WO2005049767A2 - In-situ gasification of soot contained in exothermically generated syngas stream - Google Patents

In-situ gasification of soot contained in exothermically generated syngas stream Download PDF

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Publication number
WO2005049767A2
WO2005049767A2 PCT/US2004/038577 US2004038577W WO2005049767A2 WO 2005049767 A2 WO2005049767 A2 WO 2005049767A2 US 2004038577 W US2004038577 W US 2004038577W WO 2005049767 A2 WO2005049767 A2 WO 2005049767A2
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WIPO (PCT)
Prior art keywords
soot
syngas
reactor
carbonaceous material
byproducts
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PCT/US2004/038577
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French (fr)
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WO2005049767A3 (en
Inventor
William Robert Licht
Shankar Nataraj
Xiang-Dong Peng
John Michael Repasky
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National Institute For Strategic Technology Acquisition And Commercialization
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Priority to EP04819174A priority Critical patent/EP1692247A4/en
Priority to CA2546705A priority patent/CA2546705C/en
Publication of WO2005049767A2 publication Critical patent/WO2005049767A2/en
Publication of WO2005049767A3 publication Critical patent/WO2005049767A3/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
    • C10K3/003—Reducing the tar content
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/049—Composition of the impurity the impurity being carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/06—Catalysts as integral part of gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/094—Char
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only

Definitions

  • Synthesis gas comprising carbon monoxide and hydrogen (hereafter syngas) is
  • POX partial oxidation
  • hydrocarbon-containing fuel hereafter, the POX process.
  • the POX process is a highly exothermic process and produces a syngas stream at temperatures typically in range of 2100 to 2800 °F.
  • soot the entrained solid carbon
  • soot the soot that is generated in the POX reactor will tend to foul conventionally designed heat exchangers that are used to recover a portion of the heat from the exothermically generated syngas stream.
  • special boilers have been developed to process soot-containing syngas, these designs cannot be readily transferred to heat exchange reforming wherein a portion of the heat is recovered from the POX generated syngas stream and used as at least a portion of the heat to facilitate the additional production of syngas via the (endothermic) catalytic reforming of natural gas and steam.
  • a system which can remove soot from syngas at high temperature offers a key advantage to the practice of heat exchange reforming.
  • the soot is removed by quenching and scrubbing the syngas with water.
  • JP 50040117 teaches directly filtering the syngas through a
  • JP "117 introduces the syngas (or "reducing gas” as referred to therein) into a blast furnace.
  • carbonaceous material as the material for trapping the soot and subsequently allowing it to be
  • the carbonaceous material gasified by reaction with the byproduct CO 2 and/or H 2 O.
  • the carbonaceous material gasified by reaction with the byproduct CO 2 and/or H 2 O.
  • the carbonaceous material gasified by reaction with the byproduct CO 2 and/or H 2 O.
  • the present invention addresses this concern by using a non-carbonaceous material
  • the present invention is a system for the exothermic generation of syngas by the
  • a key to the present invention is that the material used to trap the soot in the second
  • reactor is a non-carbonaceous material. This is key because if a carbonaceous material were used
  • the system further comprises a heat
  • Alumina is one example of the material that can be used as the non-carbonaceous
  • the material is packed in the second reactor in the form of spherical particles to
  • the pressure drop is 16 psi while the removal efficiency is such that 85% of the soot
  • carbonaceous material could also have a catalytic functionality to facilitate the gasification of the
  • POX reactors can operate over a temperature range from about 1700F to 3500F;
  • the hydrocarbon feed to the partial oxidation step is overly oxidized, resulting in less syngas and
  • the system described here is designed to operate at a

Abstract

A system is set forth for the exothermic generation of soot depleted syngas comprising (i) reacting a hydrocarbon-containing fuel with an oxygen containing gas in a first reactor to produce the syngas and byproducts comprising CO2,H20 and soot; and (ii) introducing the syngas and byproducts into a second reactor containing a non-carbonaceous material that traps the soot for a sufficient time such that the majority of the byproduct soot is gasified via reaction with the byproduct CO2 and/or H20 to produce a syngas stream that is depleted in the soot. The system is particularly suitable for the practice of heat exchange reforming wherein a portion of the heat is recovered from the soot depleted syngas stream and used as at least a portion of the heat to facilitate the additional production of syngas via the (endothermic) catalytic reforming of natural gas and steam.

Description

TITLE OF THE INVENTION: LN-SITU GASIFICATION OF SOOT CONTAINED IN EXOTHERMICALLY GENERATED SYNGAS STREAM BACKGROUND OF THE INVENTION
[0001] Synthesis gas comprising carbon monoxide and hydrogen (hereafter syngas) is
commonly produced by the partial oxidation (POX) of a hydrocarbon-containing fuel (hereafter, the POX process. The POX process is a highly exothermic process and produces a syngas stream at temperatures typically in range of 2100 to 2800 °F.
[0002] A key challenge in the POX process, especially for carbon heavy fuels, is the removal
of the entrained solid carbon (hereafter soot) produced as an undesirable byproduct. In particular, the soot that is generated in the POX reactor will tend to foul conventionally designed heat exchangers that are used to recover a portion of the heat from the exothermically generated syngas stream. Although special boilers have been developed to process soot-containing syngas, these designs cannot be readily transferred to heat exchange reforming wherein a portion of the heat is recovered from the POX generated syngas stream and used as at least a portion of the heat to facilitate the additional production of syngas via the (endothermic) catalytic reforming of natural gas and steam. Thus a system which can remove soot from syngas at high temperature offers a key advantage to the practice of heat exchange reforming.
[0003] Typically, the soot is removed by quenching and scrubbing the syngas with water.
See for example EPO 648 828 Bl and WO 00/29323, both assigned to Texaco Development Corporation. [0004] Alternatively, JP 50040117 teaches directly filtering the syngas through a
carbonaceous material that traps the soot for a sufficient time period such that the oxygen
containing molecules that are also produced as byproduct in the POX process [i.e. C02 and H2O]
are given an opportunity to react with, and gasify, the soot. After such in-situ gasification of the
soot, JP "117 introduces the syngas (or "reducing gas" as referred to therein) into a blast furnace.
[0005] A concern with the in-situ gasification scheme as taught in JP v 117 is the use of a
carbonaceous material as the material for trapping the soot and subsequently allowing it to be
gasified by reaction with the byproduct CO2 and/or H2O. In particular, the carbonaceous material
will be susceptible to the very same gasification reactions that the carbonaceous soot is intended
to undergo (i.e. via reaction against the byproduct CO2 and/or H2O). Consequently, a carbonaceous
material will require more frequent replacing than a non-carbonaceous material.
[0006] The present invention addresses this concern by using a non-carbonaceous material
to trap the soot.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention is a system for the exothermic generation of syngas by the
partial oxidation of a hydrocarbon-containing fuel comprising:
(i) reacting the hydrocarbon-containing fuel with an oxygen containing gas in a first
reactor to produce the syngas and byproducts comprising CO2, H2O and soot; and
(ii) introducing the syngas and byproducts into a second reactor containing a non-
carbonaceous material that traps the soot for a sufficient time such that the majority of the
byproduct soot is gasified via reaction with the byproduct CO2 and/or H2O to produce a syngas
stream that is depleted in the soot. DETAILED DESCRIPTION OF THE INVENTION
[0008] A key to the present invention is that the material used to trap the soot in the second
reactor is a non-carbonaceous material. This is key because if a carbonaceous material were used
(i.e. such as in JP 50040117), the material would be susceptible to the very same gasification
reactions that the carbonaceous soot is intended to undergo (i.e. via reaction against the byproduct
CO2 and/or H2O). Consequently, a carbonaceous material will require more frequent replacing than
a non-carbonaceous material.
[0009] In a key embodiment of the present invention, the system further comprises a heat
exchange reformer for recovering a portion of the heat from the soot depleted syngas stream and
using at least a portion of the recovered heat to facilitate the additional production of syngas via the
(endothermic) catalytic reforming of natural gas and steam.
[0010] Alumina is one example of the material that can be used as the non-carbonaceous
material in the present invention. Various other refractory materials such as zirconia or lanthana
could also be used, optionally in combination with alumina. In one embodiment of the present
invention, the material is packed in the second reactor in the form of spherical particles to
efficiently trap the soot without creating excessive pressure drop. The pressure drop and removal
efficiency for an example reactor consisting of 2 feet of 3 inch diameter spheres and 1 foot each of
2 inch, 1 inch, and 0.5 inch diameter spheres has been calculated. With a superficial gas velocity
of 7ft/s, the pressure drop is 16 psi while the removal efficiency is such that 85% of the soot
particles 21 microns in diameter are removed (larger soot particles are removed almost completely
and smaller particle are passed through the bed almost completely). By arranging the spherical
particles in this manner, soot particles of different sizes are trapped within each zone. This
distributes the soot along the direction of flow and increases the capacity of the bed to hold soot
without plugging.
[0011] Alternate packing shapes such as rings could also be used to allow more complete
removal of a wider range of soot sizes while minimizing pressure drop. In addition, the non-
carbonaceous material could also have a catalytic functionality to facilitate the gasification of the
soot.
[0012] POX reactors can operate over a temperature range from about 1700F to 3500F;
however, the most common operating range is from about 2100 to 2800F. The system described
here is preferentially operated in a temperature range from 2100F to 2800F. At higher temperatures,
the hydrocarbon feed to the partial oxidation step is overly oxidized, resulting in less syngas and
more byproduct CO2 and H2O. At lower temperatures, there is a substantial amount of unconverted
hydrocarbon feed. Additionally at lower temperature, the quantity of soot held in the packing
becomes too great and the packing plugs. The system described here is designed to operate at a
steady state in which the gasification rate is equal to the rate at which the soot is trapped. For every
100F drop in temperature between 2500F and 2100F the quantity of soot which must be held on the
bed for the gasification rate to equal the amount of soot generated in the POX unit increases by
approximately an order-of-magnitude. [0013] It is within the scope of the present invention to include a fluid addition step between the first and second reactors. Potential benefits include managing the high temperatures and increasing the driving force for soot gasification. For example, steam could be added to the syngas and byproducts produced by the first reactor prior to introducing the syngas and byproducts into the second reactor.
[0014] The skilled practitioner will appreciate that there are many other embodiments
of the present invention which are within the scope of the following claims.

Claims

1. A process for the exothermic generation of syngas by the partial oxidation of a
hydrocarbon-containing fuel comprising: (i) reacting the hydrocarbon-containing fuel with an oxygen containing gas in a first reactor
to produce the syngas and byproducts comprising CO2, H2O and soot; and
(ii) introducing the syngas and byproducts into a second reactor containing a non-
carbonaceous material that traps the soot for a sufficient time such that the majority of the
byproduct soot is gasified via reaction with the byproduct CO2 and/or H2O to produce a syngas
stream that is depleted in the soot.
2. The process of Claim 1 which further comprises:
(iii) recovering a portion of the heat from the soot depleted syngas stream and using at least
a portion of the recovered heat to facilitate the additional production of syngas via the (endothermic)
catalytic reforming of natural gas and steam.
3. The process of Claim 1 wherein substantially all of the byproduct soot is gasified in step
(ii)-
4. The process of Claim 1 wherein the non-carbonaceous material comprises alumina.
5. The process of Claim 1 wherein the non-carbonaceous material contained in the second
reactor is in the form of spherical particles.
6. The process of Claim 1 wherein the non-carbonaceous material contained in the second
reactor is in the form of rings.
7. The process of Claim 1 wherein the non-carbonaceous material contained in the second reactor has a catalytic functionality to facilitate the gasification of the soot.
8. The process of Claim 1 wherein first and second reactors are operated in a temperature range from 2100F to 2800F.
9. The process of Claim 1 wherein a fluid is added to the syngas and byproducts produced
by the first reactor prior to introducing the syngas and byproducts into the second reactor.
10. In an apparatus for the exothermic generation of syngas by the partial oxidation of a hydrocarbon-containing fuel comprising: (i) a first reactor for reacting the hydrocarbon-containing fuel with an oxygen containing gas to produce the syngas and byproducts comprising CO2, H2O and soot; and
(ii) a second reactor for receiving the syngas and byproducts containing a non-carbonaceous material that traps the soot for a sufficient time such that the majority of the byproduct soot is gasified via reaction with the byproduct CO2 and/or H2O to produce a syngas stream that is depleted in the soot.
11. The apparatus of Claim 10 which further comprises:
(iii) a heat exchange reformer for recovering a portion of the heat from the soot depleted syngas stream and using at least a portion of the recovered heat to facilitate the additional production of syngas via the (endothermic) catalytic reforming of natural gas and steam.
12. The apparatus of Claim 10 wherein substantially all of the byproduct soot is gasified in the second reactor.
13. The apparatus of Claim 10 wherein the non-carbonaceous material comprises alumina.
14. The apparatus of Claim 10 wherein the non-carbonaceous material contained in the second reactor is in the form of spherical particles.
15. The apparatus of Claim 10 wherein the non-carbonaceous material contained in the
second reactor is in the form of rings.
16. The apparatus of Claim 10 wherein the non-carbonaceous material contained in the
second reactor has a catalytic functionality to facilitate the gasification of the soot.
17. The apparatus of Claim 10 wherein first and second reactors are operated in a
temperature range from 2100F to 2800F.
18. The apparatus of Claim 10 further comprising a means to add a fluid to the syngas and
byproducts produced by the first reactor prior to the second reactor receiving the syngas and
byproducts.
PCT/US2004/038577 2003-11-18 2004-11-15 In-situ gasification of soot contained in exothermically generated syngas stream WO2005049767A2 (en)

Priority Applications (2)

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EP04819174A EP1692247A4 (en) 2003-11-18 2004-11-15 In-situ gasification of soot contained in exothermically generated syngas stream
CA2546705A CA2546705C (en) 2003-11-18 2004-11-15 In-situ gasification of soot contained in exothermically generated syngas stream

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US10/715,757 US7534276B2 (en) 2003-11-18 2003-11-18 In-situ gasification of soot contained in exothermically generated syngas stream
US10/715,757 2003-11-18

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US7534276B2 (en) 2009-05-19
CA2546705A1 (en) 2005-06-02
US20090220393A1 (en) 2009-09-03
US8771386B2 (en) 2014-07-08
US20050102901A1 (en) 2005-05-19
US20140250785A1 (en) 2014-09-11
CA2546705C (en) 2012-10-30
WO2005049767A3 (en) 2006-04-20
EP1692247A4 (en) 2009-07-22
EP1692247A2 (en) 2006-08-23

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