US20090165383A1 - Catalytic Gasification Process with Recovery of Alkali Metal from Char - Google Patents

Catalytic Gasification Process with Recovery of Alkali Metal from Char Download PDF

Info

Publication number
US20090165383A1
US20090165383A1 US12/342,554 US34255408A US2009165383A1 US 20090165383 A1 US20090165383 A1 US 20090165383A1 US 34255408 A US34255408 A US 34255408A US 2009165383 A1 US2009165383 A1 US 2009165383A1
Authority
US
United States
Prior art keywords
alkali metal
char
metal compounds
insoluble matter
stream
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/342,554
Inventor
Alkis S. Rappas
Robert A. Spitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SURE CHAMPION INVESTMENT LIMITED
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
Priority to US1729307P priority Critical
Application filed by Greatpoint Energy Inc filed Critical Greatpoint Energy Inc
Priority to US12/342,554 priority patent/US20090165383A1/en
Assigned to GREATPOINT ENERGY, INC. reassignment GREATPOINT ENERGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SPITZ, ROBERT A., RAPPAS, ALKIS S.
Publication of US20090165383A1 publication Critical patent/US20090165383A1/en
Assigned to SURE CHAMPION INVESTMENT LIMITED reassignment SURE CHAMPION INVESTMENT LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREATPOINT ENERGY, INC.
Application status is Abandoned legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/463Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903Feed preparation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0943Coke
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0973Water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983Additives
    • C10J2300/0986Catalysts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C10J2300/1628Ash post-treatment
    • C10J2300/1631Ash recycling
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/169Integration of gasification processes with another plant or parts within the plant with water treatments
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1853Steam reforming, i.e. injection of steam only

Abstract

Processes are described for the extraction and recovery of alkali metal from the char that results from catalytic gasification of a carbonaceous material. Among other steps, the processes of the invention include a hydrothermal leaching step in which a slurry of insoluble particulate comprising insoluble alkali metal compounds is treated with carbon dioxide and steam at elevated temperatures and pressures to effect the conversion of insoluble alkali metal compounds to soluble alkali metal compounds. Further, processes are described for the catalytic gasification of a carbonaceous material where a substantial portion of alkali metal is extracted and recovered from the char that results from the catalytic gasification process.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims priority under 35 U.S.C. §119 from U.S. Provisional Application Ser. No. 61/017,293 (filed Dec. 28, 2007), the disclosure of which is incorporated by reference herein for all purposes as if fully set forth.
  • This application is related to commonly owned U.S. application Ser. No. 11/421,511, filed Jun. 1, 2006, entitled “CATALYTIC STEAM GASIFICATION PROCESS WITH RECOVERY AND RECYCLE OF ALKALI METAL COMPOUNDS”; U.S. application Ser. No. ______, (filed concurrently herewith), entitled “CATALYTIC GASIFICATION PROCESS WITH RECOVERY OF ALKALI METAL FROM CHAR” (attorney docket no. FN-0014 US NP1); U.S. application Ser. No. ______, (filed concurrently herewith), entitled “CATALYTIC GASIFICATION PROCESS WITH RECOVERY OF ALKALI METAL FROM CHAR” (attorney docket no. FN-0015 US NP1); and U.S. application Ser. No. ______, (filed concurrently herewith), entitled “CATALYTIC GASIFICATION PROCESS WITH RECOVERY OF ALKALI METAL FROM CHAR” (attorney docket no. FN-0016 US NP1).
  • FIELD OF THE INVENTION
  • 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.
  • BACKGROUND OF THE INVENTION
  • In view of numerous factors such as higher energy prices and environmental concerns, the production of value-added gaseous products from lower-fuel-value carbonaceous feedstocks, such as petroleum coke and coal, is receiving renewed attention. The catalytic gasification of such materials to produce methane and other value-added gases is disclosed, for example, in U.S. Pat. No. 3,828,474, U.S. Pat. No. 3,998,607, U.S. Pat. No. 4,057,512, U.S. Pat. No. 4,092,125, U.S. Pat. No. 4,094,650, U.S. Pat. No. 4,204,843, U.S. Pat. No. 4,468,231, U.S. Pat. No. 4,500,323, U.S. Pat. No. 4,541,841, U.S. Pat. No. 4,551,155, U.S. Pat. No. 4,558,027, U.S. Pat. No. 4,606,105, U.S. Pat. No. 4,617,027, U.S. Pat. No. 4,609,456, U.S. Pat. No. 5,017,282, U.S. Pat. No. 5,055,181, U.S. Pat. No. 6,187,465, U.S. Pat. No. 6,790,430, U.S. Pat. No. 6,894,183, U.S. Pat. No. 6,955,695, US2003/0167961A1, US2006/0265953A1, US2007/000177A1, US2007/083072A1, US2007/0277437A1 and GB 1599932.
  • Gasification of a carbonaceous material, such as coal or petroleum coke, can be catalyzed by loading the carbonaceous material with a catalyst comprising an alkali metal source. U.S. Patent Application Publication Nos. US2007/0000177A1 and US2007/0083072A1, both incorporated herein by reference, disclose the alkali-metal-catalyzed gasification of carbonaceous materials. Lower-fuel-value carbon sources, such as coal, typically contain quantities of inorganic matter, including compounds of silicon, aluminum, calcium, iron, vanadium, sulfur, and the like. This inorganic content is referred to as ash. Silica and alumina are especially common ash components. At temperatures above 500-600° C., alkali metal compounds can react with the alumina and silica to form alkali metal aluminosilicates. As an aluminosilicate, the alkali metal compound is substantially insoluble in water and has little effectiveness as a gasification catalyst.
  • At typical gasification temperatures, most components of ash are not gasified, and thus build up with other compounds in the gasification reactor as a solid residue referred to as char. For catalytic gasification, 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.
  • SUMMARY OF THE INVENTION
  • 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.
  • In a first aspect, 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° C. to 600° 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 hydroxide, or both, 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 comprising soluble alkali metal compounds and partially extracted insoluble matter, wherein the partially extracted insoluble matter comprises insoluble alkali metal compounds; (f) contacting the first leached slurry with carbon dioxide under suitable pressure and temperature so to convert at least a 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 soluble alkali metal compounds and a residual insoluble matter; (g) separating the second leached slurry into a second liquid stream and a residual insoluble matter stream, the second liquid stream comprising a predominant portion of the soluble alkali metal compounds from the second leached slurry, and the residual insoluble matter stream comprising residual soluble alkali metal compounds and residual insoluble alkali metal compounds; (h) recovering the second liquid stream; and (i) washing the residual insoluble matter stream to recover substantially all of the residual soluble alkali metal compounds in the residual insoluble matter stream as a first wash stream, wherein the quenching and contacting are performed in the substantial absence of gaseous oxygen.
  • In a second aspect, 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) removing a portion of the char and from the gasification reactor; (d) extracting and recovering a substantial portion of the alkali metal from the char according to any process of the first aspect; and (e) at least partially separating the plurality of gaseous products to produce a stream comprising a predominant amount of one of the gaseous products.
  • 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.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 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.
  • DETAILED DESCRIPTION
  • 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. Among other steps, 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. In this manner, 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 Ser. No. 12/178,380 (filed 23 Jul. 2008), Ser. No. 12/234,012 (filed 19 Sep. 2008) and Ser. No. 12/234,018 (filed 19 Sep. 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: Ser. No. ______, entitled “PETROLEUM COKE COMPOSITIONS FOR CATALYTIC GASIFICATION” (attorney docket no. FN-0008 US NP1); Ser. No. ______, entitled “STEAM GENERATING SLURRY GASIFIER FOR THE CATALYTIC GASIFICATION OF A CARBONACEOUS FEEDSTOCK” (attorney docket no. FN-0017 US NP1); Ser. No. ______, entitled “PETROLEUM COKE COMPOSITIONS FOR CATALYTIC GASIFICATION” (attorney docket no. FN-0011 US NP1); Ser. No. ______, entitled “COAL COMPOSITIONS FOR CATALYTIC GASIFICATION” (attorney docket no. FN-0009 US NP1); Ser. No. ______, entitled “PROCESSES FOR MAKING SYNTHESIS GAS AND SYNGAS-DERIVED PRODUCTS” (attorney docket no. FN-0010 US NP1); Ser. No. ______, entitled “CARBONACEOUS FUELS AND PROCESSES FOR MAKING AND USING THEM” (attorney docket no. FN-0013 US NP1); and Ser. No. ______, entitled “PROCESSES FOR MAKING SYNGAS-DERIVED PRODUCTS” (attorney docket no. FN-0012 US NP1).
  • All publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth.
  • Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.
  • Except where expressly noted, trademarks are shown in upper case.
  • Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein.
  • Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
  • When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range.
  • When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.
  • As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, 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. Further, unless expressly stated to the contrary, “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).
  • The use of “a” or “an” to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
  • The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting.
  • Carbonaceous Composition
  • The term “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. Typically, 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. Typically, 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. Typically, the petroleum coke comprises less than about 20 wt % percent inorganic compounds, based on the weight of the petroleum coke.
  • The term “asphaltene” 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.
  • The term “liquid petroleum residue” as used herein 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. Typically, 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. Typically, the ash in such higher-ash residues predominantly comprises materials such as compounds of silicon and/or aluminum.
  • The term “coal” as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof. In certain embodiments, 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. In other embodiments, 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 (N.D.), 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. However, 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.
  • The term “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 Compounds
  • As used herein, the terms “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.” Examples of an insoluble alkali metal compound 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 polysulfides. For example, the catalyst can comprise one or more of Na2CO3, K2CO3, Rb2CO3, Li2CO3, Cs2CO3, NaOH, KOH, RbOH, or CsOH, and particularly, potassium carbonate and/or potassium hydroxide.
  • Catalyst-Loaded Carbonaceous Feedstock
  • The carbonaceous composition is generally loaded with an amount of an alkali metal. Typically, 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. Further, 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.
  • 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 U.S. Pat. No. 4,069,304 and U.S. Pat. No. 5,435,940; previously incorporated U.S. Pat. No. 4,092,125, U.S. Pat. No. 4,468,231 and U.S. Pat. No. 4,551,155; previously incorporated U.S. patent application Ser. Nos. 12/234,012 and 12/234,018; and previously incorporated U.S. patent applications Ser. No. ______, entitled “PETROLEUM COKE COMPOSITIONS FOR CATALYTIC GASIFICATION” (attorney docket no. FN-0008 US NP1), Ser. No. ______, entitled “PETROLEUM COKE COMPOSITIONS FOR CATALYTIC GASIFICATION” (attorney docket no. FN-0011 US NP1), Ser. No. ______, entitled “CONTINUOUS PROCESS FOR CONVERTING CARBONACEOUS FEEDSTOCK INTO GASEOUS PRODUCTS” (attorney docket no. FN-0018 US NP1), and Ser. No. ______, entitled “COAL COMPOSITIONS FOR CATALYTIC GASIFICATION” (attorney docket no. FN-0009 US NP1).
  • One particular method suitable for combining the coal particulate with a gasification catalyst to provide a catalyzed carbonaceous feedstock where the catalyst has been associated with the coal particulate via ion exchange is described in previously incorporated U.S. patent application Ser. No. 12/178,380 (filed 23 Jul. 2008). The catalyst loading by ion exchange mechanism is maximized (based on adsorption isotherms specifically developed for the coal), and the additional catalyst retained on the wet cake, including inside the pores, is controlled so that the total catalyst target value is obtained in a controlled manner. Such loading provides a catalyzed coal particulate as a wet cake. The catalyst loaded and dewatered wet coal cake typically contains, for example, about 50% moisture. The total amount of catalyst loaded is controlled by controlling the concentration of catalyst components in the solution, as well as the contact time, temperature and method, as can be readily determined by those of ordinary skill in the relevant art based on the characteristics of the starting coal.
  • 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.
  • Catalytic Gasification Methods
  • 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. 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° C., or of at least about 600° C. or above, to about 900° C., or to about 750° C., or to about 700° 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. For example, 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. For example, when 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. In one method, compressed recycle gas of CO and H2 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 H2 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 CH4, CO2, H2 and CO, H2S, NH3, 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 H2S, CO2, CO, H2 and CH4. Methods for COS hydrolysis are known to those skilled in the art, for example, see U.S. Pat. No. 4,100,256.
  • 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 H2S, CO2 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 H2S and CO2 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. One method can involve the use of Selexol® (UOP LLC, Des Plaines, Ill. USA) or Rectisol® (Lurgi AG, Frankfurt am Main, Germany) solvent having two trains; each train consisting of an H2S absorber and a CO2 absorber. The spent solvent containing H2S, CO2 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 CH4, H2 and CO and, typically, small amounts of CO2 and H2O. Any recovered H2S 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 CH4 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 CH4 from the cleaned gas stream involves the combined use of molecular sieve absorbers to remove residual H2O and CO2 and cryogenic distillation to fractionate and recover CH4. Typically, two gas streams can be produced by the gas separation process, a methane product stream and a syngas stream (H2 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
  • The term “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.
  • Catalyst Recovery
  • Alkali metal salts, particularly sodium and potassium 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.
  • After gasification, the alkali metal may exist in the char as species that are either soluble or insoluble. In particular, alkali metal can react with mineral ash at temperatures above about 500-600° C. to form insoluble alkali metal aluminosilicates, such as kaliophilite. As an aluminosilicate, or other insoluble compounds, the alkali metal is ineffective as a catalyst.
  • As discussed, supra, 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.
  • 1. Char Quenching (100)
  • Referring to FIG. 1, 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. 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. In some embodiments, however, 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. Additionally, in some embodiments, the aqueous medium has a temperature that ranges from about 95° C. up to about 110° C., or up to about 140° C., or up to about 200° C., or up to about 300° C. The pressure need not be elevated above atmospheric pressure. In some embodiments, however, the quenching occurs at pressures higher than atmospheric pressure. For example, 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 CO2). 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. For example, the temperature of the char may range from about 35° C., or from about 50° C., or from about 75° C., up to about 200° C., or up to about 300° C., or up to about 400° C. In some embodiments, the char has an elevated temperature ranging from about 50° C. to about 600° C. In other embodiments, the char has an elevated temperature ranging from about 50° C. to about 300° 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. For example, 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.
  • In some embodiments, the aqueous medium used in the quenching may comprise a wash stream that results from a washing step of the present invention, described, infra.
  • 2. Separation of Quenched Char Slurry (200)
  • 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. For example, 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.
  • In general, 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.
  • 3. Contacting of Quenched Char Slurry With an Alkali Metal Hydroxide and a Calcium Source (300)
  • 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. Generally, 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. Alternatively, 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. In some embodiments, 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.
  • Thus, 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. For example, the temperature of the slurry can range from about 100° C., or from about 125° C., or from about 150° C., up to about 240° C., up to about 270° C., or up to about 300° C. In some embodiments, the slurry has an elevated temperature ranging from about 150° C. to about 240° C. In some embodiments, the slurry has an elevated temperature ranging from about 100° C. to about 150° C.
  • In any combination with the preceding temperature ranges, 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.
  • In one embodiment, 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).
  • 4. Contacting the First Leached Slurry With Carbon Dioxide (400)
  • 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. In the alternative, this process step is referred to as a leaching or a hydrothermal leaching.
  • In some instances, as can be determined by one skilled in the art, prior to contacting the first leached slurry with carbon dioxide, 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. For example, 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. In one embodiment, the first leached slurry may be cooled to a temperature ranging from about 120° 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 sulfidic 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. For example, in some embodiments, the first hydrothermal leaching step is carried out in three pressurized continuous flow stirred tank reactors (CSTRs) in series (in three co-current stages). In other embodiments, for example, 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.
  • For the first hydrothermal leaching step, suitable temperatures and pressure (including partial pressures of various gases), and the 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 90° C., or from about 100° C., or from about 110° C., up to about 120° C., or up to about 130° C., or up to about 140° C., or up to about 160° C. The leaching is typically carried out in the presence of steam. Suitable partial pressures of steam, for example, range from about 3 psig, or from about 6 psig, up to about 14 psig, up to about 20 psig. 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. 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. Suitable durations, for example, range from about 15 minutes, or from about 30 minutes, or from about 45 minutes, up to about 60 minutes, or up to about 90 minutes, or up to about 120 minutes.
  • 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. As used in this first leaching process, 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. For example, 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.
  • In some embodiments of the invention, 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. In these embodiments, 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 90° C., or from about 100° C., or from about 110° C., up to about 120° C., or up to about 130° C., or up to about 140° C., or up to about 160° 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. At these elevated temperatures and pressures, the partial pressures of carbon dioxide and steam are similar to those for the first leaching step. By performing the char quenching under the temperature and pressure conditions typical of the first leaching step, the two steps are effectively combined. In these embodiments, 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.
  • By performing the alkali metal hydroxide hydrolysis and carbonation prior to before filtration of the slurry, the bulk of the slurry solids will act as a filtering aid for any fine (e.g., colloidal) silica and alumina precipitate.
  • 5. Separation and Recovery of Liquid from Extracted Insoluble Matter (500)
  • 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. For example, 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. For example, 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.
  • Optionally, 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. For these embodiments, a suitable temperature may be, for example, about 130° C. or higher, or about 140° C. or higher, about 145° C. or higher, or about 150° C. or higher. For these embodiments, after flashing into the flash drum, the slurry temperature may drop to 120° C. or less, or 110° C. or less, or 100° C. or less, or 95° C. or less. For these embodiments, suitable pressures range from about 10 to about 20 psig, or at about atmospheric pressure.
  • As necessary, depending on the pressure and temperature at which any preceding steps are performed, 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. In some embodiments, the slurry may be cooled prior to being fed into a first pressure let-down vessel, for example to a suitable temperature of about 170° C. or below, or to about 150° C. or below, or to about 130° 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. For example, 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. In some embodiments, 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. For example, 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. For example, 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.
  • 6. Washing (600)
  • Following separation from the second liquid stream, 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.
  • In some embodiments of the invention, 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.
  • As used herein, the term “washing” is not limited to a single flush of the insoluble matter with an aqueous medium, such as water. Rather, each washing step may include multiple staged counter-washings of the insoluble matter. In some embodiments of the invention, the washing of the residual insoluble matter stream comprises at least two staged counter-washings. In some embodiments, 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. For example, the washing step may be performed using a continuous multi-stage counter-current system whereby solids and liquids travel in opposite directions. As known to those of skill in the art, 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.
  • In some embodiments, the recovered first wash stream may be used as at least part of the aqueous medium used for quenching the char.
  • EXAMPLES 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° C., and the steam that is generated (about 6-10% of the water) is condensed and recycled as wash water in the integrated process.
  • At this point, 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° 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 SiO2 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 CO2. The temperature is between 100-150° 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 K2CO3 containing wash solution is recycled to the char quenching (supra).

Claims (16)

1. 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 a char at an elevated temperature ranging from 50° C. to 600° 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 hydroxide, or both, 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 comprising soluble alkali metal compounds and a partially extracted insoluble matter, wherein the partially extracted insoluble matter comprises insoluble alkali metal compounds;
(f) contacting the first leached slurry with carbon dioxide under suitable pressure and temperature so to convert at least a 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 soluble alkali metal compounds and a residual insoluble matter;
(g) separating the second leached slurry into a second liquid stream and a residual insoluble matter stream, the second liquid stream comprising a predominant portion of the soluble alkali metal compounds from the second leached slurry, and the residual insoluble matter stream comprising residual soluble alkali metal compounds and residual insoluble alkali metal compounds;
(h) recovering the second liquid stream; and
(i) washing the residual insoluble matter stream to recover substantially all of the residual soluble alkali metal compounds in the residual insoluble matter stream as a first wash stream,
wherein the quenching and contacting are performed in the substantial absence of gaseous oxygen.
2. The process according to claim 1, wherein the char is a solid residue derived from gasification of a carbonaceous material in the presence of an alkali metal.
3. The process according to claim 2, wherein the carbonaceous material comprises one or more of coal, petroleum coke, asphaltene, liquid petroleum residue or biomass.
4. The process according to claim 1, further comprising the step of recovering the first wash stream for use as the aqueous medium.
5. The process according to claim 1, wherein the alkali metal comprises sodium and/or potassium.
6. The process according to claim 1, wherein the alkali metal is potassium.
7. The process according to claim 1, wherein the source of alkali metal is an alkali metal salt selected from the group consisting of carbonate, hydroxide, acetate, halide and nitrate salts.
8. The process according to claim 1, wherein the source of alkali metal is potassium carbonate.
9. The process according to claim 1, wherein the contacting of the first insoluble matter with an alkali metal hydroxide and calcium oxide, calcium hydroxide, or both is performed at a temperature ranging from about 150 to about 250° C.
10. The process according to claim 1, further comprising the step of degassing the second leached slurry under suitable pressure and temperature so as to remove excess carbon dioxide and hydrogen sulfide.
11. The process according to claim 1, wherein the char is a solid residue derived from gasification of a carbonaceous material in the presence of an alkali metal; the carbonaceous materials comprises one or more of coal, petroleum coke, asphaltene, liquid petroleum residue or biomass; and the alkali metal comprises sodium and/or potassium, and wherein the process further comprises the step of degassing the second leached slurry under suitable pressure and temperature so as to remove excess carbon dioxide and hydrogen sulfide.
12. The process according to claim 4, wherein the char is a solid residue derived from gasification of a carbonaceous material in the presence of an alkali metal; the carbonaceous materials comprises one or more of coal, petroleum coke, asphaltene, liquid petroleum residue or biomass; and the alkali metal comprises sodium and/or potassium, and wherein the process further comprises the step of degassing the second leached slurry under suitable pressure and temperature so as to remove excess carbon dioxide and hydrogen sulfide.
13. The process according to claim 9, wherein the char is a solid residue derived from gasification of a carbonaceous material in the presence of an alkali metal; the carbonaceous materials comprises one or more of coal, petroleum coke, asphaltene, liquid petroleum residue or biomass; and the alkali metal comprises sodium and/or potassium, and wherein the process further comprises the step of degassing the second leached slurry under suitable pressure and temperature so as to remove excess carbon dioxide and hydrogen sulfide.
14. 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) removing a portion of the char and from the gasification reactor;
(d) extracting and recovering a substantial portion of the alkali metal from the char according to the process of claim 1; and
(e) at least partially separating the plurality of gaseous products to produce a stream comprising a predominant amount of one of the gaseous products.
15. The process according to claim 14, wherein the carbonaceous composition comprises one or more of coal, petroleum coke, asphaltene, liquid petroleum residue or biomass.
16. The process according to claim 14, wherein the stream comprises a predominant amount of methane.
US12/342,554 2007-12-28 2008-12-23 Catalytic Gasification Process with Recovery of Alkali Metal from Char Abandoned US20090165383A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US1729307P true 2007-12-28 2007-12-28
US12/342,554 US20090165383A1 (en) 2007-12-28 2008-12-23 Catalytic Gasification Process with Recovery of Alkali Metal from Char

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12/342,554 US20090165383A1 (en) 2007-12-28 2008-12-23 Catalytic Gasification Process with Recovery of Alkali Metal from Char

Publications (1)

Publication Number Publication Date
US20090165383A1 true US20090165383A1 (en) 2009-07-02

Family

ID=40445551

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/342,554 Abandoned US20090165383A1 (en) 2007-12-28 2008-12-23 Catalytic Gasification Process with Recovery of Alkali Metal from Char

Country Status (2)

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

Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010033852A2 (en) 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US20100071262A1 (en) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
WO2010078297A1 (en) 2008-12-30 2010-07-08 Greatpoint Energy, Inc. Processes for preparing a catalyzed carbonaceous particulate
WO2010078298A1 (en) 2008-12-30 2010-07-08 Greatpoint Energy, Inc. Processes for preparing a catalyzed coal particulate
US20100244448A1 (en) * 2009-03-31 2010-09-30 General Electric Company Method and apparatus for blending lignite and coke slurries
US20110011721A1 (en) * 2009-07-16 2011-01-20 Champagne Gary E Vacuum Pyrolytic Gasification And Liquefaction To Produce Liquid And Gaseous Fuels From Biomass
WO2011017630A1 (en) 2009-08-06 2011-02-10 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US7897126B2 (en) 2007-12-28 2011-03-01 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
US7901644B2 (en) 2007-12-28 2011-03-08 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
US20110064648A1 (en) * 2009-09-16 2011-03-17 Greatpoint Energy, Inc. Two-mode process for hydrogen production
WO2011034889A1 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Integrated hydromethanation combined cycle process
WO2011034890A2 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Integrated hydromethanation combined cycle process
WO2011034888A1 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US7922782B2 (en) 2006-06-01 2011-04-12 Greatpoint Energy, Inc. Catalytic steam gasification process with recovery and recycle of alkali metal compounds
US7926750B2 (en) 2008-02-29 2011-04-19 Greatpoint Energy, Inc. Compactor feeder
WO2011049858A2 (en) 2009-10-19 2011-04-28 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011049861A2 (en) 2009-10-19 2011-04-28 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011084580A2 (en) 2009-12-17 2011-07-14 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011084581A1 (en) 2009-12-17 2011-07-14 Greatpoint Energy, Inc. Integrated enhanced oil recovery process injecting nitrogen
WO2011106285A1 (en) 2010-02-23 2011-09-01 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
WO2011139694A1 (en) 2010-04-26 2011-11-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with vanadium recovery
WO2011150217A2 (en) 2010-05-28 2011-12-01 Greatpoint Energy, Inc. Conversion of liquid heavy hydrocarbon feedstocks to gaseous products
US8114177B2 (en) 2008-02-29 2012-02-14 Greatpoint Energy, Inc. Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
US8114176B2 (en) 2005-10-12 2012-02-14 Great Point Energy, Inc. Catalytic steam gasification of petroleum coke to methane
WO2012024369A1 (en) 2010-08-18 2012-02-23 Greatpoint Energy, Inc. Hydromethanation of carbonaceous feedstock
US8123827B2 (en) 2007-12-28 2012-02-28 Greatpoint Energy, Inc. Processes for making syngas-derived products
WO2012033997A1 (en) 2010-09-10 2012-03-15 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US8163048B2 (en) 2007-08-02 2012-04-24 Greatpoint Energy, Inc. Catalyst-loaded coal compositions, methods of making and use
WO2012061238A1 (en) 2010-11-01 2012-05-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2012061235A1 (en) 2010-11-01 2012-05-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US8192716B2 (en) 2008-04-01 2012-06-05 Greatpoint Energy, Inc. Sour shift process for the removal of carbon monoxide from a gas stream
US8202913B2 (en) 2008-10-23 2012-06-19 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
WO2012116003A1 (en) 2011-02-23 2012-08-30 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with nickel recovery
US8268899B2 (en) 2009-05-13 2012-09-18 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US8286901B2 (en) 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
WO2012145497A1 (en) 2011-04-22 2012-10-26 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with char beneficiation
US8297542B2 (en) 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
WO2012166879A1 (en) 2011-06-03 2012-12-06 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US8349039B2 (en) 2008-02-29 2013-01-08 Greatpoint Energy, Inc. Carbonaceous fines recycle
US8361428B2 (en) 2008-02-29 2013-01-29 Greatpoint Energy, Inc. Reduced carbon footprint steam generation processes
US8366795B2 (en) 2008-02-29 2013-02-05 Greatpoint Energy, Inc. Catalytic gasification particulate compositions
WO2013025812A1 (en) 2011-08-17 2013-02-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2013025808A1 (en) 2011-08-17 2013-02-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US8502007B2 (en) 2008-09-19 2013-08-06 Greatpoint Energy, Inc. Char methanation catalyst and its use in gasification processes
US8652696B2 (en) 2010-03-08 2014-02-18 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
US8652222B2 (en) 2008-02-29 2014-02-18 Greatpoint Energy, Inc. Biomass compositions for catalytic gasification
WO2014055351A1 (en) 2012-10-01 2014-04-10 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US8709113B2 (en) 2008-02-29 2014-04-29 Greatpoint Energy, Inc. Steam generation processes utilizing biomass feedstocks
US8728182B2 (en) 2009-05-13 2014-05-20 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US8728183B2 (en) 2009-05-13 2014-05-20 Greatpoint Energy, Inc. Processes for hydromethanation 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
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
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
EP2870224A4 (en) * 2012-07-03 2016-03-02 Battelle Memorial Institute Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass
US9328920B2 (en) 2012-10-01 2016-05-03 Greatpoint Energy, Inc. Use of contaminated low-rank coal for combustion
US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
WO2017141186A1 (en) 2016-02-18 2017-08-24 8 Rivers Capital, Llc System and method for power production including methanation
CN108753360A (en) * 2018-06-01 2018-11-06 新奥科技发展有限公司 A kind of dreg removing system, catalytic coal gasifaction system and catalytic coal gasifaction method
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
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

Citations (98)

* 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
US3958957A (en) * 1974-07-01 1976-05-25 Exxon Research And Engineering Company Methane production
US3969089A (en) * 1971-11-12 1976-07-13 Exxon Research And Engineering Company Manufacture of combustible gases
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
US4021370A (en) * 1973-07-24 1977-05-03 Davy Powergas Limited Fuel gas production
US4069304A (en) * 1975-12-31 1978-01-17 Trw Hydrogen production by catalytic coal gasification
US4077778A (en) * 1975-09-29 1978-03-07 Exxon Research & Engineering Co. Process for the catalytic gasification of coal
US4091073A (en) * 1975-08-29 1978-05-23 Shell Oil Company Process for the removal of H2 S and CO2 from gaseous streams
US4092125A (en) * 1975-03-31 1978-05-30 Battelle Development Corporation Treating solid fuel
US4094650A (en) * 1972-09-08 1978-06-13 Exxon Research & Engineering Co. Integrated catalytic gasification process
US4100256A (en) * 1977-03-18 1978-07-11 The Dow Chemical Company Hydrolysis of carbon oxysulfide
US4101449A (en) * 1976-07-20 1978-07-18 Fujimi Kenmazai Kogyo Co., Ltd. Catalyst and its method of preparation
US4152119A (en) * 1977-08-01 1979-05-01 Dynecology Incorporated Briquette comprising caking coal and municipal solid waste
US4157246A (en) * 1978-01-27 1979-06-05 Exxon Research & Engineering Co. Hydrothermal alkali metal catalyst recovery process
US4159195A (en) * 1977-01-24 1979-06-26 Exxon Research & Engineering Co. Hydrothermal alkali metal recovery process
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
US4200439A (en) * 1977-12-19 1980-04-29 Exxon Research & Engineering Co. Gasification process using ion-exchanged coal
US4204843A (en) * 1977-12-19 1980-05-27 Exxon Research & Engineering Co. Gasification process
US4211538A (en) * 1977-02-25 1980-07-08 Exxon Research & Engineering Co. Process for the production of an intermediate Btu gas
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
US4260421A (en) * 1979-05-18 1981-04-07 Exxon Research & Engineering Co. Cement production from coal conversion residues
US4265868A (en) * 1978-02-08 1981-05-05 Koppers Company, Inc. Production of carbon monoxide by the gasification of carbonaceous materials
US4315758A (en) * 1979-10-15 1982-02-16 Institute Of Gas Technology Process for the production of fuel gas from coal
US4318712A (en) * 1978-07-17 1982-03-09 Exxon Research & Engineering Co. Catalytic coal gasification process
US4330305A (en) * 1976-03-19 1982-05-18 Basf Aktiengesellschaft Removal of CO2 and/or H2 S from gases
US4331451A (en) * 1980-02-04 1982-05-25 Mitsui Toatsu Chemicals, Inc. Catalytic gasification
US4334893A (en) * 1979-06-25 1982-06-15 Exxon Research & Engineering Co. Recovery of alkali metal catalyst constituents with sulfurous acid
US4336034A (en) * 1980-03-10 1982-06-22 Exxon Research & Engineering Co. Process for the catalytic gasification of coal
US4336233A (en) * 1975-11-18 1982-06-22 Basf Aktiengesellschaft Removal of CO2 and/or H2 S and/or COS from gases containing these constituents
US4375362A (en) * 1978-07-28 1983-03-01 Exxon Research And Engineering Co. Gasification of ash-containing solid fuels
US4433065A (en) * 1981-03-24 1984-02-21 Shell Oil Company Process for the preparation of hydrocarbons from carbon-containing material
US4432773A (en) * 1981-09-14 1984-02-21 Euker Jr Charles A Fluidized bed catalytic coal gasification process
US4436531A (en) * 1982-08-27 1984-03-13 Texaco Development Corporation Synthesis gas from slurries of solid carbonaceous fuels
US4439210A (en) * 1981-09-25 1984-03-27 Conoco Inc. Method of catalytic gasification with increased ash fusion temperature
US4444568A (en) * 1981-04-07 1984-04-24 Metallgesellschaft, Aktiengesellschaft Method of producing fuel gas and process heat fron carbonaceous materials
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
US4462814A (en) * 1979-11-14 1984-07-31 Koch Process Systems, Inc. Distillative separations of gas mixtures containing methane, carbon dioxide and other components
US4500323A (en) * 1981-08-26 1985-02-19 Kraftwerk Union Aktiengesellschaft Process for the gasification of raw carboniferous materials
US4508544A (en) * 1981-03-24 1985-04-02 Exxon Research & Engineering Co. Converting a fuel to combustible gas
US4515764A (en) * 1983-12-20 1985-05-07 Shell Oil Company Removal of H2 S from gaseous streams
US4515604A (en) * 1982-05-08 1985-05-07 Metallgesellschaft Aktiengesellschaft Process of producing a synthesis gas which has a low inert gas content
US4597775A (en) * 1984-04-20 1986-07-01 Exxon Research And Engineering Co. Coking and gasification process
US4597776A (en) * 1982-10-01 1986-07-01 Rockwell International Corporation Hydropyrolysis process
US4661237A (en) * 1982-03-29 1987-04-28 Asahi Kasei Kogyo Kabushiki Kaisha Process for thermal cracking of carbonaceous substances which increases gasoline fraction and light oil conversions
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
US4675035A (en) * 1986-02-24 1987-06-23 Apffel Fred P Carbon dioxide absorption methanol process
US4678480A (en) * 1984-10-27 1987-07-07 M.A.N. Maschinenfabrik Augsburg-Nurnberg Ag Process for producing and using syngas and recovering methane enricher gas therefrom
US4682986A (en) * 1984-11-29 1987-07-28 Exxon Research And Engineering Process for separating catalytic coal gasification chars
US4720289A (en) * 1985-07-05 1988-01-19 Exxon Research And Engineering Company Process for gasifying solid carbonaceous materials
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
US4803061A (en) * 1986-12-29 1989-02-07 Texaco Inc. Partial oxidation process with magnetic separation of the ground slag
US4822935A (en) * 1986-08-26 1989-04-18 Scott Donald S Hydrogasification of biomass to produce high yields of methane
US4848983A (en) * 1986-10-09 1989-07-18 Tohoku University Catalytic coal gasification by utilizing chlorides
US4995193A (en) * 1989-09-29 1991-02-26 Ube Industries, Ltd. Method of preventing adherence of ash to gasifier wall
US5017282A (en) * 1987-10-02 1991-05-21 Eniricerche, S.P.A. Single-step coal liquefaction process
US5093094A (en) * 1989-05-05 1992-03-03 Shell Oil Company Solution removal of H2 S from gas streams
US5094737A (en) * 1990-10-01 1992-03-10 Exxon Research & Engineering Company Integrated coking-gasification process with mitigation of bogging and slagging
US5132007A (en) * 1987-06-08 1992-07-21 Carbon Fuels Corporation Co-generation system for co-producing clean, coal-based fuels and electricity
US5223173A (en) * 1986-05-01 1993-06-29 The Dow Chemical Company Method and composition for the removal of hydrogen sulfide from gaseous streams
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
US5616154A (en) * 1992-06-05 1997-04-01 Battelle Memorial Institute Method for the catalytic conversion of organic materials into a product gas
US5630854A (en) * 1982-05-20 1997-05-20 Battelle Memorial Institute Method for catalytic destruction of organic materials
US5641327A (en) * 1994-12-02 1997-06-24 Leas; Arnold M. Catalytic gasification process and system for producing medium grade BTU gas
US5720785A (en) * 1993-04-30 1998-02-24 Shell Oil Company Method of reducing hydrogen cyanide and ammonia in synthesis gas
US5733515A (en) * 1993-01-21 1998-03-31 Calgon Carbon Corporation Purification of air in enclosed spaces
US5855631A (en) * 1994-12-02 1999-01-05 Leas; Arnold M. Catalytic gasification process and system
US5865898A (en) * 1992-08-06 1999-02-02 The Texas A&M University System Methods of biomass pretreatment
US6013158A (en) * 1994-02-02 2000-01-11 Wootten; William A. Apparatus for converting coal to hydrocarbons
US6015104A (en) * 1998-03-20 2000-01-18 Rich, Jr.; John W. Process and apparatus for preparing feedstock for a coal gasification plant
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
US6389820B1 (en) * 1999-02-12 2002-05-21 Mississippi State University Surfactant process for promoting gas hydrate formation and application of the same
US6506361B1 (en) * 2000-05-18 2003-01-14 Air Products And Chemicals, Inc. Gas-liquid reaction process including ejector and monolith catalyst
US6506349B1 (en) * 1994-11-03 2003-01-14 Tofik K. Khanmamedov Process for removal of contaminants from a gas stream
US20040020123A1 (en) * 2001-08-31 2004-02-05 Takahiro Kimura Dewatering device and method for gas hydrate slurrys
US6692711B1 (en) * 1998-01-23 2004-02-17 Exxonmobil Research And Engineering Company Production of low sulfur syngas from natural gas with C4+/C5+ hydrocarbon recovery
US6855852B1 (en) * 1999-06-24 2005-02-15 Metasource Pty Ltd Natural gas hydrate and method for producing same
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
US20050107648A1 (en) * 2001-03-29 2005-05-19 Takahiro Kimura Gas hydrate production device and gas hydrate dehydrating device
US20050137442A1 (en) * 2003-12-19 2005-06-23 Gajda Gregory J. 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
US20070051043A1 (en) * 2005-09-07 2007-03-08 Future Energy Gmbh And Manfred Schingnitz Method and device for producing synthesis by partial oxidation of slurries made from fuels containing ash with partial quenching and waste heat recovery
US20070083072A1 (en) * 2005-10-12 2007-04-12 Nahas Nicholas C Catalytic steam gasification of petroleum coke to methane
US7220502B2 (en) * 2002-06-27 2007-05-22 Intellergy Corporation Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US20090048476A1 (en) * 2007-08-02 2009-02-19 Greatpoint Energy, Inc. Catalyst-Loaded Coal Compositions, Methods of Making and Use
US20090090055A1 (en) * 2007-10-09 2009-04-09 Greatpoint Energy, Inc. Compositions for Catalytic Gasification of a Petroleum Coke
US20090090056A1 (en) * 2007-10-09 2009-04-09 Greatpoint Energy, Inc. Compositions for Catalytic Gasification of a Petroleum Coke
US20100076235A1 (en) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
US20100071262A1 (en) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
US20100121125A1 (en) * 2008-09-19 2010-05-13 Greatpoint Energy, Inc. Char Methanation Catalyst and its Use in Gasification Processes
US20100120926A1 (en) * 2008-09-19 2010-05-13 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock

Family Cites Families (2)

* 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
US7922782B2 (en) * 2006-06-01 2011-04-12 Greatpoint Energy, Inc. Catalytic steam gasification process with recovery and recycle of alkali metal compounds

Patent Citations (99)

* 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
US4092125A (en) * 1975-03-31 1978-05-30 Battelle Development Corporation 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
US4336233A (en) * 1975-11-18 1982-06-22 Basf Aktiengesellschaft Removal of CO2 and/or H2 S and/or COS from gases containing these constituents
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
US4101449A (en) * 1976-07-20 1978-07-18 Fujimi Kenmazai Kogyo Co., Ltd. Catalyst and its method of preparation
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
US4200439A (en) * 1977-12-19 1980-04-29 Exxon Research & Engineering Co. Gasification process using ion-exchanged coal
US4204843A (en) * 1977-12-19 1980-05-27 Exxon Research & Engineering Co. Gasification process
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
US4375362A (en) * 1978-07-28 1983-03-01 Exxon Research And 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
US4260421A (en) * 1979-05-18 1981-04-07 Exxon Research & Engineering Co. Cement production from coal conversion residues
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
US4508544A (en) * 1981-03-24 1985-04-02 Exxon Research & Engineering Co. Converting a fuel to combustible gas
US4433065A (en) * 1981-03-24 1984-02-21 Shell Oil Company Process for the preparation of hydrocarbons from carbon-containing material
US4444568A (en) * 1981-04-07 1984-04-24 Metallgesellschaft, Aktiengesellschaft Method of producing fuel gas and process heat fron carbonaceous materials
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
US4661237A (en) * 1982-03-29 1987-04-28 Asahi Kasei Kogyo Kabushiki Kaisha Process for thermal cracking of carbonaceous substances which increases gasoline fraction and light oil conversions
US4515604A (en) * 1982-05-08 1985-05-07 Metallgesellschaft Aktiengesellschaft Process of producing a synthesis gas which has a low inert gas content
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
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
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
US4678480A (en) * 1984-10-27 1987-07-07 M.A.N. Maschinenfabrik Augsburg-Nurnberg Ag Process for producing and using syngas and recovering methane enricher gas therefrom
US4682986A (en) * 1984-11-29 1987-07-28 Exxon Research And Engineering Process for separating catalytic coal gasification chars
US4668429A (en) * 1985-06-27 1987-05-26 Texaco Inc. Partial oxidation process
US4668428A (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
US4822935A (en) * 1986-08-26 1989-04-18 Scott Donald S Hydrogasification of biomass to produce high yields of methane
US4848983A (en) * 1986-10-09 1989-07-18 Tohoku University Catalytic coal gasification by utilizing chlorides
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
US5017282A (en) * 1987-10-02 1991-05-21 Eniricerche, S.P.A. Single-step coal liquefaction process
US5093094A (en) * 1989-05-05 1992-03-03 Shell Oil Company Solution removal of H2 S from gas streams
US4995193A (en) * 1989-09-29 1991-02-26 Ube Industries, Ltd. Method of preventing adherence of ash to gasifier wall
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
US5616154A (en) * 1992-06-05 1997-04-01 Battelle Memorial Institute Method for the catalytic conversion of organic materials into a product gas
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
US6013158A (en) * 1994-02-02 2000-01-11 Wootten; William A. Apparatus for converting coal to hydrocarbons
US6506349B1 (en) * 1994-11-03 2003-01-14 Tofik K. Khanmamedov Process for removal of contaminants from a gas stream
US5855631A (en) * 1994-12-02 1999-01-05 Leas; Arnold M. Catalytic gasification process and system
US5641327A (en) * 1994-12-02 1997-06-24 Leas; Arnold M. Catalytic gasification process and system for producing medium grade BTU gas
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
US6692711B1 (en) * 1998-01-23 2004-02-17 Exxonmobil Research And Engineering Company Production of low sulfur 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
US6855852B1 (en) * 1999-06-24 2005-02-15 Metasource Pty Ltd 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
US20050107648A1 (en) * 2001-03-29 2005-05-19 Takahiro Kimura Gas hydrate production device and gas hydrate dehydrating device
US20040020123A1 (en) * 2001-08-31 2004-02-05 Takahiro Kimura Dewatering device and method for gas hydrate slurrys
US7220502B2 (en) * 2002-06-27 2007-05-22 Intellergy Corporation Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US20050137442A1 (en) * 2003-12-19 2005-06-23 Gajda Gregory J. Process for the removal of nitrogen compounds from a fluid stream
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
US20070051043A1 (en) * 2005-09-07 2007-03-08 Future Energy Gmbh And Manfred Schingnitz Method and device for producing synthesis by partial oxidation of slurries made from fuels containing ash with partial quenching and waste heat recovery
US20070083072A1 (en) * 2005-10-12 2007-04-12 Nahas Nicholas C Catalytic steam gasification of petroleum coke to methane
US20090048476A1 (en) * 2007-08-02 2009-02-19 Greatpoint Energy, Inc. Catalyst-Loaded Coal Compositions, Methods of Making and Use
US20090090056A1 (en) * 2007-10-09 2009-04-09 Greatpoint Energy, Inc. Compositions for Catalytic Gasification of a Petroleum Coke
US20090090055A1 (en) * 2007-10-09 2009-04-09 Greatpoint Energy, Inc. Compositions for Catalytic Gasification of a Petroleum Coke
US20100120926A1 (en) * 2008-09-19 2010-05-13 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
US20100076235A1 (en) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
US20100071262A1 (en) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
US20100121125A1 (en) * 2008-09-19 2010-05-13 Greatpoint Energy, Inc. Char Methanation Catalyst and its Use in Gasification Processes

Cited By (81)

* 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
US8163048B2 (en) 2007-08-02 2012-04-24 Greatpoint Energy, Inc. Catalyst-loaded coal compositions, methods of making and use
US8123827B2 (en) 2007-12-28 2012-02-28 Greatpoint Energy, Inc. Processes for making syngas-derived products
US7901644B2 (en) 2007-12-28 2011-03-08 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
US7897126B2 (en) 2007-12-28 2011-03-01 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US8366795B2 (en) 2008-02-29 2013-02-05 Greatpoint Energy, Inc. Catalytic gasification particulate compositions
US8652222B2 (en) 2008-02-29 2014-02-18 Greatpoint Energy, Inc. Biomass compositions for catalytic gasification
US8361428B2 (en) 2008-02-29 2013-01-29 Greatpoint Energy, Inc. Reduced carbon footprint steam generation processes
US8286901B2 (en) 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8709113B2 (en) 2008-02-29 2014-04-29 Greatpoint Energy, Inc. Steam generation processes utilizing biomass feedstocks
US7926750B2 (en) 2008-02-29 2011-04-19 Greatpoint Energy, Inc. Compactor feeder
US8297542B2 (en) 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8349039B2 (en) 2008-02-29 2013-01-08 Greatpoint Energy, Inc. Carbonaceous fines recycle
US8114177B2 (en) 2008-02-29 2012-02-14 Greatpoint Energy, Inc. Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
US8192716B2 (en) 2008-04-01 2012-06-05 Greatpoint Energy, Inc. Sour shift process for the removal of carbon monoxide from a gas stream
US8999020B2 (en) 2008-04-01 2015-04-07 Greatpoint Energy, Inc. Processes for the separation of methane from a gas stream
WO2010033852A2 (en) 2008-09-19 2010-03-25 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
US20100071262A1 (en) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processes for Gasification of a Carbonaceous Feedstock
US8328890B2 (en) 2008-09-19 2012-12-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8647402B2 (en) 2008-09-19 2014-02-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8202913B2 (en) 2008-10-23 2012-06-19 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8734547B2 (en) 2008-12-30 2014-05-27 Greatpoint Energy, Inc. Processes for preparing a catalyzed carbonaceous particulate
WO2010078297A1 (en) 2008-12-30 2010-07-08 Greatpoint Energy, Inc. Processes for preparing a catalyzed carbonaceous particulate
WO2010078298A1 (en) 2008-12-30 2010-07-08 Greatpoint Energy, Inc. Processes for preparing a catalyzed coal particulate
US8734548B2 (en) 2008-12-30 2014-05-27 Greatpoint Energy, Inc. Processes for preparing a catalyzed coal particulate
US8343243B2 (en) * 2009-03-31 2013-01-01 General Electric Company Method and apparatus for blending lignite and coke slurries
US20100244448A1 (en) * 2009-03-31 2010-09-30 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
US8728182B2 (en) 2009-05-13 2014-05-20 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US8728183B2 (en) 2009-05-13 2014-05-20 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US20110011721A1 (en) * 2009-07-16 2011-01-20 Champagne Gary E Vacuum Pyrolytic Gasification And Liquefaction To Produce Liquid And Gaseous Fuels From Biomass
WO2011017630A1 (en) 2009-08-06 2011-02-10 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
WO2011034890A2 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Integrated hydromethanation combined cycle process
WO2011034891A1 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Two-mode process for hydrogen production
US20110064648A1 (en) * 2009-09-16 2011-03-17 Greatpoint Energy, Inc. Two-mode process for hydrogen production
WO2011034888A1 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
WO2011034889A1 (en) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Integrated hydromethanation combined cycle process
US8479834B2 (en) 2009-10-19 2013-07-09 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011049858A2 (en) 2009-10-19 2011-04-28 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011049861A2 (en) 2009-10-19 2011-04-28 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
US8479833B2 (en) 2009-10-19 2013-07-09 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
WO2011084581A1 (en) 2009-12-17 2011-07-14 Greatpoint Energy, Inc. Integrated enhanced oil recovery process injecting nitrogen
WO2011084580A2 (en) 2009-12-17 2011-07-14 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
US8733459B2 (en) 2009-12-17 2014-05-27 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
US8669013B2 (en) 2010-02-23 2014-03-11 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
WO2011106285A1 (en) 2010-02-23 2011-09-01 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
US8652696B2 (en) 2010-03-08 2014-02-18 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
US8557878B2 (en) 2010-04-26 2013-10-15 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with vanadium recovery
WO2011139694A1 (en) 2010-04-26 2011-11-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with vanadium recovery
US8653149B2 (en) 2010-05-28 2014-02-18 Greatpoint Energy, Inc. Conversion of liquid heavy hydrocarbon feedstocks to gaseous products
WO2011150217A2 (en) 2010-05-28 2011-12-01 Greatpoint Energy, Inc. Conversion of liquid heavy hydrocarbon feedstocks to gaseous products
WO2012024369A1 (en) 2010-08-18 2012-02-23 Greatpoint Energy, Inc. Hydromethanation of carbonaceous feedstock
US8748687B2 (en) 2010-08-18 2014-06-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2012033997A1 (en) 2010-09-10 2012-03-15 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2012061238A1 (en) 2010-11-01 2012-05-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2012061235A1 (en) 2010-11-01 2012-05-10 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US8648121B2 (en) 2011-02-23 2014-02-11 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with nickel recovery
WO2012116003A1 (en) 2011-02-23 2012-08-30 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with nickel recovery
US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
WO2012145497A1 (en) 2011-04-22 2012-10-26 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with char beneficiation
WO2012166879A1 (en) 2011-06-03 2012-12-06 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9127221B2 (en) 2011-06-03 2015-09-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2013025808A1 (en) 2011-08-17 2013-02-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2013025812A1 (en) 2011-08-17 2013-02-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9012524B2 (en) 2011-10-06 2015-04-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
EP2870224A4 (en) * 2012-07-03 2016-03-02 Battelle Memorial Institute Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass
US9034058B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
WO2014055351A1 (en) 2012-10-01 2014-04-10 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
US9034061B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9273260B2 (en) 2012-10-01 2016-03-01 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
WO2017141186A1 (en) 2016-02-18 2017-08-24 8 Rivers Capital, Llc System and method for power production including methanation
CN108753360A (en) * 2018-06-01 2018-11-06 新奥科技发展有限公司 A kind of dreg removing system, catalytic coal gasifaction system and catalytic coal gasifaction method
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

Also Published As

Publication number Publication date
WO2009086361A2 (en) 2009-07-09
WO2009086361A3 (en) 2009-11-19

Similar Documents

Publication Publication Date Title
EP2403926B1 (en) Process for thermochemical conversion of biomass
US3922148A (en) Production of methane-rich gas
US4284416A (en) Integrated coal drying and steam gasification process
US4199327A (en) Process for gasification of coal to maximize coal utilization and minimize quantity and ecological impact of waste products
CN102197117B (en) Processes for gasification of a carbonaceous feedstock
US4017272A (en) Process for gasifying solid carbonaceous fuel
EP2274404B1 (en) Production and conditioning of synthesis gas obtained from biomass
US4157246A (en) Hydrothermal alkali metal catalyst recovery process
CA1131266A (en) Cement production from coal conversion residues
US20070000177A1 (en) Mild catalytic steam gasification process
US9738579B2 (en) Processes for producing high biogenic concentration Fischer-Tropsch liquids derived from municipal solid wastes (MSW) feedstocks
US4057512A (en) Alkali metal catalyst recovery system
CN102272268B (en) Processes for preparing a catalyzed coal particulate
CN103210068B (en) Hydromethanation of a carbonaceous feedstock
US6448441B1 (en) Gasification process for ammonia/urea production
KR101350061B1 (en) Processes for hydromethanation of a carbonaceous feedstock
US3958957A (en) Methane production
US8652696B2 (en) Integrated hydromethanation fuel cell power generation
CN1038044C (en) Partial oxidation process for producing stream of hot purified gas
CA1125208A (en) Alkali metal recovery process
US4094650A (en) Integrated catalytic gasification process
US4334893A (en) Recovery of alkali metal catalyst constituents with sulfurous acid
US8669013B2 (en) Integrated hydromethanation fuel cell power generation
US9528057B2 (en) System and method for dual fluidized bed gasification
US4159195A (en) Hydrothermal alkali metal recovery process

Legal Events

Date Code Title Description
AS Assignment

Owner name: GREATPOINT ENERGY, INC., ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RAPPAS, ALKIS S.;SPITZ, ROBERT A.;REEL/FRAME:022091/0863;SIGNING DATES FROM 20081210 TO 20081212

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION