+

WO2009086361A2 - Procédé de gazéification catalytique avec récupération de métal alcalin à partir du résidu carboné - Google Patents

Procédé de gazéification catalytique avec récupération de métal alcalin à partir du résidu carboné Download PDF

Info

Publication number
WO2009086361A2
WO2009086361A2 PCT/US2008/088140 US2008088140W WO2009086361A2 WO 2009086361 A2 WO2009086361 A2 WO 2009086361A2 US 2008088140 W US2008088140 W US 2008088140W WO 2009086361 A2 WO2009086361 A2 WO 2009086361A2
Authority
WO
WIPO (PCT)
Prior art keywords
alkali metal
char
metal compounds
insoluble matter
insoluble
Prior art date
Application number
PCT/US2008/088140
Other languages
English (en)
Other versions
WO2009086361A3 (fr
Inventor
Alkis S. Rappas
Robert A. Spitz
Original Assignee
Greatpoint Energy, 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 Greatpoint Energy, Inc. filed Critical Greatpoint Energy, Inc.
Publication of WO2009086361A2 publication Critical patent/WO2009086361A2/fr
Publication of WO2009086361A3 publication Critical patent/WO2009086361A3/fr

Links

Classifications

    • 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
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • 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
    • 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
    • C10J2300/0903—Feed preparation
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0943—Coke
    • 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
    • C10J2300/0973—Water
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C10J2300/1628—Ash post-treatment
    • C10J2300/1631—Ash recycling
    • 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
    • C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
    • 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
    • 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
    • C10J2300/1853—Steam reforming, i.e. injection of steam only

Definitions

  • the present invention relates to a catalytic gasification process that involves the extraction and recovery of alkali metal from char that remains following catalytic gasification of a carbonaceous composition. Further, the invention relates to processes for extracting and recovering alkali metal from char by reacting a char particulate with an alkali hydroxide, calcium oxide and/or calcium hydroxide, and carbon dioxide under suitable temperature and pressure so as to convert insoluble alkali metal compounds contained in the insoluble char particulate to soluble alkali metal compounds.
  • alkali metal compounds can react with the alumina and silica to form alkali metal aluminosilicates.
  • the alkali metal compound is substantially insoluble in water and has little effectiveness as a gasification catalyst.
  • char generally includes ash, unconverted carbonaceous material, and alkali metal compounds (from the catalyst). The char must be periodically withdrawn from the reactor through a solid purge. The char may contain substantial quantities of alkali metal compounds.
  • the alkali metal compounds may exist in the char as soluble species, such as potassium carbonate, but may also exist as insoluble species, such as potassium aluminosilicate (e.g., kaliophilite). It is desirable to recover the soluble and the insoluble alkali metal compounds from the solid purge for subsequent reuse as a gasification catalyst. A need remains for efficient processes for recovering soluble and insoluble alkali metal compounds from char. Such processes should effect substantial recovery of alkali metal compounds from the char, minimize the complexity of the processing steps, reduce the use of consumable raw materials, and generate few waste products that require disposal.
  • the present invention provides processes for converting a carbonaceous composition into a plurality of gaseous products with recovery of soluble alkali metal compounds that can be reused as a gasification catalyst.
  • the invention further provides processes for extracting and recovering catalytically useful alkali metal compounds from soluble and insoluble alkali metal compounds contained in char, where the processes involve thermal quenching of the char in an aqueous medium followed by treatment of the char particulate with an alkali metal hydroxide, calcium oxide and/or calcium hydroxide, and carbon dioxide gas under hydrothermal conditions.
  • the invention provides a process for extracting and recovering alkali metal from a char, the char comprising (i) one or more soluble alkali metal compounds and (ii) insoluble matter comprising one or more insoluble alkali metal compounds, the process comprising the steps of: (a) providing char at an elevated temperature ranging from 50 0 C to 600 0 C; (b) quenching the char in an aqueous medium to fracture the char and form a quenched char slurry; (c) separating the quenched char slurry into a first liquid stream and an insoluble matter stream, the first liquid stream comprising at least a portion of the soluble alkali metal compounds from the char, and the insoluble matter stream comprising residual soluble alkali metal compounds and a first insoluble matter comprising insoluble alkali metal compounds; (d) recovering the first liquid stream; (e) contacting the first insoluble matter with an alkali metal hydroxide and calcium oxide, calcium hydrox
  • the invention provides a process for catalytically converting a carbonaceous composition, in the presence of an alkali metal gasification catalyst, into a plurality of gaseous products and recovering a gasification catalyst, the process comprising the steps of: (a) supplying a carbonaceous composition to a gasification reactor, the carbonaceous composition comprising an ash; (b) reacting the carbonaceous composition in the gasifying gasification reactor in the presence of steam and an alkali metal gasification catalyst under suitable temperature and pressure to form (i) a char comprising the alkali metal from the alkali metal gasification catalyst in the form of one or more soluble alkali metal compounds and one or more insoluble alkali metal compounds, and (ii) a plurality of gaseous products comprising methane and at least one or more of hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, ammonia, and other higher hydrocarbons, the gasification catalyst comprising an alkali metal; (c)
  • the process can be run continuously, and the recovered alkali metal can be recycled back into the process to minimize the amount of makeup catalyst required.
  • Figure 1 provides a schematic diagram for one example of a process for recovering alkali metal from char for reuse as a catalyst in a catalytic gasification process.
  • the present invention relates to processes for the catalytic conversion of a carbonaceous composition into a plurality of gaseous products with substantial recovery of alkali metal used as the gasification catalyst.
  • the alkali metal is recovered from char that develops as a result of the catalyzed gasification of a carbonaceous material in a gasification reactor.
  • the alkali metal may exist in the char in either water-soluble or water-insoluble forms.
  • the present invention provides efficient processes for extracting and recovering substantially all of the soluble and insoluble alkali metal from char.
  • these processes include the quenching of the char in an aqueous solution to fracture the char, dissolving substantially all of the water-soluble alkali metal compounds, separating the water soluble alkali metal compounds as a first liquid stream, and reacting the remaining insoluble alkali metal compounds with an alkali metal hydroxide, calcium oxide and/or calcium hydroxide, and carbon dioxide at suitable pressures and temperatures to solubilize and extract insoluble alkali metal compounds.
  • soluble and insoluble alkali metal compounds are substantially removed from char using simplified processes that require few consumable raw materials.
  • the present invention can be practiced, for example, using any of the developments to catalytic gasification technology disclosed in commonly owned US2007/0000177A1, US2007/0083072A1 and US2007/0277437A1; and U.S. Patent Application Serial Nos. 12/178,380 (filed 23 July 2008), 12/234,012 (filed 19 September 2008) and 12/234,018 (filed 19 September 2008). Moreover, the present invention can be practiced using developments described in the following U.S. Patent Applications, each of which was filed on even date herewith and is hereby incorporated herein by reference: Serial No. , entitled
  • PROCESSES FOR MAKING SYNGAS -DERIVED PRODUCTS (attorney docket no. FN- 0012 US NPl).
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • carbonaceous material or "carbonaceous composition” as used herein includes a carbon source, typically coal, petroleum coke, asphaltene and/or liquid petroleum residue, but may broadly include any source of carbon suitable for gasification, including biomass.
  • the carbonaceous composition will generally include at least some ash, typically at least about 3 wt% ash (based on the weight of the carbonaceous composition).
  • the term "petroleum coke” as used herein includes both (i) the solid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues - "resid petcoke") and (ii) the solid thermal decomposition product of processing tar sands (bituminous sands or oil sands - "tar sands petcoke”).
  • Such carbonization products include, for example, green, calcined, needle and fluidized bed petroleum coke.
  • Resid petcoke can be derived from a crude oil, for example, by coking processes used for upgrading heavy-gravity residual crude oil, which petroleum coke contains ash as a minor component, typically about 1.0 wt% or less, and more typically about 0.5 wt% of less, based on the weight of the coke.
  • the ash in such lower-ash cokes predominantly comprises metals such as nickel and vanadium.
  • Tar sands petcoke can be derived from an oil sand, for example, by coking processes used for upgrading oil sand.
  • Tar sands petcoke contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the tar sands petcoke.
  • the ash in such higher-ash cokes predominantly comprises materials such as compounds of silicon and/or aluminum.
  • the petroleum coke can comprise at least about 70 wt% carbon, at least about 80 wt% carbon, or at least about 90 wt% carbon, based on the total weight of the petroleum coke.
  • the petroleum coke comprises less than about 20 wt% percent inorganic compounds, based on the weight of the petroleum coke.
  • asphalte as used herein is an aromatic carbonaceous solid at room temperature, and can be derived, from example, from the processing of crude oil and crude oil tar sands.
  • liquid petroleum residue includes both (i) the liquid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues - "resid liquid petroleum residue") and (ii) the liquid thermal decomposition product of processing tar sands (bituminous sands or oil sands - "tar sands liquid petroleum residue”).
  • the liquid petroleum residue is substantially non-solid; for example, it can take the form of a thick fluid or a sludge.
  • Resid liquid petroleum residue can be derived from a crude oil, for example, by processes used for upgrading heavy-gravity crude oil distillation residue.
  • Such liquid petroleum residue contains ash as a minor component, typically about 1.0 wt% or less, and more typically about 0.5 wt% of less, based on the weight of the residue.
  • the ash in such lower-ash residues predominantly comprises metals such as nickel and vanadium.
  • Tar sands liquid petroleum residue can be derived from an oil sand, for example, by processes used for upgrading oil sand.
  • Tar sands liquid petroleum residue contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the residue.
  • the ash in such higher-ash residues predominantly comprises materials such as compounds of silicon and/or aluminum.
  • coal as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof.
  • the coal has a carbon content of less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% by weight, based on the total coal weight.
  • the coal has a carbon content ranging up to about 85%, or up to about 80%, or up to about 75% by weight, based on total coal weight.
  • Examples of useful coals include, but are not limited to, Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon, and Powder River Basin (PRB) coals.
  • Anthracite, bituminous coal, sub-bituminous coal, and lignite coal may contain about 10 wt%, from about 5 to about 7 wt%, from about 4 to about 8 wt %, and from about 9 to about 11 wt%, ash by total weight of the coal on a dry basis, respectively.
  • the ash content of any particular coal source will depend on the rank and source of the coal, as is familiar to those skilled in the art. See, for example, "Coal Data: A Reference", Energy Information Administration, Office of Coal, Nuclear, Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), February 1995.
  • ash as used herein includes inorganic compounds that occur within the carbon source.
  • the ash typically includes compounds of silicon, aluminum, calcium, iron, vanadium, sulfur, and the like.
  • Such compounds include inorganic oxides, such as silica, alumina, ferric oxide, etc., but may also include a variety of minerals containing one or more of silicon, aluminum, calcium, iron, and vanadium.
  • the term “ash” may be used to refer to such compounds present in the carbon source prior to gasification, and may also be used to refer to such compounds present in the char after gasification.
  • alkali metal compound refers to a free alkali metal, as a neutral atom or ion, or to a molecular entity, such as a salt, that contains an alkali metal. Additionally, the term “alkali metal” may refer either to an individual alkali metal compound, as heretofore defined, or may also refer to a plurality of such alkali metal compounds. An alkali metal compound capable of being substantially solubilized by water is referred to as a "soluble alkali metal compound.” Examples of a soluble alkali metal compound include free alkali metal cations and water-soluble alkali metal salts, such as potassium carbonate, potassium hydroxide, and the like.
  • an alkali metal compound incapable of being substantially solubilized by water is referred to as an "insoluble alkali metal compound.”
  • insoluble alkali metal compound examples include water-insoluble alkali metal salts and/or molecular entities, such as potassium aluminosilicate.
  • Alkali metal compounds suitable for use as a gasification catalyst include compounds selected from the group consisting of alkali metal carbonates, bicarbonates, formates, oxalates, amides, hydroxides, acetates, halides, nitrates, sulfides, and polysulf ⁇ des.
  • the catalyst can comprise one or more of Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , Li 2 CO 3 , Cs 2 CO 3 , NaOH, KOH, RbOH, or CsOH, and particularly, potassium carbonate and/or potassium hydroxide.
  • the carbonaceous composition is generally loaded with an amount of an alkali metal.
  • the quantity of the alkali metal in the composition is sufficient to provide a ratio of alkali metal atoms to carbon atoms ranging from about 0.01, or from about 0.02, or from about 0.03, or from about 0.04, to about 0.06, or to about 0.07, or to about 0.08.
  • the alkali metal is typically loaded onto a carbon source to achieve an alkali metal content of from about 3 to about 10 times more than the combined ash content of the carbonaceous material (e.g., coal and/or petroleum coke), on a mass basis.
  • any methods known to those skilled in the art can be used to associate one or more gasification catalysts with the carbonaceous composition. Such methods include, but are not limited to, admixing with a solid catalyst source and impregnating the catalyst onto the carbonaceous solid. Several impregnation methods known to those skilled in the art can be employed to incorporate the gasification catalysts. These methods include, but are not limited to, incipient wetness impregnation, evaporative impregnation, vacuum impregnation, dip impregnation, and combinations of these methods. Gasification catalysts can be impregnated into the carbonaceous solids by slurrying with a solution (e.g., aqueous) of the catalyst.
  • a solution e.g., aqueous
  • That portion of the carbonaceous feedstock of a particle size suitable for use in the gasifying reactor can then be further processed, for example, to impregnate one or more catalysts and/or cocatalysts by methods known in the art, for example, as disclosed in US4069304 and US5435940; previously incorporated US4092125, US4468231 and US4551155; previously incorporated U.S. Patent Application Serial Nos. 12/234,012 and 12/234,018; and previously incorporated U.S. Patent Applications Serial No. entitled "PETROLEUM COKE COMPOSITIONS FOR CATALYTIC GASIFICATION"
  • the catalyzed feedstock can be stored for future use or transferred to a feed operation for introduction into the gasification reactor.
  • the catalyzed feedstock can be conveyed to storage or feed operations according to any methods known to those skilled in the art, for example, a screw conveyer or pneumatic transport.
  • the extraction and recovery methods of the present invention are particularly useful in integrated gasification processes for converting carbonaceous feedstocks, such as petroleum coke, liquid petroleum residue and/or coal, to combustible gases, such as methane.
  • the gasification reactors for such processes are typically operated at moderately high pressures and temperature, requiring introduction of a carbonaceous material (i.e. a feedstock) to the reaction zone of the gasification reactor while maintaining the required temperature, pressure, and flow rate of the feedstock.
  • a carbonaceous material i.e. a feedstock
  • Those skilled in the art are familiar with feed systems for providing feedstocks to high pressure and/or temperature environments, including, star feeders, screw feeders, rotary pistons, and lock-hoppers. It should be understood that the feed system can include two or more pressure-balanced elements, such as lock hoppers, which would be used alternately.
  • Suitable gasification reactors include counter-current fixed bed, co-current fixed bed, fluidized bed, entrained flow, and moving bed reactors.
  • the gasification reactor typically will be operated at moderate temperatures of at least about 450 0 C, or of at least about 600 0 C or above, to about 900 0 C, or to about 750 0 C, or to about 700 0 C; and at pressures of at least about 50 psig, or at least about 200 psig, or at least about 400 psig, to about 1000 psig, or to about 700 psig, or to about 600 psig.
  • the gas utilized in the gasification reactor for pressurization and reactions of the particulate composition typically comprises steam, and optionally, oxygen or air, and are supplied to the reactor according to methods known to those skilled in the art.
  • any of the steam boilers known to those skilled in the art can supply steam to the reactor.
  • Such boilers can be powered, for example, through the use of any carbonaceous material such as powdered coal, biomass etc., and including but not limited to rejected carbonaceous materials from the particulate composition preparation operation ⁇ e.g., fines, supra).
  • Steam can also be supplied from a second gasification reactor coupled to a combustion turbine where the exhaust from the reactor is thermally exchanged to a water source and produce steam.
  • Recycled steam from other process operations can also be used for supplying steam to the reactor.
  • the slurried particulate composition is dried with a fluid bed slurry drier, as discussed previously, the steam generated through vaporization can be fed to the gasification reactor.
  • the small amount of required heat input for the catalytic coal gasification reaction can be provided by superheating a gas mixture of steam and recycle gas feeding the gasification reactor by any method known to one skilled in the art.
  • compressed recycle gas of CO and H 2 can be mixed with steam and the resulting steam/recycle gas mixture can be further superheated by heat exchange with the gasification reactor effluent followed by superheating in a recycle gas furnace.
  • a methane reformer can be included in the process to supplement the recycle CO and H 2 fed to the reactor to ensure that the reaction is run under thermally neutral (adiabatic) conditions. In such instances, methane can be supplied for the reformer from the methane product, as described below.
  • Reaction of the particulate composition under the described conditions typically provides a crude product gas and a char.
  • the char produced in the gasification reactor during the present processes typically is removed from the gasification reactor for sampling, purging, and/or catalyst recovery. Methods for removing char are well known to those skilled in the art. One such method taught by EP-A-0102828, for example, can be employed.
  • the char can be periodically withdrawn from the gasification reactor through a lock hopper system, although other methods are known to those skilled in the art.
  • Crude product gas effluent leaving the gasification reactor can pass through a portion of the gasification reactor which serves as a disengagement zone where particles too heavy to be entrained by the gas leaving the gasification reactor (i.e., fines) are returned to the fluidized bed.
  • the disengagement zone can include one or more internal cyclone separators or similar devices for removing fines and particulates from the gas.
  • the gas effluent passing through the disengagement zone and leaving the gasification reactor generally contains CH 4 , CO 2 , H 2 and CO, H 2 S, NH 3 , unreacted steam, entrained fines, and other contaminants such as COS.
  • the gas stream from which the fines have been removed can then be passed through a heat exchanger to cool the gas and the recovered heat can be used to preheat recycle gas and generate high pressure steam. Residual entrained fines can also be removed by any suitable means such as external cyclone separators followed by Venturi scrubbers. The recovered fines can be processed to recover alkali metal catalyst.
  • the gas stream exiting the Venturi scrubbers can be fed to COS hydrolysis reactors for COS removal (sour process) and further cooled in a heat exchanger to recover residual heat prior to entering water scrubbers for ammonia recovery, yielding a scrubbed gas comprising at least H 2 S, CO 2 , CO, H 2 and CH 4 .
  • COS hydrolysis reactors for COS removal sour process
  • a heat exchanger to recover residual heat prior to entering water scrubbers for ammonia recovery, yielding a scrubbed gas comprising at least H 2 S, CO 2 , CO, H 2 and CH 4 .
  • the residual heat from the scrubbed gas can be used to generate low pressure steam.
  • Scrubber water and sour process condensate can be processed to strip and recover H 2 S, CO 2 and NH3; such processes are well known to those skilled in the art.
  • NH3 can typically be recovered as an aqueous solution (e.g., 20 wt%).
  • a subsequent acid gas removal process can be used to remove H 2 S and CO 2 from the scrubbed gas stream by a physical absorption method involving solvent treatment of the gas to give a cleaned gas stream.
  • Such processes involve contacting the scrubbed gas with a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like.
  • a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like.
  • One method can involve the use of Selexol ® (UOP LLC, Des Plaines, IL USA) or Rectisol ® (Lurgi AG, Frankfurt am Main, Germany) solvent having two trains; each train consisting of an H 2 S absorber and a CO 2 absorber.
  • the spent solvent containing H 2 S, CO 2 and other contaminants can be regenerated by any method known to those skilled in the art, including contacting the spent solvent with steam or other stripping gas to remove the contaminants or by passing the spent solvent through stripper columns.
  • Recovered acid gases can be sent for sulfur recovery processing.
  • the resulting cleaned gas stream contains mostly CH 4 , H 2 and CO and, typically, small amounts of CO 2 and H 2 O.
  • Any recovered H 2 S from the acid gas removal and sour water stripping can be converted to elemental sulfur by any method known to those skilled in the art, including the Claus process.
  • Sulfur can be recovered as a molten liquid.
  • the cleaned gas stream can be further processed to separate and recover CH 4 by any suitable gas separation method known to those skilled in the art including, but not limited to, cryogenic distillation and the use of molecular sieves or ceramic membranes.
  • One method for recovering CH 4 from the cleaned gas stream involves the combined use of molecular sieve absorbers to remove residual H 2 O and CO 2 and cryogenic distillation to fractionate and recover CH 4 .
  • two gas streams can be produced by the gas separation process, a methane product stream and a syngas stream (H 2 and CO).
  • the syngas stream can be compressed and recycled to the gasification reactor. If necessary, a portion of the methane product can be directed to a reformer, as discussed previously and/or a portion of the methane product can be used as plant fuel.
  • char as used herein includes mineral ash, unconverted carbonaceous material, and water-soluble alkali metal compounds and water-insoluble alkali metal compounds within the other solids.
  • the char produced in the gasification reactor typically is removed from the gasification reactor for sampling, purging, and/or catalyst recovery. Methods for removing char are well known to those skilled in the art. One such method, described in previously incorporated EP-A-0102828, for example, can be employed.
  • the char can be periodically withdrawn from the gasification reactor through a lock hopper system, although other methods are known to those skilled in the art.
  • Alkali metal salts are useful as catalysts in catalytic coal gasification reactions.
  • Alkali metal catalyst-loaded carbonaceous mixtures are generally prepared and then introduced into a gasification reactor, or can be formed in situ by introducing alkali metal catalyst and carbonaceous particles separately into the reactor.
  • the alkali metal may exist in the char as species that are either soluble or insoluble.
  • alkali metal can react with mineral ash at temperatures above about 500-600 0 C to form insoluble alkali metal aluminosilicates, such as kaliophilite.
  • insoluble alkali metal aluminosilicates such as kaliophilite.
  • the alkali metal is ineffective as a catalyst.
  • char is periodically removed from the gasification reactor through a solid purge. Because the char has a substantial quantity of soluble and insoluble alkali metal, it is desirable to recover the alkali metal from the char for reuse as a gasification catalyst. Catalyst loss in the solid purge must generally be compensated for by a reintroduction of additional catalyst, i.e., a catalyst make-up stream. Processes have been developed to recover alkali metal from the solid purge in order to reduce raw material costs and to minimize environmental impact of a catalytic gasification process. For example, a recovery and recycling process is described in previously incorporated US2007/0277437A1.
  • the present invention provides a novel process for extracting and recovering soluble and insoluble alkali metal from char.
  • a char (10) removed from a gasification reactor can be quenched in an aqueous medium (15) by any suitable means known to those of skill in the art to fracture the char and form a quenched char slurry (20) where the quenched char slurry comprises soluble alkali metal compounds and insoluble matter comprising insoluble alkali metal compounds.
  • a quenched char slurry comprises soluble alkali metal compounds and insoluble matter comprising insoluble alkali metal compounds.
  • One particularly useful quenching method is described in previously incorporated US2007/0277437A1.
  • the invention places no particular limits on the ratio of aqueous medium to char, or on the temperature of the aqueous medium.
  • the wt/wt ratio of water in the aqueous medium to the water-insoluble component of the char ranges from about 3:1, or from about 5:1, up to about 7:1, or up to about 15:1.
  • the aqueous medium has a temperature that ranges from about 95 0 C up to about HO 0 C, or up to about 14O 0 C, or up to about 200 0 C, or up to about 300 0 C.
  • the pressure need not be elevated above atmospheric pressure. In some embodiments, however, the quenching occurs at pressures higher than atmospheric pressure.
  • the quenching may occur at pressures up to about 25 psig, or up to about 40 psig, or up to about 60 psig, or up to about 80 psig, or up to about 400 psig (including the partial pressure of CO 2 ).
  • the quenching process preferably occurs under a stream of gas that is substantially free of oxygen or other oxidants and comprises carbon dioxide.
  • the quenching step fractures the heated char by dissolving the rather large amount of water soluble alkali metal compounds (e.g. , carbonates) that holds it together such that a quenched char slurry results.
  • the char leaves the gasification reactor at high temperature, and it is typically cooled down.
  • the temperature of the char may range from about 35 0 C, or from about 5O 0 C, or from about 75 0 C, up to about 200 0 C, or up to about 300 0 C, or up to about 400 0 C.
  • the char has an elevated temperature ranging from about 5O 0 C to about 600 0 C.
  • the char has an elevated temperature ranging from about 5O 0 C to about 300 0 C.
  • the quenched char slurry comprises both soluble alkali metal and insoluble alkali metal. As the char fractures, soluble alkali metal leaches into the aqueous solution.
  • the char quenching is preferably performed in the substantial absence of gaseous oxygen.
  • the leaching environment has less than about 1% gaseous oxygen, or less than about 0.5% gaseous oxygen, less than about 0.1% gaseous oxygen, less than about 0.01% gaseous oxygen, or less than about 0.005% gaseous oxygen, based on the total volume.
  • the aqueous medium used in the quenching may comprise a wash stream that results from a washing step of the present invention, described, infra.
  • the quenched char slurry (20) can be separated into at least a first liquid stream (25) and an insoluble matter stream (30).
  • the first liquid stream comprises recovered soluble alkali metal compounds solubilized in the quenching process (100) and the insoluble matter stream (30) comprises residual soluble alkali metal compounds and a first insoluble matter.
  • the first insoluble matter generally comprises insoluble alkali metal compounds.
  • the separation and recovery of the first liquid stream from the first insoluble matter (30) may be carried out by typical methods of separating a liquid from a solid particulate.
  • Illustrative methods include, but are not limited to, filtration (gravity or vacuum), centrifugation, use of a fluid press, decantation, and use of hydrocyclones.
  • the recovered first liquid stream will contain soluble alkali metal compounds that may be captured for reuse as a gasification catalyst.
  • Methods for recovery of soluble alkali metal from an aqueous solvent for reuse as a gasification catalyst are known in the art. See, for example, previously incorporated US2007/0277437A1.
  • the recovered first liquid stream comprises at least a portion, or a predominant portion, of the soluble alkali metal compounds from the quenched char slurry.
  • the first liquid stream comprises at least about 50 molar percent, or at least about 55 molar percent, or at least about 60 molar percent, or at least about 65 molar percent, or at least about 70 molar percent, of the soluble alkali metal compounds from the quenched char slurry.
  • the first insoluble matter stream will contain residual moisture (e.g. entrained aqueous solution) ranging from about 30%, at least 40%, or at least 50%, up to about 60%, or up to 70%, based on the total weight of the insoluble matter .
  • residual moisture e.g. entrained aqueous solution
  • the first insoluble matter (30) can be contacted with an alkali metal hydroxide and calcium oxide, calcium hydroxide, or both (35) under suitable pressure and temperature so as to convert at least a portion of the insoluble alkali metal compounds in the first insoluble matter to one or more soluble alkali metal compounds and produce a first leached slurry (40) comprising soluble alkali metal compounds and partially extracted insoluble matter, wherein the partially extracted insoluble matter comprises insoluble alkali metal compounds.
  • the contacting of the first insoluble matter (30) with the alkali metal hydroxide and calcium oxide, calcium hydroxide, or both (35) typically involves contacting the matter at an elevated temperature with one or more aqueous solutions or slurries of the alkali metal hydroxide and calcium oxide, calcium hydroxide, or both such that at least a portion of the alkali metal from the first insoluble matter is extracted.
  • the alkali metal hydroxide is provided to the quenched char slurry (20) as an aqueous solution having a concentration ranging from about 1 to about 10 M alkali metal hydroxide.
  • the alkali metal hydroxide can comprise any of LiOH, NaOH, KOH, RbOH, and CsOH as well as mixtures thereof; preferably, the alkali metal comprises NaOH or KOH. Most preferably the alkali metal hydroxide comprises KOH.
  • the calcium oxide and/or calcium hydroxide is generally provided to the first insoluble matter (30) as separate aqueous solution having a concentration ranging from about 0.1 to 10 M in calcium.
  • the calcium oxide and/or calcium hydroxide may be provided to the first insoluble matter either simultaneously with the alkali metal hydroxide or separately.
  • the alkali metal hydroxide and calcium oxide, calcium hydroxide, or both may comprise a single aqueous solution which is provided to the first insoluble matter.
  • the amount of calcium oxide and/or calcium hydroxide provided to the first insoluble matter may be less than or equal to 1 : 1 molar ratio of calcium to silica in the first insoluble matter; preferably, the amount of calcium oxide and/or calcium hydroxide provided to the first insoluble matter comprises a ratio ranging from 0.1 :1 to 1 :1 molar ratio of calcium carbonate to silicon dioxide in the first insoluble matter.
  • the slurry formed from the first insoluble matter (30) and the alkali metal hydroxide and calcium oxide, calcium hydroxide, or both (35), can be pressurized and heated by the introduction of heated and pressurized steam.
  • the temperature of the slurry can range from about 100 0 C, or from about 125 0 C, or from about 15O 0 C, up to about 24O 0 C, up to about 27O 0 C, or up to about 300 0 C.
  • the slurry has an elevated temperature ranging from about 15O 0 C to about 24O 0 C.
  • the slurry has an elevated temperature ranging from about 100 0 C to about 15O 0 C.
  • the slurry can be maintained at a pressure of from about 25 psig, or from about 35 psig, or from about 50 psig, up to about 250 psig, or up to 500 psig, or up to about 750 psig, or up to 1000 psig. In some embodiments, the slurry may be maintained at a pressure of from about 50 to 500 psig. In other embodiments, the slurry may be maintained at a pressure of from about 50 to 250 psig.
  • the slurry of the first insoluble matter (30) and the alkali metal hydroxide and calcium oxide, calcium hydroxide, or both, can be maintained at an appropriate temperature and pressure for a residence time ranging from about 1 minute, or about 5 minutes, or about 15 minutes, or about 30 minutes, up to about 60 minutes, or up to about 120 minutes, or up to about 150 minutes, or up to about 180 minutes. In some embodiments, the slurry may be maintained at an appropriate temperature and pressure for a residence time ranging from 30 minutes to 150 minutes.
  • the contacting takes place in a pressurized leaching operation using at least two, and preferably three, continuous stirred-tank reactors (CSTRs), either in series (e.g. , co-current), or a single horizontal pressure vessel with internal weirs and stirrers to provide three to six internal stages for the slurry (the gas phase may optionally be separated by stages).
  • CSTRs continuous stirred-tank reactors
  • the contacting of the first leached slurry (40) with carbon dioxide (45) occurs under pressure and temperature suitable to convert at least a portion, or even a predominant portion, of the insoluble alkali metal compounds in the partially extracted insoluble matter to one or more soluble alkali metal compounds, and produce a second leached slurry comprising the soluble alkali metal compounds and a residual insoluble matter.
  • this process step is referred to as a leaching or a hydrothermal leaching.
  • the temperature and/or pressure of the first leached slurry (40) can be reduced according to those methods known to those skilled in the art.
  • the first leached slurry can be flashed into a flash drum.
  • Water can also be evaporated from the first leached slurry (40) to increase the concentration of alkali metals in the slurry solution.
  • the first leached slurry may be cooled to a temperature ranging from about 120 0 C to 145°C, and a pressure to 45 psig or less, prior to contacting the first leached slurry with carbon dioxide.
  • the hydrothermal leaching process converts a portion the insoluble alkali metal compounds in the partially extracted insoluble matter to one or more soluble alkali metal compounds, as well as neutralizes excess alkalinity, hydrolyzes carbonates, precipitates silica and/or alumina, and strips sulf ⁇ dic sulfur as hydrogen sulfide to yield a second leached slurry (50) comprising soluble alkali metal compounds and a residual insoluble matter.
  • the alkali metal in the second leached slurry (50) comprises at least alkali metal carbonate and the pH of the solution generally ranges from about seven, or about eight, or about nine, up to about ten, or up to about eleven, or up to about twelve.
  • the hydrothermal leaching may be performed by any suitable means known to those of skill in the art for performing hydrothermal leaching.
  • the first hydrothermal leaching step is carried out in three pressurized continuous flow stirred tank reactors (CSTRs) in series (in three co-current stages).
  • CSTRs continuous flow stirred tank reactors
  • the first hydrothermal leaching step is carried out in a single horizontal pressure leaching vessel with internal weirs and stirrers to provide between 3-6 internal stages for the slurry.
  • the contacting of the carbon dioxide (45) with the first leached slurry (40) may occur by any means known to those of skill in the art suitable for introducing a gas into a slurry. Suitable methods include, but are not limited to, solubilizing the gas under pressure with gas-phase entrainment stirring or bubbling the gas through the slurry.
  • suitable temperatures and pressure including partial pressures of various gases
  • duration of the leaching may be selected based on the knowledge of one skilled in the art. This choice may depend on, among other factors, the composition of the carbonaceous feedstock: Higher temperatures and/or pressures may be more suitable for carbonaceous feedstock having higher mineral ash content (e.g., Powder River Basin coal with 7-10% ash). Suitable temperatures may, for example, range from about 9O 0 C, or from about 100 0 C, or from about HO 0 C, up to about 12O 0 C, or up to about 13O 0 C, or up to about 14O 0 C, or up to about 16O 0 C.
  • the leaching is typically carried out in the presence of steam.
  • Suitable partial pressures of steam range from about 3 psig, or from about 6 psig, up to about 14 psig, up to about 20 psig.
  • Suitable total pressures range from about 30 psig, or from about 40 psig, or from about 50 psig, up to about 75 psig, or up to about 90 psig, or up to about 110 psig.
  • Suitable partial pressures of carbon dioxide may, for example, range from about 25 psig, from about 40 psig, or from about 60 psig, to about 100 psig, to about 120 psig, to about 140 psig, or to about 170 psig.
  • the first leaching process converts at least a portion, or even a predominant portion, of the insoluble alkali metal compounds to one or more soluble alkali metal compounds.
  • the conversion of insoluble alkali metal compounds to soluble alkali metal compounds generally involves the chemical conversion of a water-insoluble alkali metal compound (such as potassium aluminosilicate) into a water- soluble alkali metal compound (such as potassium carbonate).
  • the amount of insoluble alkali metal compounds converted to soluble alkali metal compounds in this leaching step will depend on a variety of factors, including the composition of the char, the temperature, the pressure (including the partial pressures of steam and carbon dioxide), and the duration of the leaching operation.
  • the amount of insoluble alkali metal compound converted will also depend on the composition of the insoluble alkali metal compounds present in the char. Some insoluble alkali metal compounds, such as kaliophilite, are more difficult to convert into soluble alkali metal compounds than others.
  • the first leaching step may convert at least about 5%, or at least about 10%, or at least about 20%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80% of the insoluble alkali metal compounds from the insoluble matter, based on the total moles of insoluble alkali metal compounds in the quenched char.
  • the alkali metal hydroxide and calcium contacting and/or the first hydrothermal leaching step is combined with the char quenching step into a single step.
  • the char quenching is performed at a pressure and temperature more typical for the first hydrothermal leaching step. Suitable temperatures may, for example, range from about 9O 0 C, or from about 100 0 C, or from about HO 0 C, up to about 12O 0 C, or up to about 13O 0 C, or up to about 14O 0 C, or up to about 16O 0 C.
  • Suitable total pressures for example, range from about 30 psig, or from about 40 psig, or from about 50 psig, up to about 75 psig, or up to about 90 psig, or up to about 110 psig.
  • the partial pressures of carbon dioxide and steam are similar to those for the first leaching step.
  • the combined quenching/leaching step substantially leaches the water- soluble alkali metal compounds from the insoluble matter and converts at least a portion of the insoluble alkali metal compounds in the char to one or more soluble alkali metal compounds, and thereby produces a second leached slurry comprising soluble alkali metal compounds and residual insoluble matter.
  • the bulk of the slurry solids will act as a filtering aid for any fine (e.g., colloidal) silica and alumina precipitate.
  • the second leached slurry (50) can be separated into at least a second liquid stream (55) and a residual insoluble matter stream (60).
  • the second liquid stream comprises recovered soluble alkali metal compounds, including soluble alkali metal compounds that were converted from insoluble alkali metal compounds in the char.
  • the residual insoluble matter steam (60) comprises at least a portion of the alkali metal contained in the insoluble matter of the char.
  • the residual insoluble matter steam comprises less than about 95 molar percent, or less than about 90 molar percent, or less than about 80 molar percent, or less than about 60 molar percent, or less than about 50 molar percent, or less than about 40 molar percent, or less than about 30 molar percent, of the alkali metal contained in the insoluble matter of the char.
  • the separation and recovery of the second liquid stream from the solid stream (60) may be carried out by typical methods of separating a liquid from a solid particulate.
  • Illustrative methods include, but are not limited to, filtration (gravity or vacuum), centrifugation, use of a fluid press, decantation, and use of hydrocyclones.
  • Separation and recovery steps are generally performed following contacting of the insoluble matter with carbon dioxide and degassing to remove excess carbon dioxide and hydrogen sulfide.
  • the recovered second liquid stream will contain soluble alkali metal compounds that may be captured for reuse as a gasification catalyst.
  • Methods for recovery of soluble alkali metal from an aqueous solvent for reuse as a gasification catalyst are known in the art. See, for example, previously incorporated US2007/0277437A1.
  • the recovered second liquid stream comprises at least a portion, or even a predominant portion of the soluble alkali metal compounds from the second leached slurry.
  • the second liquid stream comprises at least about 50 molar percent, or at least about 55 molar percent, or at least about 60 molar percent, or at least about 65 molar percent, or at least about 70 molar percent, of the soluble alkali metal compounds from the second leached slurry.
  • the second leached slurry (50) may be degassed under suitable pressures and temperatures so as to remove a substantial portion of the excess carbon dioxide and hydrogen sulfide, if present, and produce a degassed second leached slurry (50) prior to separating the second liquid stream (55) and a residual insoluble matter stream (60).
  • any suitable degassing methods known to those of skill in the art may be used to perform the degassing step.
  • the degassing may be performed by pumping and heating the second leached slurry and flashing it into a flash drum.
  • a suitable temperature may be, for example, about 13O 0 C or higher, or about 14O 0 C or higher, about 145 0 C or higher, or about 15O 0 C or higher.
  • the slurry temperature may drop to 12O 0 C or less, or HO 0 C or less, or 100 0 C or less, or 95 0 C or less.
  • suitable pressures range from about 10 to about 20 psig, or at about atmospheric pressure.
  • the degassing may be performed by feeding a heated pressurized solution into a series of staged pressure let-down vessels equipped with stirring or other recirculation mechanisms.
  • the slurry may be cooled prior to being fed into a first pressure let-down vessel, for example to a suitable temperature of about 17O 0 C or below, or to about 15O 0 C or below, or to about 13O 0 C or below.
  • Suitable pressures will depend on the pressure under which the first hydrothermal leaching was performed. Suitable pressures for degassing are, for example, about 300 psig or less, or about 100 psig or less, or about 50 psig or less, or about 25 psig or less.
  • the off-stream gas may be handled by any means known to those of skill in the art.
  • the off gases from a let-down vessel may be fed, as needed, through gas/water breakdown drums and the separated water recycled into the degassed slurry.
  • the degassing apparatus is equipped with safety features for handling hydrogen sulfide as an off gas.
  • the degassing step results in the substantial removal of excess carbon dioxide.
  • the partial pressure of carbon dioxide is reduced to less than about 10 psig, or less than about 5 psig, or less than about 2 psig.
  • the degassing also results in the substantial removal of excess hydrogen sulfide, if present.
  • the partial pressure of hydrogen sulfide is reduced to less than about 1 psig, or less than about 0.1 psig, less than about 0.05 psig, or less than about 0.01 psig.
  • the residual insoluble matter stream (60) is produced comprising a residual amount of soluble alkali metal compounds in addition to residual insoluble alkali metal compounds.
  • the residual insoluble matter stream (60) can be washed with an aqueous medium (65) to substantially recover the residual soluble alkali metal compounds present in the residual insoluble matter as a first wash stream (70).
  • the residual soluble alkali metal compounds consists of soluble alkali metal compounds that failed to separate into the second liquid stream during separation ⁇ e.g., entrained aqueous solution).
  • the amount of entrained solution in the residual insoluble matter stream will depend on the particle size of the residual insoluble matter as well as the concentration of the soluble alkali metal compounds in the entrained solution, as are familiar to those skilled in the art.
  • the residual insoluble matter stream is washed with an aqueous medium to produce a first wash stream comprising at least a portion, or a predominant portion, or substantially all of the residual soluble alkali metal compounds in the residual insoluble matter stream.
  • the first wash stream may, for example, comprise more than about 60%, or more than about 75%, or more than about 90%, or more than about 95%, of the residual alkali metal in the residual insoluble matter stream, based on the total weight of residual alkali metal.
  • each washing step may include multiple staged counter-washings of the insoluble matter.
  • the washing of the residual insoluble matter stream comprises at least two staged counter- washings.
  • the washing of the residual insoluble matter stream comprises at least five staged counter- washings.
  • the washing may be performed according to any suitable method known to those of skill in the art.
  • the washing step may be performed using a continuous multi-stage counter-current system whereby solids and liquids travel in opposite directions.
  • the multi-stage counter current wash system may include mixers/settlers (CCD or decantation), mixers/filters, mixers/hydrocyclones, mixers/centrifuges, belt filters, and the like.
  • the first wash stream (70) is recovered by typical means of separating a solid particulate from a liquid.
  • Illustrative methods include, but are not limited to, filtration (gravity or vacuum), centrifugation, and use of a fluid press.
  • the recovered first wash stream may be used as at least part of the aqueous medium used for quenching the char.
  • Example 1 Process that can be used for catalyst extraction from a carbonaceous char
  • Hot char produced from the gasification of a potassium- loaded coal feedstock (lignite) is discharged directly into a quench slurry tank at about atmospheric pressure.
  • Wash solution is introduced (recycled from a downstream CC Washing operation) containing about 25-40% of the total K.
  • the concentration is such that the water insoluble char solids and the liquid phase gives a slurry density of about 20% solids.
  • the temperature of the quench solution is about 95-100 0 C, and the steam that is generated (about 6-10% of the water) is condensed and recycled as wash water in the integrated process.
  • the main K species will be carbonates with possible amounts of hydroxide.
  • the hot quench slurry is thoroughly dewatered by filtration and the filtered solids are washed (displacement washing on filter) with a KOH solution.
  • the filtrate and the displacement KOH wash solution are each split into 2 streams: one of each stream is fed into the following section, while the other goes to an evaporator for recycling for catalyst loading on the coal feedstock.
  • the filter cake from the filtration will contain char residue with water insoluble potassium minerals, and the wetting solution containing potassium hydroxide and some reduced amount of potassium carbonate.
  • the filter cake is introduced into a horizontal pressure vessel (autoclave) with three internal stages (weirs and stirrers).
  • a KOH solution (recovered from below), plus a concentrated ⁇ e.g., 30-85%) process make-up KOH are introduced co-currently with the filter cake into the continuous multistage pressure vessel.
  • the total residence time in the continuous staged pressure vessel is about 2 hours.
  • the temperature is between 150-250 0 C, the slurry density is about 20% solids.
  • An amount of a lime slurry containing less than a 1 :1 molar ratio of calcium to SiO 2 in the char, is added into the last stage of the pressure vessel before discharge.
  • the digested slurry is discharged into a pressure let down stirred reactor also equipped with spurgers for CO 2 .
  • the temperature is between 100-150 0 C.
  • the carbonated and hydrolyzed slurry is filtered to separate solids from a rich K2CO3 solution which is recycled to a catalyst loading operation via an evaporator to concentrate the solution as needed to maintain water balance in the system.
  • the separated solids are fed into a multi stage counter current washing operation consisting of a number of mixer/separator stages where the wash solution and the solids travel counter-currently.
  • the mixers are themselves co-current multi stage (2-3 stages) CSTRs.
  • the residence time in the mixers is about 1-2 hours.
  • the water to solids ratio for efficient washing/separation is between 4:1 and 6:1 water to solids.
  • the K 2 CO 3 containing wash solution is recycled to the char quenching ⁇ supra).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Industrial Gases (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne des procédés permettant l'extraction et la récupération de métal alcalin à partir du résidu carboné qui résulte de la gazéification catalytique d'une substance carbonée. Parmi d'autres étapes, les procédés de l'invention comprennent une étape de lixiviation hydrothermique dans laquelle une boue de matières particulaires insolubles comprenant des composés métalliques alcalins insolubles est traitée avec du dioxyde de carbone et de la vapeur à des températures et des pressions élevées pour effectuer la conversion des composés métalliques alcalins insolubles en composés métalliques alcalins solubles. L'invention concerne en outre des procédés de gazéification catalytique d'une substance carbonée, une partie substantielle du métal alcalin étant extrait et récupéré à partir du résidu carboné qui résulte du procédé de gazéification catalytique.
PCT/US2008/088140 2007-12-28 2008-12-23 Procédé de gazéification catalytique avec récupération de métal alcalin à partir du résidu carboné WO2009086361A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1729307P 2007-12-28 2007-12-28
US61/017,293 2007-12-28

Publications (2)

Publication Number Publication Date
WO2009086361A2 true WO2009086361A2 (fr) 2009-07-09
WO2009086361A3 WO2009086361A3 (fr) 2009-11-19

Family

ID=40445551

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/088140 WO2009086361A2 (fr) 2007-12-28 2008-12-23 Procédé de gazéification catalytique avec récupération de métal alcalin à partir du résidu carboné

Country Status (2)

Country Link
US (1) US20090165383A1 (fr)
WO (1) WO2009086361A2 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8999020B2 (en) 2008-04-01 2015-04-07 Greatpoint Energy, Inc. Processes for the separation of methane from a gas stream
US9012524B2 (en) 2011-10-06 2015-04-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9034058B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9034061B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9127221B2 (en) 2011-06-03 2015-09-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US9273260B2 (en) 2012-10-01 2016-03-01 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9328920B2 (en) 2012-10-01 2016-05-03 Greatpoint Energy, Inc. Use of contaminated low-rank coal for combustion
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

Families Citing this family (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8114176B2 (en) 2005-10-12 2012-02-14 Great Point Energy, Inc. Catalytic steam gasification of petroleum coke to methane
US7922782B2 (en) 2006-06-01 2011-04-12 Greatpoint Energy, Inc. Catalytic steam gasification process with recovery and recycle of alkali metal compounds
AU2008282518B2 (en) 2007-08-02 2012-03-01 Greatpoint Energy, Inc. Catalyst-loaded coal compositions, methods of making and use
US7897126B2 (en) 2007-12-28 2011-03-01 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
WO2009086377A2 (fr) 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Procédé de gazéification catalytique avec récupération de métal alcalin à partir du résidu carboné
US8123827B2 (en) 2007-12-28 2012-02-28 Greatpoint Energy, Inc. Processes for making syngas-derived products
US8286901B2 (en) 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8349039B2 (en) 2008-02-29 2013-01-08 Greatpoint Energy, Inc. Carbonaceous fines recycle
US8709113B2 (en) 2008-02-29 2014-04-29 Greatpoint Energy, Inc. Steam generation processes utilizing biomass feedstocks
WO2009111345A2 (fr) 2008-02-29 2009-09-11 Greatpoint Energy, Inc. Compositions particulaires de gazéification catalytique
US7926750B2 (en) 2008-02-29 2011-04-19 Greatpoint Energy, Inc. Compactor feeder
US8652222B2 (en) 2008-02-29 2014-02-18 Greatpoint Energy, Inc. Biomass compositions for catalytic gasification
US8114177B2 (en) 2008-02-29 2012-02-14 Greatpoint Energy, Inc. Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
WO2009111332A2 (fr) 2008-02-29 2009-09-11 Greatpoint Energy, Inc. Procédés de génération de vapeur à bilan co2 réduit
US8297542B2 (en) 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
CN101983228A (zh) 2008-04-01 2011-03-02 格雷特波因特能源公司 从气流中除去一氧化碳的酸性变换方法
CA2735137C (fr) 2008-09-19 2013-05-21 Greatpoint Energy, Inc. Traitements pour la gazeification d'une matiere carbonee
US8647402B2 (en) * 2008-09-19 2014-02-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8502007B2 (en) 2008-09-19 2013-08-06 Greatpoint Energy, Inc. Char methanation catalyst and its use in gasification processes
US8202913B2 (en) 2008-10-23 2012-06-19 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8734548B2 (en) 2008-12-30 2014-05-27 Greatpoint Energy, Inc. Processes for preparing a catalyzed coal particulate
US8734547B2 (en) 2008-12-30 2014-05-27 Greatpoint Energy, Inc. Processes for preparing a catalyzed carbonaceous particulate
US8343243B2 (en) * 2009-03-31 2013-01-01 General Electric Company Method and apparatus for blending lignite and coke slurries
US8268899B2 (en) 2009-05-13 2012-09-18 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
CA2759961C (fr) 2009-05-13 2013-12-17 Greatpoint Energy, Inc. Procedes d'hydromethanation de charges d'alimentation carbonees
CN102459525B (zh) 2009-05-13 2016-09-21 格雷特波因特能源公司 进行含碳原料的加氢甲烷化的方法
US20110011721A1 (en) * 2009-07-16 2011-01-20 Champagne Gary E Vacuum Pyrolytic Gasification And Liquefaction To Produce Liquid And Gaseous Fuels From Biomass
US20110031439A1 (en) 2009-08-06 2011-02-10 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US20110064648A1 (en) * 2009-09-16 2011-03-17 Greatpoint Energy, Inc. Two-mode process for hydrogen production
WO2011034889A1 (fr) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Processus intégré d'hydrométhanation à cycle combiné
WO2011034890A2 (fr) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Processus intégré à cycle combiné d'hydrométhanation
EP2478071A1 (fr) 2009-09-16 2012-07-25 Greatpoint Energy, Inc. Procédés d'hydrométhanation d'une charge d'alimentation carbonée
CN102597417B (zh) 2009-10-19 2014-10-01 格雷特波因特能源公司 整合的强化采油方法
AU2010310846B2 (en) 2009-10-19 2013-05-30 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011084580A2 (fr) 2009-12-17 2011-07-14 Greatpoint Energy, Inc. Processus intégré de récupération assistée des hydrocarbures
US20110146978A1 (en) 2009-12-17 2011-06-23 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
CN102754266B (zh) 2010-02-23 2015-09-02 格雷特波因特能源公司 集成的加氢甲烷化燃料电池发电
US8652696B2 (en) 2010-03-08 2014-02-18 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
WO2011139694A1 (fr) 2010-04-26 2011-11-10 Greatpoint Energy, Inc. Hydrométhanation d'une charge carbonée à récupération de vanadium
CN102906230B (zh) 2010-05-28 2015-09-02 格雷特波因特能源公司 液体重烃进料向气态产物的转化
EP2606109A1 (fr) 2010-08-18 2013-06-26 Greatpoint Energy, Inc. Hydrométhanation de charges carbonées
CN103080285A (zh) 2010-09-10 2013-05-01 格雷特波因特能源公司 含碳原料的加氢甲烷化
WO2012061238A1 (fr) 2010-11-01 2012-05-10 Greatpoint Energy, Inc. Hydrométhanation d'une charge de départ carbonée
CN103391989B (zh) 2011-02-23 2015-03-25 格雷特波因特能源公司 伴有镍回收的碳质原料加氢甲烷化
EP3354711A1 (fr) 2011-03-29 2018-08-01 Fuelina Technologies, LLC Carburant hybride et son procédé de fabrication
WO2012145497A1 (fr) 2011-04-22 2012-10-26 Greatpoint Energy, Inc. Hydrométhanation d'une matière première carbonée avec valorisation des produits de carbonisation
CN103890147A (zh) 2011-08-17 2014-06-25 格雷特波因特能源公司 碳质原料的加氢甲烷化
WO2013025808A1 (fr) 2011-08-17 2013-02-21 Greatpoint Energy, Inc. Hydrométhanation d'une charge d'alimentation carbonée
WO2014007898A1 (fr) * 2012-07-03 2014-01-09 Battelle Memorial Institute Procédés d'élimination de sulfate dans une gazéification hydrothermale catalytique en phase liquide d'une biomasse
US11268038B2 (en) 2014-09-05 2022-03-08 Raven Sr, Inc. Process for duplex rotary reformer
WO2016089994A1 (fr) 2014-12-03 2016-06-09 Drexel University Incorporation directe de gaz naturel dans des combustibles liquides hydrocarbonés
JP6960930B2 (ja) 2016-02-18 2021-11-05 ８ リバーズ キャピタル，エルエルシー メタン生成を含む電力生産のためのシステムおよび方法
CN108753360B (zh) * 2018-06-01 2020-08-28 新奥科技发展有限公司 一种排渣系统、煤催化气化系统及煤催化气化方法
CN111171889B (zh) * 2019-12-05 2021-06-22 南京工业大学 高浓度有机废水及有机固废处理工艺及系统
CN115888673A (zh) * 2022-11-14 2023-04-04 陕西煤业新型能源科技股份有限公司 一种利用煤气化细渣制备吸附材料的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219338A (en) * 1978-05-17 1980-08-26 Exxon Research & Engineering Co. Hydrothermal alkali metal recovery process
US4260421A (en) * 1979-05-18 1981-04-07 Exxon Research & Engineering Co. Cement production from coal conversion residues
US4459138A (en) * 1982-12-06 1984-07-10 The United States Of America As Represented By The United States Department Of Energy Recovery of alkali metal constituents from catalytic coal conversion residues
US20070277437A1 (en) * 2006-06-01 2007-12-06 Sheth Atul C Catalytic steam gasification process with recovery and recycle of alkali metal compounds

Family Cites Families (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2886405A (en) * 1956-02-24 1959-05-12 Benson Homer Edwin Method for separating co2 and h2s from gas mixtures
US3435590A (en) * 1967-09-01 1969-04-01 Chevron Res Co2 and h2s removal
US3594985A (en) * 1969-06-11 1971-07-27 Allied Chem Acid gas removal from gas mixtures
US3740193A (en) * 1971-03-18 1973-06-19 Exxon Research Engineering Co Hydrogen production by catalytic steam gasification of carbonaceous materials
US3969089A (en) * 1971-11-12 1976-07-13 Exxon Research And Engineering Company Manufacture of combustible gases
US4094650A (en) * 1972-09-08 1978-06-13 Exxon Research & Engineering Co. Integrated catalytic gasification process
US4021370A (en) * 1973-07-24 1977-05-03 Davy Powergas Limited Fuel gas production
US3958957A (en) * 1974-07-01 1976-05-25 Exxon Research And Engineering Company Methane production
GB1508712A (en) * 1975-03-31 1978-04-26 Battelle Memorial Institute Treating solid fuel
US4091073A (en) * 1975-08-29 1978-05-23 Shell Oil Company Process for the removal of H2 S and CO2 from gaseous streams
US4005996A (en) * 1975-09-04 1977-02-01 El Paso Natural Gas Company Methanation process for the production of an alternate fuel for natural gas
US4077778A (en) * 1975-09-29 1978-03-07 Exxon Research & Engineering Co. Process for the catalytic gasification of coal
DE2551717C3 (de) * 1975-11-18 1980-11-13 Basf Ag, 6700 Ludwigshafen und ggf. COS aus Gasen
US4069304A (en) * 1975-12-31 1978-01-17 Trw Hydrogen production by catalytic coal gasification
US4330305A (en) * 1976-03-19 1982-05-18 Basf Aktiengesellschaft Removal of CO2 and/or H2 S from gases
JPS5311893A (en) * 1976-07-20 1978-02-02 Fujimi Kenmazai Kougiyou Kk Catalysts
US4159195A (en) * 1977-01-24 1979-06-26 Exxon Research & Engineering Co. Hydrothermal alkali metal recovery process
US4211538A (en) * 1977-02-25 1980-07-08 Exxon Research & Engineering Co. Process for the production of an intermediate Btu gas
US4100256A (en) * 1977-03-18 1978-07-11 The Dow Chemical Company Hydrolysis of carbon oxysulfide
US4152119A (en) * 1977-08-01 1979-05-01 Dynecology Incorporated Briquette comprising caking coal and municipal solid waste
US4204843A (en) * 1977-12-19 1980-05-27 Exxon Research & Engineering Co. Gasification process
US4200439A (en) * 1977-12-19 1980-04-29 Exxon Research & Engineering Co. Gasification process using ion-exchanged coal
US4157246A (en) * 1978-01-27 1979-06-05 Exxon Research & Engineering Co. Hydrothermal alkali metal catalyst recovery process
US4265868A (en) * 1978-02-08 1981-05-05 Koppers Company, Inc. Production of carbon monoxide by the gasification of carbonaceous materials
US4193771A (en) * 1978-05-08 1980-03-18 Exxon Research & Engineering Co. Alkali metal recovery from carbonaceous material conversion process
US4193772A (en) * 1978-06-05 1980-03-18 Exxon Research & Engineering Co. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue
US4318712A (en) * 1978-07-17 1982-03-09 Exxon Research & Engineering Co. Catalytic coal gasification process
GB2027444B (en) * 1978-07-28 1983-03-02 Exxon Research Engineering Co Gasification of ash-containing solid fuels
US4211669A (en) * 1978-11-09 1980-07-08 Exxon Research & Engineering Co. Process for the production of a chemical synthesis gas from coal
US4243639A (en) * 1979-05-10 1981-01-06 Tosco Corporation Method for recovering vanadium from petroleum coke
US4334893A (en) * 1979-06-25 1982-06-15 Exxon Research & Engineering Co. Recovery of alkali metal catalyst constituents with sulfurous acid
US4315758A (en) * 1979-10-15 1982-02-16 Institute Of Gas Technology Process for the production of fuel gas from coal
US4462814A (en) * 1979-11-14 1984-07-31 Koch Process Systems, Inc. Distillative separations of gas mixtures containing methane, carbon dioxide and other components
US4331451A (en) * 1980-02-04 1982-05-25 Mitsui Toatsu Chemicals, Inc. Catalytic gasification
US4336034A (en) * 1980-03-10 1982-06-22 Exxon Research & Engineering Co. Process for the catalytic gasification of coal
EP0061326B1 (fr) * 1981-03-24 1985-06-19 Exxon Research And Engineering Company Appareil pour convertir un combustible en gaz de combustion
NL8101447A (nl) * 1981-03-24 1982-10-18 Shell Int Research Werkwijze voor de bereiding van koolwaterstoffen uit koolstofhoudend materiaal.
DE3113993A1 (de) * 1981-04-07 1982-11-11 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur gleichzeitigen erzeugung von brenngas und prozesswaerme aus kohlenstoffhaltigen materialien
US4500323A (en) * 1981-08-26 1985-02-19 Kraftwerk Union Aktiengesellschaft Process for the gasification of raw carboniferous materials
US4432773A (en) * 1981-09-14 1984-02-21 Euker Jr Charles A Fluidized bed catalytic coal gasification process
US4439210A (en) * 1981-09-25 1984-03-27 Conoco Inc. Method of catalytic gasification with increased ash fusion temperature
EP0093501B1 (fr) * 1982-03-29 1988-07-13 Asahi Kasei Kogyo Kabushiki Kaisha Procédé de craquage thermique de matières carbonées qui augmente la conversion en essence et en huiles légères
DE3217366A1 (de) * 1982-05-08 1983-11-10 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur herstellung eines weitgehend inertfreien gases zur synthese
US5630854A (en) * 1982-05-20 1997-05-20 Battelle Memorial Institute Method for catalytic destruction of organic materials
US4436531A (en) * 1982-08-27 1984-03-13 Texaco Development Corporation Synthesis gas from slurries of solid carbonaceous fuels
US4597776A (en) * 1982-10-01 1986-07-01 Rockwell International Corporation Hydropyrolysis process
US4515764A (en) * 1983-12-20 1985-05-07 Shell Oil Company Removal of H2 S from gaseous streams
US4597775A (en) * 1984-04-20 1986-07-01 Exxon Research And Engineering Co. Coking and gasification process
DE3439487A1 (de) * 1984-10-27 1986-06-26 M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 4200 Oberhausen Energieguenstiges verfahren zur erzeugung von synthesegas mit einem hohen methangehalt
US4682986A (en) * 1984-11-29 1987-07-28 Exxon Research And Engineering Process for separating catalytic coal gasification chars
US4668428A (en) * 1985-06-27 1987-05-26 Texaco Inc. Partial oxidation process
US4668429A (en) * 1985-06-27 1987-05-26 Texaco Inc. Partial oxidation process
US4720289A (en) * 1985-07-05 1988-01-19 Exxon Research And Engineering Company Process for gasifying solid carbonaceous materials
US4675035A (en) * 1986-02-24 1987-06-23 Apffel Fred P Carbon dioxide absorption methanol process
US4747938A (en) * 1986-04-17 1988-05-31 The United States Of America As Represented By The United States Department Of Energy Low temperature pyrolysis of coal or oil shale in the presence of calcium compounds
US5223173A (en) * 1986-05-01 1993-06-29 The Dow Chemical Company Method and composition for the removal of hydrogen sulfide from gaseous streams
CA1300885C (fr) * 1986-08-26 1992-05-19 Donald S. Scott Hydrogazeification de biomasse pour la production de rendements eleves de methane
JPS6395292A (ja) * 1986-10-09 1988-04-26 Univ Tohoku 塩化物を利用した石炭の接触ガス化法
US4803061A (en) * 1986-12-29 1989-02-07 Texaco Inc. Partial oxidation process with magnetic separation of the ground slag
US5132007A (en) * 1987-06-08 1992-07-21 Carbon Fuels Corporation Co-generation system for co-producing clean, coal-based fuels and electricity
IT1222811B (it) * 1987-10-02 1990-09-12 Eniricerche Spa Procedimento per la liquefazione del carbone in un unico stadio
US5093094A (en) * 1989-05-05 1992-03-03 Shell Oil Company Solution removal of H2 S from gas streams
JPH075895B2 (ja) * 1989-09-29 1995-01-25 宇部興産株式会社 ガス化炉壁へのアッシュ分の付着防止法
US5094737A (en) * 1990-10-01 1992-03-10 Exxon Research & Engineering Company Integrated coking-gasification process with mitigation of bogging and slagging
US5277884A (en) * 1992-03-02 1994-01-11 Reuel Shinnar Solvents for the selective removal of H2 S from gases containing both H2 S and CO2
DK0643756T3 (da) * 1992-06-05 1999-02-15 Battelle Memorial Institute Fremgangsmåde til katalytisk omdannelse af organisk materiale til et gasprodukt
US5865898A (en) * 1992-08-06 1999-02-02 The Texas A&M University System Methods of biomass pretreatment
US5733515A (en) * 1993-01-21 1998-03-31 Calgon Carbon Corporation Purification of air in enclosed spaces
US5720785A (en) * 1993-04-30 1998-02-24 Shell Oil Company Method of reducing hydrogen cyanide and ammonia in synthesis gas
US5964985A (en) * 1994-02-02 1999-10-12 Wootten; William A. Method and apparatus for converting coal to liquid hydrocarbons
US6506349B1 (en) * 1994-11-03 2003-01-14 Tofik K. Khanmamedov Process for removal of contaminants from a gas stream
US5641327A (en) * 1994-12-02 1997-06-24 Leas; Arnold M. Catalytic gasification process and system for producing medium grade BTU gas
US5855631A (en) * 1994-12-02 1999-01-05 Leas; Arnold M. Catalytic gasification process and system
US6028234A (en) * 1996-12-17 2000-02-22 Mobil Oil Corporation Process for making gas hydrates
US6180843B1 (en) * 1997-10-14 2001-01-30 Mobil Oil Corporation Method for producing gas hydrates utilizing a fluidized bed
US6187465B1 (en) * 1997-11-07 2001-02-13 Terry R. Galloway Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US6168768B1 (en) * 1998-01-23 2001-01-02 Exxon Research And Engineering Company Production of low sulfer syngas from natural gas with C4+/C5+ hydrocarbon recovery
US6015104A (en) * 1998-03-20 2000-01-18 Rich, Jr.; John W. Process and apparatus for preparing feedstock for a coal gasification plant
US6389820B1 (en) * 1999-02-12 2002-05-21 Mississippi State University Surfactant process for promoting gas hydrate formation and application of the same
AUPQ118899A0 (en) * 1999-06-24 1999-07-22 Woodside Energy Limited Natural gas hydrate and method for producing same
US6506361B1 (en) * 2000-05-18 2003-01-14 Air Products And Chemicals, Inc. Gas-liquid reaction process including ejector and monolith catalyst
US6894183B2 (en) * 2001-03-26 2005-05-17 Council Of Scientific And Industrial Research Method for gas—solid contacting in a bubbling fluidized bed reactor
EP1375630A1 (fr) * 2001-03-29 2004-01-02 Mitsubishi Heavy Industries, Ltd. Dispositif de production d'hydrate de gaz et dispositif de deshydratation d'hydrate de gaz
JP5019683B2 (ja) * 2001-08-31 2012-09-05 三菱重工業株式会社 ガスハイドレートスラリーの脱水装置及び脱水方法
US7220502B2 (en) * 2002-06-27 2007-05-22 Intellergy Corporation Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US7205448B2 (en) * 2003-12-19 2007-04-17 Uop Llc Process for the removal of nitrogen compounds from a fluid stream
US20070000177A1 (en) * 2005-07-01 2007-01-04 Hippo Edwin J Mild catalytic steam gasification process
DE202005021662U1 (de) * 2005-09-07 2009-03-05 Siemens Aktiengesellschaft Vorrichtung zur Erzeugung von Synthesegasen durch Partialoxidation von aus aschehaltigen Brennstoffen erzeugten Slurries mit Teilquenchung und Abhitzegewinnung
US8114176B2 (en) * 2005-10-12 2012-02-14 Great Point Energy, Inc. Catalytic steam gasification of petroleum coke to methane
AU2008282518B2 (en) * 2007-08-02 2012-03-01 Greatpoint Energy, Inc. Catalyst-loaded coal compositions, methods of making and use
WO2009048723A2 (fr) * 2007-10-09 2009-04-16 Greatpoint Energy, Inc. Compositions pour la gazéification catalytique d'un coke de pétrole
US20090090056A1 (en) * 2007-10-09 2009-04-09 Greatpoint Energy, Inc. Compositions for Catalytic Gasification of a Petroleum Coke
WO2010033848A2 (fr) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processus de gazéification d’une charge carbonée
US8502007B2 (en) * 2008-09-19 2013-08-06 Greatpoint Energy, Inc. Char methanation catalyst and its use in gasification processes
US8647402B2 (en) * 2008-09-19 2014-02-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
CA2735137C (fr) * 2008-09-19 2013-05-21 Greatpoint Energy, Inc. Traitements pour la gazeification d'une matiere carbonee

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219338A (en) * 1978-05-17 1980-08-26 Exxon Research & Engineering Co. Hydrothermal alkali metal recovery process
US4260421A (en) * 1979-05-18 1981-04-07 Exxon Research & Engineering Co. Cement production from coal conversion residues
US4459138A (en) * 1982-12-06 1984-07-10 The United States Of America As Represented By The United States Department Of Energy Recovery of alkali metal constituents from catalytic coal conversion residues
US20070277437A1 (en) * 2006-06-01 2007-12-06 Sheth Atul C Catalytic steam gasification process with recovery and recycle of alkali metal compounds

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US8999020B2 (en) 2008-04-01 2015-04-07 Greatpoint Energy, Inc. Processes for the separation of methane from a gas stream
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9127221B2 (en) 2011-06-03 2015-09-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9012524B2 (en) 2011-10-06 2015-04-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9273260B2 (en) 2012-10-01 2016-03-01 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9034061B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9328920B2 (en) 2012-10-01 2016-05-03 Greatpoint Energy, Inc. Use of contaminated low-rank coal for combustion
US9034058B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

Also Published As

Publication number Publication date
WO2009086361A3 (fr) 2009-11-19
US20090165383A1 (en) 2009-07-02

Similar Documents

Publication Publication Date Title
US7897126B2 (en) Catalytic gasification process with recovery of alkali metal from char
US7901644B2 (en) Catalytic gasification process with recovery of alkali metal from char
US20090165383A1 (en) Catalytic Gasification Process with Recovery of Alkali Metal from Char
US20090165382A1 (en) Catalytic Gasification Process with Recovery of Alkali Metal from Char
CA2716135C (fr) Composition particulaire pour gazeification, preparation et conversion continue connexe
US9234149B2 (en) Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US20090165384A1 (en) Continuous Process for Converting Carbonaceous Feedstock into Gaseous Products
US20090217582A1 (en) Processes for Making Adsorbents and Processes for Removing Contaminants from Fluids Using Them
CA2709520C (fr) Compositions de coke de petrole pour gazeification catalytique
US8114177B2 (en) Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
US8286901B2 (en) Coal compositions for catalytic gasification
US20090220406A1 (en) Selective Removal and Recovery of Acid Gases from Gasification Products
US20090165380A1 (en) Petroleum Coke Compositions for Catalytic Gasification
WO2009086363A1 (fr) Compositions de charbon pour gazéification catalytique et leur procédé de préparation
WO2009111335A2 (fr) Compositions de charbon pour gazéification catalytique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08867975

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08867975

Country of ref document: EP

Kind code of ref document: A2

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载