reactors able to operate, at least partially, under autothermal conditions.
  • the reactor may include a liquid metal that does not result in the accumulation of metal oxides within the reactor (at least under certain operating conditions) while a carbon- containing material is oxidized to produce carbon monoxide and/or carbon dioxide; one non- limiting example of such a metal is copper, e.g., as previously discussed.
  • autothermal operation is, in part, a function of the amount of carbon-containing material fed to the reactor (which can be oxidized to produce heat as well as carbon monoxide and/or carbon dioxide), metals having such properties can allow for faster reaction and/or conversion of carbon- containing material, which may be enough to maintain the temperature of the liquid metal without requiring another source of heat, at least under certain conditions.
  • suitable amounts of an oxygen-containing material can also be fed to the reactor, for example as air, enriched air, or oxygen gas, to maintain a suitable overall molar ratio of carbon to oxygen in the feed materials, as noted above.
  • Such reactions can also produce metal oxides in some cases, e.g., due to the relatively high amounts of carbon and/or oxygen that are fed to the reactor in order to produce sufficient heat to operate the reactor under autothermal conditions.
  • the metal can be chosen such that any metal oxides that are produced may be readily eliminated from the reactor, for example, by exposing the metal oxides to a suitable reducing environment and/or a suitable carbon-containing material to reduce the metal oxides to metal.
  • some metals, such as iron irreversibly form iron oxides under such conditions, and thus, reactors employing liquid iron baths would not be suitable for autothermal operation.
  • a reactor containing a suitable liquid metal can be operated under autothermal conditions, at least partially, by feeding a carbon- containing material at a relatively fast rate into the reactor (e.g., in combination with other feed materials to supply sufficient oxygen to the reactor to oxidize the carbon-containing material), while not supplying any external heat to the reactor.
  • the rate of feed of the carbon-containing material and/or the oxygen-containing material may be controlled to maintain the temperature of the liquid metal.
  • the temperature of the liquid metal may be monitored, and the flow rate of incoming carbon-containing material and/or the flow rate of incoming oxygen-containing material can be correspondingly increased or decreased, depending on the variation in temperature of the liquid metal.
  • the rate at which a carbon-containing material is fed to the reactor, in combination with rate at which an oxygen-containing material is fed to the reactor may be such that metal oxides can be produced.
  • metal oxides can be produced.
  • such high feed rates were typically avoided in the past, for example, in reactors containing liquid iron, as high amounts of oxygen fed to the reactor would cause the irreversible creation of iron oxides, thereby preventing long-term or sustained use of the reactor.
  • the use of certain metals that do not essentially irreversibly produce metal oxides may be used even when relatively high amounts of carbon-containing materials and/or oxygen-containing materials are fed to the reactor.
  • a reactor can be operated such that at a first time, the reactor is used to react a carbon-containing material to produce carbon monoxide (and/or syngas), e.g., as previously discussed; some of the metal may also be oxidized to produce a metal oxide, at least in some cases.
  • the rate at which a carbon- containing material and an oxygen-containing material are supplied to the reactor e.g., under autothermal conditions, or other conditions as discussed herein
  • the reactor can be operated to chemically reduce the metal oxide within the reactor to metal.
  • such reaction may occur without the production of carbon monoxide, and/or such that a smaller amount of carbon monoxide is produced.
  • a reducing agent such as natural gas, hydrogen, additional feed material, etc. may be added to the reactor, or additional carbon- containing material may be added to the reactor that any metal oxides present within the reactor are reduced to metal, e.g., as was discussed above.
  • any of the modes of operation previously described can be repeated any number of times (2, 3, 4, 5, 7, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 100, etc.) during steady operation of the reactor (i.e., while the liquid metal within the reactor is continually maintained in a liquid state).
  • the reactor in the first mode of operation, the reactor is operated to produce carbon monoxide and/or syngas, while in the second mode of operation, the reactor is operated to reduce any metal oxides present within the reactor, and this process can be repeated indefinitely or as necessary during operation of the reactor.
  • any metal oxides that are produced within the reactor are also removed from the reactor; thus substantially no oxide of the metal accumulates within the reactor, i.e., under normal operating conditions.
  • the amount of time the reactor spends in each mode of operation can be the same or different.
  • the time the reactor spends in each mode may be constant, or may vary, and in some cases the amount of time need not be predetermined, although in some embodiments, the time is predetermined or preset. For example, when a certain amount of metal oxide is observed to be present within the reactor, the reactor may be switched into the second mode of operation in order to reduce the metal oxides present within the reactor, before returning to the first mode of operation.
  • a reactor may be spend about 90% of its operating time in the first mode of operation and about 10% in the second mode of operation, about 80% in the first mode and about 20% in the second mode, about 70% in the first mode and about 30% in the second mode, about 60% in the first mode and about 40% in the second mode, about 50% in the first mode and about 50% in the second mode, about 40% in the first mode and about 60% in the second mode, about 30% in the first mode and about 70% in the second mode, about 20% in the first mode and about 80% in the second mode, or about 10% in the first mode and about 90% in the second mode.
  • the reactor containing the metal in the liquid state can have any size or configuration, in various aspects, and can be formed from any suitable material.
  • the reactor may be a refractory-lined reactor, for example, an induction furnace, an arc furnace, or any other type of high-temperature reactor able to contain a liquid metal.
  • a refractory material typically is one that retains its strength at high temperatures, and thus, may be useful as part of a reactor.
  • the refractory may be a non-metallic material having chemical and/or physical properties that makes the refractory applicable for reactors, or as components of reactors, that are exposed to environments above 1,000 °F (811 K).
  • Non-limiting examples of refractory materials include aluminum oxide (AI 2 O 3 ), silicon oxide (silica, Si0 2 ), magnesium oxide (magnesia, MgO), calcium oxide (quicklime, CaO), zirconia (Zr0 2 ), fireclays, chromia (Cr 2 0 3 ), or the like.
  • the reactor can, in some embodiments, be selected to be sufficiently sized for the selected rates of feed of the feed materials, and/or be selected such that the amount of liquid metal contained therein can be controlled at any given time.
  • the reactor may also be selected to have additional volume above the liquid metal (headspace), e.g., to allow at least some of the feed material to react therein, as previously discussed, and/or to accommodate gases exiting the liquid metal and/or foaming of material within the reactor, etc.
  • the size of the reactor, the positioning of nozzles for feed materials such as carbon-containing materials, oxygen-containing feed materials, etc., and the form of the exhaust gas passageway, can also be selected based on factors such as product throughput, on the type or feed rate of the feed materials, etc.
  • the volume of the reactor may be at least about 10 ft , at least about 25 ft 3 , at least about 50 ft 3 , at least about 100 ft 3 , at least about 150 ft 3 , at least about 200 ft 3 , at least about 250 ft 3 , at least about 300 ft 3 , at least about 350 ft 3 , at least about 400 ft 3 , at least about 450 ft 3 , or at least about 500 ft 3 , depending on the application (1 ft 3 is about 0.0283 m ).
  • the weight of liquid metal within the reactor during operation of the reactor can be at least about 1 ton, at least about 2 tons, at least about 3 tons, at least about 5 tons, at least about 7 tons, at least about 10 tons, at least about 15 tons, at least about 20 tons, at least about 25 tons, at least about 30 tons, at least about 50 tons, at least about 75 tons, or at least about 100 tons (1 ton is about 907 kg).
  • the reactor may have any suitable shape, for example, rectangular, cylindrical, spherical, irregular, etc.
  • the reactor may be operated using any suitable technique, e.g., as a continuous process, as a batch process, or as a semi-batch process.
  • various parameters of the reactor can be monitored, e.g., periodically or continuously.
  • Non-limiting examples include the temperature and/or pressure within the headspace and/or within the liquid metal, the level or amount of the liquid metal within the reactor, the incoming flow rates and/or compositions of one or more of the feed materials (e.g., carbon-containing materials and/or oxygen-containing materials), the outgoing flow rates and/or compositions of gases from the reactor, or the like.
  • one or more feed materials can be fed to any suitable location in the reactor.
  • the feed materials can be fed from the top of the reactor (e.g., into the headspace), or fed directly into the metal layer itself (e.g., using a feeding tube, a lance, a tuyere, etc.).
  • each of the feed materials may be co-fed or independently fed to any suitable location within the reactor.
  • a carbon-containing material may be fed to the headspace, and an oxygen- containing material may also be fed to the headspace and/or fed to the liquid metal.
  • feed mechanisms include auger extruder feeders (e.g., Model No. GPT2-2- 400-00, manufactured by Komar Industries, Columbus, Ohio), ram feeders (e.g., as
  • lime can be added in certain embodiments to neutralize such compounds.
  • Certain fluxes such as but not limited to, soda ash and borax, may also be added, e.g., to lower melting temperatures for some of the oxides that are produced. Lime may also be added to achieve and/or maintain a desired pH in some embodiments.
  • feed materials e.g., MSW
  • the feed materials can be analyzed for their heat values prior to injection into the reactor, and the input of one or more feed materials into the reactor may be controlled, for example, so that the reactor can be used to produce syngas and/or energy at a certain target value.
  • two or more feed materials having various heat contents can be blended together to produce a final heat content, and/or the feed rate of one or more feed materials into the reactor may be sped up or slowed down to produce a substantially constant production rate of syngas in the reactor. Examples of such systems are disclosed in International Patent Application No.
  • oxygen can also be fed to the reactor in an oxygen-containing material, e.g., as oxygen gas (e.g., substantially pure oxygen gas), air, enriched air (i.e., enriched in oxygen over atmospheric levels), etc.
  • oxygen gas e.g., substantially pure oxygen gas
  • air enriched air
  • the oxygen-containing material may be fed to the liquid metal and/or in the headspace above the metal.
  • techniques to inject an oxygen- containing material into the reactor include lances to inject the material from the top of the reactor, or lances or tuyeres to inject the material from the bottom of the reactor.
  • an oxygen-containing material can be supplied using one or more supersonic gas lances (e.g., Praxair type J burners), which generate a gas stream capable of penetrating into the metal liquid (e.g., the exit of the lances are above the liquid metal, but sufficiently adjacent thereto so that that the supersonic stream penetrates the liquid metal).
  • supersonic gas lances e.g., Praxair type J burners
  • lances or tuyere tubes to inject an oxygen-containing material into the liquid metal from the bottom of the reactor may also be used.
  • Submerged lances or tuyeres can also be used in other
  • One non-limiting example of a lance manufacturer is Process Technology International Inc, Tucker, Georgia.
  • the reactor may, in some embodiments, be equipped with a tapping mechanism, which may be of the same type which is used to tap blast furnaces and electric arc furnaces.
  • the reactor can be equipped with tapping mechanisms for removal or sampling of excess metal or vitreous materials.
  • the vitreous materials or metals may be periodically tapped, for example, to maintain a constant level of the liquid metal in the reactor.
  • Suitable tapping mechanisms include tapping drills, which are supplied by a number of manufacturers (e.g., Woodings Industrial Corporation, Mars, Pa.) or a mud gun to plug the drilled hole.
  • similar results can be achieved with periodic tapping of the reactor. While in operation, other materials such as vitreous material, oxides, etc. may accumulate in the reactor.
  • the level of the liquid metal may be controlled such that if it rises above a pre-set point, the tapping mechanism for the metal and/or other materials will be activated.
  • the reactor includes one or more steam injection ports.
  • the ports may be positioned in any suitable location within the reactor, e.g., above the liquid metal.
  • suitable injection systems include, but are not limited to, stainless steel nozzles manufactured by Spraying Systems Inc.
  • Steam injection may be used, for example, to control the temperature of the process due to the endothermic reaction of water and carbon.
  • the reaction of steam with carbon present within the reactor is an endothermic reaction, which can rapidly and efficiently reduce the temperature in the reactor without, in certain embodiments, jeopardizing synthesis gas output.
  • Syngas and other materials can be removed through one or more outlets from the reactor, and the removal can be accomplished by any suitable technique.
  • syngas may exit the reactor through an opening on top of the reactor.
  • the reactor volume and dimensions above the metal may be designed to allow efficient production of syngas, and/or to reduce particulate load in the gas stream. Additional boilers, scrubbers, and compressors can be installed downstream, depending on the specific application.
  • the exiting stream containing syngas (and/or other gases) may be further treated and/or purified as necessary or desirable.
  • One non-limiting example of treating particulate and impurities in a syngas output stream is to treat the stream with plasma discharge in a manner which treats these particulate and impurities, but does not significantly oxidize or "burn" the CO portion of the syngas.
  • types of plasma discharge include microwave and inductive coupling plasma, which are capable of generating an appropriate type of non-equilibrium plasma electrode-less discharge.
  • a dry scrubber injecting sodium hydroxide or lime, can be installed in the exhaust.
  • ceramic filters or cyclone separators may be used to treat gases, e.g., in order to eliminate any residual particulates.
  • Another method is to use a sodium hydroxide solution in a wet scrubber installed before the compressor.
  • Heat contained in the exiting gases can be recuperated in a heat exchanger, in certain embodiments.
  • the syngas may include water as previously discussed, which may in some embodiments be removed after the gas is compressed and cooled below its dew point.
  • reactor 10 includes feed inlet 15, burner ports 20, and air injection port 25. Contained within reactor 10 is liquid copper 30, which may be stirred using gas injected through one or both of porous plugs 55.
  • liquid copper 30 fills the reactor to a depth of 16 inches, although other depths or volumes may be used. Also shown in these figures is outlet port 35, pyrometer view port 40, optional burner port 45, copper drain port 60, and burner port 70. Port 5 is used for access to the reactor, e.g., for acquiring samples therein or insertion of a thermocouple. Slag that is produced during operation of the reactor may be removed through one of slag ports 50.
  • the outer dimensions of the reactor (L x W x H) were 184 inches x 76 inches x 78 inches (467 cm x 193 cm x 198 cm).
  • the reactor was fabricated of an outer stainless steel shell filled with several layers of refractory and insulation. In particular, from the innermost layer to the outermost layer, the materials were: refractory (Tuffcrete 608, 13.25 inches or 33.7 cm thickness), firebrick
  • the reactor was operated with the copper being heated to a temperature of 2300 °F (approximately 1300 °C) with a slightly negative pressure (-0.5 inH 2 0, or about -124 Pa relative to ambient pressure).
  • Ground wooden railroad ties were fed into the reactor/gasifier via the feed inlet 15 at feed rates of 200 lb/hr and 250 lb/hr (about 90 kg/hr and 113 kg/hr, respectively).
  • natural gas was introduced concomitantly with the feed.
  • Figs. 4A and 4B are respective graphs showing the record of syngas composition throughout the runs at these flow rates. Table 1 shows all of the inputs into the gasifier and measured outputs.
  • 1 lb/hr is about 0.454 kg/hr and scfm ("standard cubic feet per minute") is the molar flow rate of a gas corrected to standardized conditions of 1 atm and 25 °C (298 K) using the ideal gas law and the composition of the gas.
  • Example 2 a reactor similar to the one used in Example 1, containing liquid copper, was used to generate syngas with varying C:0 ratios with railroad ties as a feed material.
  • the moisture content in the railroad ties varied from 15% to 50%.
  • the feed rate of air was altered, relative to the feed rate of the railroad ties, in order to obtain various C:0 ratios as discussed below.
  • Natural gas flow rates for the feed side burner varied from 4.50 scfm to 10.0 scfm, and flow rates for the center burner varied from 2.5 scfm to 5.0 scfm.
  • the burners in the reactor were run at slightly sub stoichiometric conditions with oxygen.
  • Fig. 6 A shows data from an experiment using a reactor similar to the one discussed in Example 1, except that the inner bath width was 8 inches (20 cm) wider.
  • the headspace temperature was measured continuously, while the bath temperature (liquid copper) was measured at the start and end of the run. In both cases, the temperature remained relatively consistent.
  • railroad ties used as a feed material contained 40% moisture, and were fed at 150 lb/hr for 8 hours.
  • the feed burner and center burner flow rates were fixed and had natural gas flows of 5.2 scfm and 3.2 scfm, respectively. Both burners were run at slightly sub stoichiometric conditions.
  • the syngas produced in this experiment comprised 10% CO (dry) and 9% H 2 (dry), with the remainder mostly comprising nitrogen, carbon dioxide, and steam.
  • Fig. 6B shows another experiment using railroads with 50% moisture.
  • the railroad ties were fed 150 lb/hr for 20 hours.
  • the feed burner and center burner flows were fixed and had natural gas flows of 5.2 and 3.2 scfm, respectively. Both burners were run at slightly sub stoichiometric conditions.
  • the headspace temperature was measured continuously, while the liquid metal bath temperature was measured at the start and end of the run.
  • the syngas produced in this experiment comprised 6% CO (dry) and 6.5% H 2 (dry), with the remainder mostly comprising nitrogen, carbon dioxide, and steam.
  • the reactor was operated autothermally, i.e., essentially all of the heat necessary to keep the copper within the reactor liquid came from exothermic partial oxidation of the railroad ties and natural gas that were fed to the reactor.
  • a problem with operation of the reactor caused a slag object to form within the reactor.
  • the slag object was about 10 inches wide (25 cm) and 6-8 inches (15 cm to 20 cm) above the bath level.
  • the object withstood relatively high inlet gas velocities, suggesting that the object was not feed material or char.
  • Part of the object was removed from the reactor, and its color was reddish with fine porosity.
  • Preliminary chemical analysis of this suggested that the object was a mixture of slag and copper oxide.
  • Further analysis of the reactor showed that the location where the object was formed had the highest oxygen partial pressure inside the gasifier, again suggesting that the object was formed from copper oxide.
  • a reference to "A and/or B", when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • the phrase "at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified.
  • At least one of A and B can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

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Abstract

La présente invention concerne de manière générale des réacteurs contenant un ou plusieurs métaux à un état liquide pour oxyder au moins partiellement des matériaux d'alimentation, p. ex. pour produire un gaz de synthèse ou d'autres produits, par exemple des gaz tels que des gas combustibles. Les métaux contenus dans le réacteur peuvent comprendre par exemple un ou plusieurs métaux choisis parmi le cuivre, le fer, l'étain, le zinc, l'argent, le palladium, l'or et/ou d'autres métaux et leurs alliages. Dans certains cas, le réacteur peut être utilisé de manière à ce qu'essentiellement aucun oxyde des métaux ne s'accumule dans le réacteur et/ou de manière à ce qu'essentiellement la totalité de l'oxygène entrant dans le réacteur soit utilisé par le matériau d'alimentation ou les produits de carbonisation dans le réacteur. Selon certains modes de réalisation, un matériau contenant du carbone peut être introduit dans le réacteur pour réduire chimiquement tout oxyde métallique présent. Le réacteur peut également être utilisé de manière à ce qu'essentiellement aucune effervescence du carbone n'ait lieu dans le réacteur. Par ailleurs, le réacteur peut être utilisé de manière autotherme dans certains cas, c.-à-d. qu'essentiellement toute la chaleur nécessaire pour maintenir le métal contenu dans le réacteur à un état liquide provient exclusivement de l'oxydation partielle exothermique d'un ou de plusieurs des matériaux d'alimentation introduits dans le réacteur. Par ailleurs, la génération de chaleur peut être ajustée par le degré d'oxydation du matériau d'alimentation sans oxyder le bain de métal. D'autres aspects de l'invention concernent de manière générale des procédés d'utilisation de tels réacteurs, des procédés de production de tels réacteurs ou analogues.
PCT/US2012/042521 2011-06-17 2012-06-14 Réacteurs contenant un métal liquide Ceased WO2012174284A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1980002151A1 (fr) * 1979-04-02 1980-10-16 Cosden Technology Procede de conversion de materiaux carbones
JPS56167789A (en) * 1980-05-30 1981-12-23 Nippon Kokan Kk <Nkk> Gasification of carbonaceous material
RU2064003C1 (ru) * 1993-02-19 1996-07-20 Мечев Валерий Валентинович Способ газификации твердого топлива
US5577346A (en) * 1990-06-21 1996-11-26 Ashland Inc. Multi-zone molten-metal hydrogen and fuel gas generation process
US6350289B1 (en) * 1995-04-13 2002-02-26 Marathon Ashland Petroleum Llc Two-zone molten metal hydrogen-rich and carbon monoxide-rich gas generation process
US20070256360A1 (en) * 2006-05-08 2007-11-08 Alchemix Corporation Method for the gasification of moisture-containing hydrocarbon feedstocks

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1980002151A1 (fr) * 1979-04-02 1980-10-16 Cosden Technology Procede de conversion de materiaux carbones
JPS56167789A (en) * 1980-05-30 1981-12-23 Nippon Kokan Kk <Nkk> Gasification of carbonaceous material
US5577346A (en) * 1990-06-21 1996-11-26 Ashland Inc. Multi-zone molten-metal hydrogen and fuel gas generation process
RU2064003C1 (ru) * 1993-02-19 1996-07-20 Мечев Валерий Валентинович Способ газификации твердого топлива
US6350289B1 (en) * 1995-04-13 2002-02-26 Marathon Ashland Petroleum Llc Two-zone molten metal hydrogen-rich and carbon monoxide-rich gas generation process
US20070256360A1 (en) * 2006-05-08 2007-11-08 Alchemix Corporation Method for the gasification of moisture-containing hydrocarbon feedstocks

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