WO2012162302A1 - Procédés et appareil utilisables en vue de la liquéfaction de substances organiques solides - Google Patents

Procédés et appareil utilisables en vue de la liquéfaction de substances organiques solides Download PDF

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WO2012162302A1
WO2012162302A1 PCT/US2012/038966 US2012038966W WO2012162302A1 WO 2012162302 A1 WO2012162302 A1 WO 2012162302A1 US 2012038966 W US2012038966 W US 2012038966W WO 2012162302 A1 WO2012162302 A1 WO 2012162302A1
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vessel
magnetite
conditions
reaction
electromagnetic radiation
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PCT/US2012/038966
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English (en)
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Ben Zion Livneh
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Ben Zion Livneh
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Priority to US14/119,384 priority Critical patent/US20140346030A1/en
Publication of WO2012162302A1 publication Critical patent/WO2012162302A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B23/00—Other methods of heating coke ovens
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • 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
    • C10J2300/093—Coal
    • 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
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • 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
    • C10J2300/12—Heating the gasifier
    • C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1643—Conversion of synthesis gas to energy
    • C10J2300/1653—Conversion of synthesis gas to energy integrated in a gasification combined cycle [IGCC]
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This disclosure relates generally to methods of liquefying organic minerals, such as coal, biomass and shale. This disclosure also relates to apparatus useful to effect such changes.
  • CTL coal-to-liquid
  • This application uses the term "coal” in a conventional sense to mean a combustible black or brownish black sedimentary rock comprising carbon.
  • peat is used to denote partially carbonized vegetation with high water content.
  • shale is used to denote a sedimentary rock with a large organic concentration.
  • biomass is used to denote materials of biological origin.
  • solid organic material is used to denote carbonaceous materials which are in a solid physical state at ambient temperature and pressure, such as, without limitation, any one or more of the group comprising coal, peat, shale or biomass.
  • Embodiments of the present invention feature methods and apparatus for forming liquid or gas hydrocarbons from solid organic materials such as coal, peat, shale, and biomass.
  • non-solid refers to the physical state of being a liquid or gas at or about standard ambient temperatures and pressures.
  • hydrocarbon is used in the normal chemical sense of a composition having at least one carbon atom and one hydrogen atom.
  • the present invention relates to a process for making non-solid hydrocarbons comprising the steps of subjecting a solid organic material and a magnetite-type composition to electromagnetic radiation or similar radiation to form one or more reaction products which include at least one non-solid hydrocarbon composition.
  • the electromagnetic radiation is microwave radiation typically at frequencies starting at less than 0.9 GHz (L Band) up to 40 GHz (Ka Band). In another embodiment the electromagnetic frequency may be as high as 100 GHz (W Band). In another embodiment, the electromagnetic radiation is radio frequency radiation.
  • the non-solid hydrocarbon compositions formed are suitable for use as a fuel, or a starting material for further reactions and processes typically used by oil refineries producing material for other purposes for which non- solid hydrocarbons are used.
  • One embodiment of the present invention features a process for making one or more non-solid hydrocarbons.
  • the process comprises the steps of forming a reaction mixture comprising a solid organic material and, in the presence of magnetite-type compositions and electromagnetic radiation, forming reaction and catalysis conditions that cause the reaction mixture to form reaction products comprising one or more non-solid hydrocarbons.
  • the reaction conditions are selected from one or more of the group consisting of liquefaction conditions and gasification conditions.
  • the reaction mixture further comprises one or more further reactants selected from the group consisting of water and oxygen.
  • Embodiments of the present process feature reaction conditions comprising gasification conditions and liquefaction conditions.
  • One embodiment features liquefaction conditions comprising Fischer-Tropsch synthetic conditions.
  • One embodiment features a reaction mixture in the presence of magnetite-type composition subjected to electromagnetic radiation prior to the liquefaction stage. That is, the reaction mixture undergoes a gasification process and enters a liquefaction stage with the presence of the appropriate catalysis agent.
  • embodiments of the present invention feature reactants of solid organic matter selected from the group consisting of coal, shale, peat, biomass, and combinations thereof; the reactants can possess non-solid hydrocarbons such as oils, tar, waxes and paraffins in free form or embedded in solids such as clay.
  • the magnetite-type composition comprises magnetite, that is iron oxide in any variation (such as, without limitation, Fe 3 0 4 , or FeO ⁇ Fe 2 0 3 ) and may further comprise one or more metals such as nickel, cobalt, copper, silver, gallium, indium, manganese, zinc, platinum, palladium, gold, ruthenium, rhodium, iridium, and combinations thereof.
  • the magnetite-type composition is held in an immobilized matrix or can be dispersed in the reaction mixture.
  • the magnetite-type composition is recovered and recycled.
  • Embodiments of the present processes require no solvent to be added as a reactant or to facilitate the reactions.
  • the electromagnetic radiation may take several forms. One embodiment features microwave radiation. Another embodiment features radio frequency radiation.
  • a further embodiment of the present invention features an apparatus for making one or more non- solid hydrocarbons.
  • the apparatus has at least one vessel and electromagnetic radiation means.
  • the at least one vessel has at least one opening for receiving reactants and discharging a non-solid hydrocarbon.
  • the reactants comprise solid organic material, water and oxygen.
  • the at least one vessel contains a magnetite-type composition as a mixture with said reactants or as an immobilized matrix.
  • the electromagnetic radiation means is in communication with the at least one vessel for placing electromagnetic radiation into the vessel to create reaction conditions. The reaction conditions cause the reaction mixture to form one or more non-solid hydrocarbons.
  • reaction conditions are selected from the group consisting of gasification and liquefaction; for example, without limitation, Fischer- Tropsch (F-T) synthetic conditions.
  • F-T Fischer- Tropsch
  • Embodiment of the present apparatus features a vessel suited for batch or continuous processing.
  • the at least one vessel having at least one input opening for receiving the solid organic material, water and oxygen and at least one output opening for discharging the at least one non-solid hydrocarbon.
  • the electromagnetic radiation means may take several forms such as a microwave radiation emitter and/or a radio frequency radiation emitter.
  • the emitter may be inside the vessel or emit through one or more windows into the vessel.
  • One embodiment of the present apparatus comprises an electromagnetic zone vessel and a reaction vessel.
  • the electromagnetic radiation vessel has at least one opening for receiving reactants comprising solid organic material, water and oxygen, and is further in fluid communication with the reaction vessel.
  • the electromagnetic zone vessel is in communication with said electromagnetic radiation means to receive electromagnetic radiation.
  • the reaction vessel receives the reactants from the electromagnetic zone vessel and completes the reactions to form one or more non- solid hydrocarbons.
  • the present invention relates to a process for converting organic matter into liquid or gas synfuels that involves (a) subjecting an organic material and magnetite to electromagnetic radiation; and (b) subjecting the organic material from step (a) to liquefaction conditions.
  • the organic matter is coal.
  • the process involves the addition of oxygen and water.
  • the process involves a gasification and a liquefaction (e.g., an F-T) step.
  • the present invention relates to an apparatus useful for the conversion of organic matter to liquid or gas synfuels.
  • Figure 1 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the F-T gasifier chamber and electromagnetic radiation cavity are combined.
  • Figure 2 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the feed mixture is preheated in an electromagnetic radiation cavity prior to entering the F-T gasifier chamber.
  • the present inventor has discovered an efficient single step process which incorporates electromagnetic radiation (EMR) energy for converting solid organic minerals, such as coal and biomass, into liquid or gas products.
  • EMR electromagnetic radiation
  • the single step EMR process offers a cleaner, more attractive and cost effective approach to producing synthetic fuels.
  • the processes described herein are also referred to as "F-T Gasification Processes.”
  • the present invention relates to an improved process for the conversion of organic matter, such as coal, biomass, or other organic solids to liquid or gas products.
  • Coal liquefaction has its roots in Germany in the early 1900s.
  • temperature plays a decisive role in the reaction products. For example, at high temperatures (such as 430°C) only methane is produced, while at lower temperatures (such as 300°C) the reaction products include methane ( ⁇ 10%), but are predominantly paraffin hydrocarbons ( ⁇ 90%) with more than one carbon atom.
  • solid fossil fuel such as coal can be oxidized (burnt) in two main methods: combustion and gasification.
  • combustion and gasification The products of these processes are very different.
  • the complete combustion of coal produces carbon dioxide, water, nitrogen dioxide and sulfur dioxide.
  • Gasification of coal produces carbon monoxide, hydrogen, nitrogen and hydrogen sulfide.
  • the products obtained from combustion of coal have little or no commercial value, and in recent years have attracted a negative value: the production of green-house gas (GHG) carbon dioxide became a liability in terms of environmental considerations and public image.
  • GSG green-house gas
  • gasification of coal has significant commercial value as a substitute to natural gas for heat or to generate electricity by driving gas turbines (such as in the integrated gasification combined cycle process [IGCC] where the coal is gasified to drive a gas turbine, and the heat produced is used to generate steam to drive a steam turbine).
  • gasified coal can be converted to liquid fuels, which substantially increase the economic value of the coal.
  • Coal Gasification involves the breakdown of the coal structure in an oxygen deficient environment in the presence of water (steam). The chemical reactions that occur in coal gasification are summarized in the table below. No. Reaction Description ⁇ (kJ/mol)
  • the desired chemical products of gasification which can be further converted to liquid fuels by the F-T Process, are carbon monoxide, which is produced in reactions 2, 3 and 4, and hydrogen, which is produced in reaction 4.
  • the sum of these reactions is endothermic, thus, heat is required in order to maintain the process.
  • the necessary heat is typically produced by the full combustion of coal reaction 1 and the partial combustion of coal reaction 2, which are exothermic.
  • the production of carbon dioxide is not desirable, as it reduces the carbon efficiency of the process, and reduces the heat value of the synthetic gas product. Coal will spontaneously convert to the desired products only under conditions of high temperature and pressure, which must be maintained inside the gasification reactor.
  • Syngas has a very different composition to natural gas, and has a significantly lower heat value.
  • syngas contains 14.0% hydrogen, 27.0% carbon monoxide, 4.5% carbon dioxide, 0.6% oxygen, 3.0% methane and 50.9% nitrogen and has a higher heating value (HHV) of 163 BTU/scf.
  • Natural gas contains 90.0% methane, 5.0% nitrogen and 5.0% ethane and has a HHV of 1,002 BTU/scf. Due to the lack of hydrogen and carbon monoxide, the gas-to-liquid (GTL) F-T synthesis for natural gas requires an initial gas reforming stage, where the methane gas is converted to carbon monoxide and hydrogen.
  • Typical coal gasifiers suffer from inherent physical problems. For example, the continuous feed of coal solids and continuous removal of ash solids in a system that produces gas are physically difficult to perform.
  • the internal process conditions inside the gasifier are too complex to use in a batch type process, as the buildup of these conditions is energy intensive and requires long process time to achieve.
  • syngas liquefaction is a consumer of carbon dioxide, except for reaction 3 where it is produced.
  • methane gas reaction 6
  • H:C hydrogen to carbon ratio
  • the coal liquefaction process involves the shifting of the H:C ratio of the fuel from less than 1 to about 2. This is done by adding hydrogen to the hydrogen deficient organic structure of the coal. The process requires the breakdown of the coal matrix to shift the H:C ratio by adding hydrogen to the new coal structure, and the removal of non-organic material from the new product.
  • CTL fuel can be achieved in two different ways: (1) direct
  • the present invention relates to a process for converting organic matter to liquid or gas synfuels that includes subjecting an organic material and magnetite to EMR.
  • the present invention relates to a process for converting organic matter into liquid or gas synfuels that involves (a) subjecting an organic material and magnetite to EMR; and (b) subjecting the organic material from step (a) to liquefaction conditions.
  • the process involves a combination of a gasification process and a liquefaction process (e.g., F-T Process).
  • a gasification process e.g., F-T Process
  • a liquefaction process e.g., F-T Process
  • the organic material is any organic material that contains sufficient organic matter that can be liquefied. In one embodiment, the organic material is any organic material that contains sufficient organic matter that can be liquefied economically. Suitable examples of organic material, include, but are not limited to, biomass, shale, natural and refined oil products, coal, and any combination thereof. In one embodiment, the organic material is coal. In one embodiment, the organic material is shale. In one embodiment, the organic material is oil. In one embodiment, the organic material is biomass.
  • EMR Energy is provided to initiate the gasification process by applying EMR to a mixture of materials including coal and magnetite.
  • EMR energy facilitates and expedites the chemical reactions inside the reaction chamber.
  • the fundamentals of EMR heating are very different to those of thermal heating.
  • the energy absorbed per unit time and per unit volume by the payload e.g., the magnetite-coal mixture
  • the payload which contributes to microwave heating, depends on the internal characteristics of the payload under given conditions.
  • the magnetite-coal heating rate depends on its internal properties (such as, without limitation, the amount of material, the coal to magnetite ratio, the particle size and shape, the internal voltage stress of the mixture in volts per meter, and the dielectric constant), all of which determine the ability of the material to absorb EMR energy and convert it to heat.
  • Increasing the EMR power may not increase the heat rate of the magnetite-coal mixture payload beyond its capacity to absorb the energy based on the mentioned parameters.
  • changing the EMR frequency may change the heat rate.
  • EMR energy has over thermal sources of energy is that the intensity of the radiation is easily controlled, with a very quick response time. This affords the processes described herein an operating dimension that is not currently available in standard CTL processes. For example, the energy input can be dynamically changed to meet with the chemistry needs of the process.
  • the EMR energy may be varied by changing the intensity of the electrical and magnetic fields inside the F-T gasifier. In one embodiment, the EMR energy may be varied by changing the duration of the radiation, for example, by pulsating the EMR.
  • the EMR energy is applied to the payload continuously. In another embodiment, the EMR energy is applied to the payload in pulses, in which, in additional embodiments, the on-period and the off-period can be independently varied.
  • the source of EMR energy is electricity.
  • the electricity is generated from fossil fuels.
  • the electricity is generated from renewable sources, such as, for example, wind, solar and bio-fuels, thereby allowing further reductions in green-house gas emissions for the processes described herein.
  • the EMR energy can have any frequency in the range allocated for industrial applications by the Federal Communications Commission (FCC), or other process-relevant appropriate frequencies, in a closed and leak-free chamber.
  • Suitable frequencies include, but are not limited to, the range of about 300 MHz to about 300 GHz.
  • suitable frequencies for use in the processes described herein, as authorized in various countries, are listed in the table below. 1 Frequency
  • the EMR frequency is any frequency that improves performance of the processes described herein.
  • the EMR is microwave radiation. In another embodiment, the EMR is radio frequency radiation.
  • the magnetite-type composition acts in a dual role.
  • the magnetite acts as a promoter for the gasification process.
  • the magnetite acts as a catalyst for the F- T Process.
  • the magnetite acts as both a promoter for the gasification process and as a catalyst for F-T synthesis.
  • Applicant believes that, unlike other industrial microwave applications where microwave radiation is typically used for dewatering and drying, in the processes described herein, the EMR facilitates a rapid increase in temperature of the coal-magnetite mixture to a level were gasification processes can occur. Applicant also believes that the specific characteristics of magnetite, when subjected to EMR, allows for generation of the energy necessary to gasify the organic matter (e.g., coal).
  • the organic matter e.g., coal
  • the temperature of the magnetite is raised at a rate of over 450°C (750°F) per minute under microwave energy. At this rate, a mixture of coal and magnetite can reach the temperature required for gasification in about 2 minutes.
  • the magnetite-type composition includes one or more additional chemical element(s).
  • the magnetite-type composition may include, for example, nickel, cobalt, copper, silver, gallium, indium, manganese, zinc, platinum, palladium, gold, ruthenium, rhodium, iridium, and combinations thereof.
  • the properties of the magnetite-type composition can be tailored by inclusion of additional elements in order to produce the most appropriate catalysis environment for the process. In other embodiments, the properties of the magnetite-type composition can be tailored by inclusion of additional elements in order to improve the overall product blend.
  • the magnetite is regenerated. In some embodiments, the magnetite is recycled back to the process.
  • the processes described herein do not require addition of a solvent, for example, an organic solvent. In other embodiments, the processes described herein are conducted in the absence of a solvent, such as an organic solvent.
  • the processes described herein do not require the addition of hydrogen. In one embodiment, hydrogen is not added to the reactor during the processes described herein. In another embodiment, hydrogen is added to the reactor during the processes described herein.
  • Applicant has also developed new apparatus for the direct conversion of organic matter, such as CTL or gas products.
  • the apparatus are compact and efficient chambers. Therefore, in another aspect, the present invention relates to an apparatus for the direct liquefaction of organic minerals, such as coal.
  • the processes described herein are operated in a batch mode. In another embodiment, the processes described herein are performed in a continuous mode. In one embodiment, the apparatus described herein is designed to be operated in a batch mode. In one embodiment, the apparatus described herein is designed to be operated in a continuous mode.
  • the processes described herein are operated in a batch mode utilizing a combined F-T gasifier and microwave reactor.
  • the unheated feed mixture flows into the combined F-T gasifier and EMR reactor and is exposed to EMR inside the F-T gasification chamber.
  • the processes described herein are operated in a continuous mode.
  • the feed mixture is pre-heated in an EMR cavity before reaching the main F-T reaction chamber.
  • the processes described herein are operated in a hybrid of batch and continuous modes, where the preheated feed mixture is subjected to EMR inside the F-T gasifier to achieve different process selectivity.
  • Figure 1 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the F-T gasifier chamber and EMR cavity are combined. a) The Combined F-T Gasifier Process Modules As shown in Figure 1 :
  • the F-T Gasifier is a chamber in which the gasification and liquefaction processes occur. This module operates at high temperature and pressure, to sustain the necessary process conditions for the gasification and liquefaction processes to occur.
  • the Cavity is a section of the F-T Gasifier chamber in which EMR energy is transformed to heat the magnetite and elevate the internal temperature to the level required for the gasification and liquefaction processes to occur.
  • the Solids Separator/Regenerator is a system that separates the solid effluent streams, for example, the coal ash, from the magnetite. In one embodiment, the separation is performed by a magnetic separator. This module is also designed to regenerate and clean the magnetite effluent from sulfur, hydrocarbons and other contaminants, for recycling.
  • (1) represents a coal-magnetite mixture.
  • the particle size of the mixture is greater than about 210 microns. In another embodiment, the particle size of the mixture is about 50 microns.
  • the ratio of coal to magnetite (C:M) in the mixture is between about 10 % and about 90%, for example, between about 30 % and about 70 %.
  • the oxygen feed is adjusted to control an oxygen lean atmosphere to produce carbon monoxide, and reduce the production of carbon dioxide to a minimum.
  • steam acts as the main source of hydrogen in the process.
  • the steam feed is controlled to adjust the H:C ratio of the reactant.
  • (4) represents a carbon dioxide injection inlet.
  • injection of carbon dioxide maintains a fluidized bed of the coal mixture.
  • the carbon dioxide acts as another source of carbon for the process.
  • (5) represents an EMR energy input.
  • the EMR energy is created by a standard industrial microwave generator.
  • the EMR energy is created by radio frequency.
  • cooling water represents an input for cooling water to the jacket of the gasifier.
  • cooling water is added to the jacket of the gasifier to maintain a temperature inside the chamber suitable for the processes described herein.
  • (7) represents a steam outlet from the cooling water jacket.
  • the exothermic reactions which occur inside the reaction chamber will produce high temperature that will convert the cooling water in the jacket to steam.
  • the steam is used to (1) control the gasifier/cavity temperature, and (2) to generate electricity to feed the microwave generator.
  • (8) represents an outlet, whereby synfuel and syngas products are removed for oil and chemical workup to refine the products of the process to a desired marketable product range.
  • solid waste outlet represents a solid waste outlet.
  • solid waste produced in the process includes combustion ash and magnetite.
  • (10) represents ash for disposal. Coal ash may be directed to disposal facilities.
  • (11) represents a magnetite outlet stream. In certain embodiments, magnetite is regenerated to remove residual hydrocarbons and recycled back to the process feed.
  • Figure 2 shows an exemplary process flow diagram and apparatus for coal liquefaction wherein the feed mixture is preheated in an EMR cavity prior to entering the F-T gasifier chamber.
  • the EMR zone is a chamber in which the mixture of organic material (e.g., coal), magnetite and other components are heated.
  • the heating is provided by the absorption of EMR by the magnetite.
  • the F-T Gasifier is a chamber in which the gasification and F-T synthesis processes occur. This section may also include EMR to improve selectivity.
  • the Solids Separator/Regenerator is a system that separates the solid effluent streams, for example, the coal ash, from the magnetite.
  • the separation is performed by a magnetic separator.
  • This module is also designed to regenerate and clean the magnetite effluent from sulfur, hydrocarbons and other contaminants, for recycling.
  • (1) represents a coal-magnetite mixture.
  • the particle size of the mixture is greater than about 210 microns. In another embodiment, the particle size of the mixture is about 50 microns. In further embodiments, the C:M ratio in the mixture is between about 10 % and about 90%, for example, between about 30 % and about 70 %.
  • the oxygen feed is adjusted to control an oxygen lean atmosphere to produce carbon monoxide, and reduce the production of carbon dioxide to a minimum.
  • steam acts as the main source of hydrogen in the process.
  • the steam feed is controlled to adjust the H:C ratio of the reactant (4) represents a carbon dioxide injection inlet.
  • injection of carbon dioxide maintains a fhiidized bed of the coal mixture.
  • the carbon dioxide acts as another source of carbon for the process.
  • the EMR energy represents an EMR energy input.
  • the EMR energy is created by a standard industrial microwave generator. In another embodiment, the EMR energy is created by radio frequency.
  • (6) represents an input for cooling water to the jacket of the gasifier.
  • cooling water is added to the jacket of the gasifier to maintain a temperature inside the chamber suitable for the processes described herein.
  • (7) represents a steam outlet from the cooling water jacket. The exothermic reactions which occur inside the reaction chamber will produce high temperature that will convert the cooling water in the jacket to steam.
  • the steam is used to (1) control the gasifier/cavity temperature, and (2) to generate electricity to feed the microwave generator.
  • solid waste outlet represents a solid waste outlet.
  • solid waste produced in the process includes combustion ash and magnetite.
  • (10) represents ash for disposal.
  • Coal ash may be directed to disposal facilities.
  • (11) represents a magnetite outlet stream.
  • magnetite is regenerated to remove residual hydrocarbons and recycled back to the process feed.
  • the processes described herein can utilize small particles of organic material (e.g., coal) as the starting organic mineral. Restrictions on particle size that are present in dry coal processes are thereby removed and waste is eliminated.
  • organic material e.g., coal

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Abstract

La présente invention concerne des procédés de liquéfaction de substances organiques solides, telles que le charbon, la biomasse et le schiste. L'invention concerne également un appareil permettant la mise en œuvre de ladite transformation.
PCT/US2012/038966 2011-05-23 2012-05-22 Procédés et appareil utilisables en vue de la liquéfaction de substances organiques solides WO2012162302A1 (fr)

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WO2017027328A1 (fr) 2015-08-07 2017-02-16 Ecokap Technologies Llc Conversion de gaz à effet de serre par reformage à sec
WO2017078912A1 (fr) 2015-11-02 2017-05-11 Ecokap Technologies Llc Irradiation par micro-ondes d'une chambre avec une fréquence de micro-ondes à variation temporelle ou plusieurs fréquences de micro-ondes
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