+

WO2007005284A2 - Procede de gazeification a la vapeur catalytique modere - Google Patents

Procede de gazeification a la vapeur catalytique modere Download PDF

Info

Publication number
WO2007005284A2
WO2007005284A2 PCT/US2006/024050 US2006024050W WO2007005284A2 WO 2007005284 A2 WO2007005284 A2 WO 2007005284A2 US 2006024050 W US2006024050 W US 2006024050W WO 2007005284 A2 WO2007005284 A2 WO 2007005284A2
Authority
WO
WIPO (PCT)
Prior art keywords
carbonaceous material
gas
trap
methane
steam
Prior art date
Application number
PCT/US2006/024050
Other languages
English (en)
Other versions
WO2007005284A3 (fr
Inventor
Edwin J. Hippo
Atul C. Sheth
Original Assignee
Greatpoint Energy, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Greatpoint Energy, Inc. filed Critical Greatpoint Energy, Inc.
Priority to BRPI0612806A priority Critical patent/BRPI0612806A2/pt
Priority to EP06773644A priority patent/EP1910500A2/fr
Priority to CA002612249A priority patent/CA2612249A1/fr
Priority to JP2008519394A priority patent/JP2009500471A/ja
Publication of WO2007005284A2 publication Critical patent/WO2007005284A2/fr
Publication of WO2007005284A3 publication Critical patent/WO2007005284A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • 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
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • C10J2200/15—Details of feeding means
    • C10J2200/158—Screws
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • 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
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]

Definitions

  • the present invention relates to low temperature catalytic gasification of carbonaceous material. More particularly, the present invention relates to an improved process for gasifying carbonaceous material that achieves high carbon conversion to methane at mild temperatures.
  • coal or other carbonaceous materials and steam are reacted with oxygen (or air) to produce a syngas, comprised primarily of hydrogen and carbon monoxide.
  • oxygen or air
  • Syngas comprised primarily of hydrogen and carbon monoxide.
  • Commercial, non-catalyzed, coal gasification systems and designs face a number of economic and technical challenges. These processes are expensive to operate since, in order to drive the endothermic non-catalytic gasification of carbonaceous materials, they utilize severe temperatures (2400 to 2600°F) and can consume high levels of oxygen. Slagging and corrosion also can present operating and maintenance issues which reduce economic viability and increase product cost.
  • a current concept of an Integrated Gasification Combined Cycle (IGCC) system incorporates a non-catalyzed coal gasification system to produce syngas as an intermediate and burns the syngas to produce electricity.
  • the capital cost of an IGCC system is estimated to range from about $1,250 to $1,400 per KW, depending upon the design and process integration.
  • One way to reduce the cost significantly would be to develop a process that enables one to gasify coal at lower temperature and without added oxygen. Toward this end, it is useful to consider the thermodynamics of gasifying coal.
  • Mild temperature coal gasification can achieve higher direct conversion of carbon to methane and can reduce or avoid catalyst losses which can occur at higher temperatures due to binding with mineral matter in the carbonaceous feed or volatilization. Mild temperature coal gasification can also minimize the conversion of coal to significantly less reactive char. However, catalysts have not heretofore been identified that can catalyze mild temperature gasification at acceptably high reaction rates.
  • Catalytic metals in combination, can be less vulnerable to deactivation than single-metal catalysts.
  • eutectic catalyst mixtures can maintain catalytic activity longer than one constituent of the mixture.
  • Tandon reported that potassium combined with nickel or iron as a steam/graphite gasification catalyst can remain active longer than iron or nickel alone. It is possible that highly dispersed alkali metal salts can provide a reducing atmosphere for transition metal salts and thus sustain their catalytic activity.
  • CaO or lime can also be used with coal conversion processes to absorb
  • transition metals that can catalyze coal gasification are those which can oscillate between two oxidation states and participate in oxidation- reduction cycles on the carbon surface, and that gasification with alkali metal catalysts involves the alkali metals donating electrons to the carbon lattice, or forming alkali/carbon complexes, thereby increasing the number of active CO complexes on the carbon surface. It is also believed that combinations of such catalysts exhibit sustained activity because different types of active sites on the carbon surface can be activated by different catalytic moieties, making more reaction sites available and reducing the impact of the deactivation of any particular type of reaction site or reaction mechanism.
  • transition metals and alkali metals are catalytically inactive when they are oxidized, and that they can be oxidized by components of the gasification environment such as H 2 O, CO 2 , CO and H 2 S.
  • the alkali metal catalysts can also become inactive or ineffective by volatilizing and/or binding with mineral constituents of coal.
  • Calcium salts and other compounds can react with CO 2 and H 2 S and form solids which can be withdrawn in a solid purge, thereby eliminating or greatly reducing the need to treat the raw gaseous product for acid gas removal.
  • calcium salts can also bind with, and render inert or relatively inert, mineral constituents of the carbonaceous feed so the alkali metal salt catalysts can remain active longer. By preventing such minerals from reacting with and deactivating the alkali metal catalysts, greater catalyst recovery from the solid purge can be achieved and catalyst losses can be reduced. The process can allow for up to -90% catalyst recovery.
  • CO 2 in the gasifier causes the catalyst to deactivate, so that by eliminating the CO 2 , high catalytic activity can be sustained and more complete conversion can be achieved.
  • removal OfCO 2 from the gas phase can substantially alter the ratio of hydroxide to carbonate forms of the catalyst. Eliminating CO 2 effectively increases the activity of the catalyst and enables a high rate of gasification to occur at mild operating temperatures. At mild temperatures, the kinetics favor greater direct conversion of coal (or other carbonaceous materials) to methane, and the coal, which can convert to less reactive char at conventional catalytic coal gasification temperatures, can remain more reactive. Mild temperature operation can also reduce catalyst losses and corrosion of system components caused by volatilization of the catalyst and hazardous trace elements in the carbonaceous feed.
  • the catalytic gasification processes of the present invention can also be simpler and less costly to build and operate than known prior processes, and can be less prone to overheating, corrosion, char build-up and other problems long associated with other gasification processes and systems.
  • the estimated Btu in, versus Btu out, efficiency can be on the order of 80 to 85% overall.
  • a method for direct catalytic gasification of carbonaceous material to methane comprising causing a reaction of the carbonaceous material in an environment including steam and an alkali metal salt catalyst at mild temperatures in the range from about 300 to about 700 0 C and a pressure from about 15 to about 100 atmospheres, and removing CO 2 (and H 2 O) from the products of the reaction in the environment so as to produce a dry raw gaseous product consisting of from about 30% to about 90% methane.
  • the dry raw gaseous product can include at least about 40% methane, or at least about 50%, or at least about 60%, or even at least about 70% methane by volume. This embodiment can be carried out in the absence of or without extensive added or recycled H 2 or CO.
  • Another embodiment provides an improved method for direct catalytic gasification of carbonaceous material to combustible gases, which can be carried out in the absence of added or recycled H 2 or CO, wherein the gasification reaction occurs at a temperature range from about 300 to about 700 0 C and a pressure from about 15 to about 100 atmospheres in an environment including steam, an alkali catalyst, and a mineral binder material, and wherein said carbonaceous material includes silica and/or alumina, and other mineral constituents.
  • the mineral binder material can combine with at least a portion of these mineral constituents to inhibit the silica and/or alumina, and other mineral constituents from combining with the alkali catalyst.
  • FIG. 1 is a general Flow Diagram of a Mild Catalytic Coal Gasification (MCCG) Process in accordance with an embodiment of the present invention.
  • MCCG Mild Catalytic Coal Gasification
  • catalyst refers to compositions that are introduced to the process to facilitate the gasification reactions.
  • the term is not meant to be limited to the specific chemical moiety or moieties that activate the carbon surface or otherwise actually participate in the gasification reactions.
  • Standard temperature gasification means steam gasification of carbonaceous material at about 55O 0 C or lower.
  • Synigngas as used herein, means synthetically produced fuel gas, typically produced from standard coal gasification processes, comprising mostly CO and H 2 by volume.
  • “Dry raw gaseous product” as used herein means non-steam or substantially non-steam products of direct catalytic steam gasification.
  • steam can be a component of the raw gaseous reaction products from direct catalytic steam gasification of carbonaceous materials
  • reference to 'dry raw gaseous product' herein means the gaseous products, other than steam, that flow from the gasification reactor and have not been further purified.
  • "CO 2 trap material” as used herein can be CaO, Ca(OH) 2 , dolomite, limestone, Trona, or other compounds effective for regeneratively combining with CO 2 to form solid carbonates or bicarbonates, and combinations thereof.
  • Mineral binder material as used herein can be a calcium salt, such as
  • CaO, Ca(OH) 2 , CaCO 3 , or any other alkaline earth metal salts which can react with and tie up silica, alumina, and other mineral constituents of the carbonaceous feed so as to inhibit such constituents from reacting with and deactivating the catalyst.
  • the present invention provides a catalytic steam gasification process for converting carbonaceous materials to gases substantially comprising methane or other combustible gases.
  • the process can operate at mild temperatures and produce a dry raw gaseous product that can be used either directly as fuel or purified to pipeline quality methane without the need to remove therefrom substantial quantities of carbon monoxide or acid gases.
  • the process can include a feed preparation zone, a gasification reactor, a catalyst recovery system, and a CO 2 trap regeneration zone.
  • carbonaceous material can be reacted with oxidizing agents such as steam and/or oxygen in the presence of CO 2 trap material, and one or more alkali metal salt catalysts, to produce predominantly methane as the raw product gas.
  • oxidizing agents such as steam and/or oxygen in the presence of CO 2 trap material, and one or more alkali metal salt catalysts
  • the operating temperature in the reactor is below about 550 0 C
  • the pressure is in the range from about 12 to about 40 atm.
  • the gasification reactor can have a moving bed or a fluidized bed.
  • Mineral binder material can also be present in the reactor, and can bind with silica, alumina, and other mineral constituents of the carbonaceous feed and thereby prevent or inhibit such constituents from reacting with and deactivating the catalyst.
  • the feed preparation zone can include one or more mixers for combining the carbonaceous material, the alkali metal catalyst, the mineral binder material, and the CO 2 trap material, and a feed system for introducing the catalyst/carbon/CO 2 trap mixture to the gasification reactor as dry solids or as a liquid slurry.
  • the feed system can be a star feeder, screw feeder, or other mechanism effective in maintaining required temperature, pressure and flow rate of the materials to be introduced to the gasification reactor.
  • the carbonaceous material can be coal, heavy oils, petroleum coke, other petroleum products, residua, or byproducts, biomass, garbage, animal, agricultural, or biological wastes and other carbonaceous waste materials, etc., or mixtures thereof.
  • the coal or other carbonaceous material can be ground or pulverized to an average particle size of about 30 to 100 mesh before its delivery for use in the gasification process.
  • Such particles can be impregnated with alkali catalyst in aqueous solution and dried by known methods.
  • the impregnated and dried particles can be mixed with the CO 2 trap material and/or mineral binder material and introduced to the gasifier as a single stream, or such streams can be fed separately, or in combination, as convenient.
  • the carbonaceous materials for use in the process can be more coarse, with an average particle size of about 1-2 mm.
  • Such coarse particles can be combined and ground with an aqueous slurry of finely divided mineral binder material.
  • the resulting paste can be ground with alkali catalyst, dried at about 100 0 C with superheated steam to recover a fine powder of carbonaceous material with highly dispersed mineral binder and alkali catalyst having an average particle size of less than roughly 0.02 mm, pelletized to a particle size of about 30 - 100 mesh, and fed to the gasification reactor.
  • the CO 2 trap material can be combined and fed with the prepared carbonaceous material, or can be fed separately.
  • the CO 2 trap material can be CaO or Ca(OH) 2 , or any other compound that can react with CO 2 to form solid carbonates or bicarbonates, so as to shift the kinetics in the direction of increased methane concentration in the raw gas product.
  • the CO2 trap material is CaO.
  • Sufficient CO 2 trap material can be used so as to remove substantially all the CO 2 from the products of the reaction to yield a dry raw gaseous product containing less than about 2% CO 2 by volume.
  • the molar ratio of CO 2 trap material to carbon in the reactor can be in the range of about 0.1:1 to about 1 : 1, or more particularly in the range of about 0.3 : 1 to about 0.7: 1, and more particularly about 0.5:1.
  • the CaO to carbon ratio fed to the reactor can be in the range of about 0.5 : 1 to about 4: 1 , or more particularly in the range of about 1:1 to about 3:1, and more particularly about 2:1.
  • the CO 2 trap material can be effective without being highly dispersed on the carbon surface. Thus operating convenience can dictate whether the CO 2 trap material and the carbonaceous feed are mixed and then fed or introduced separately to the gasifier.
  • the alkali catalyst can comprise any OfNa 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , Li 2 CO 3 ,
  • the catalyst can be a single compound or a combination of alkali metal salts, which can be binary or ternary salt mixtures.
  • the alkali catalyst loading can be from 1 to 50 weight percent based on the carbonaceous feed on a dry, ash-free basis. Preferably, the alkali loading is in the range of about 1 to 30 wt%.
  • the alkali catalyst can be effective without the presence of any fluorinated compounds.
  • the alkali metal salt catalyst can comprise a eutectic salt mixture of
  • the eutectic salt mixture can be a binary salt mixture of about 29% Na 2 CO 3 and about 71% K 2 CO 3 , mole percent. In other embodiments the eutectic salt mixture can be a ternary composition of about 43.5% Li 2 CO 3 , 31.5% Na 2 CO 3 and 25% K 2 CO 3 , mole percent, or a ternary salt mixture of about 39% Li 2 CO 3 , 38.5% Na 2 CO 3 and 22.5% Rb 2 CO 3 , mole percent.
  • the mineral binder material can be a compound or a mixture of compounds selected from the group consisting of CaO, Ca(OH) 2 , CaCO 3 , and other alkaline earth metal salts.
  • the mineral binder can be kneaded or otherwise dispersed on the carbonaceous feed particles in a feed pretreatment step before the alkali catalyst is contacted with the carbonaceous feed.
  • kneading calcium salts with the carbonaceous feed particles can be used to help prevent mineral interactions with the alkali metal catalyst.
  • the carbonaceous feed, the mineral binder, and alkali catalyst can be mixed together simultaneously by conventional methods.
  • the mineral binder material can be fed separately to the gasifier and/or mineral binder material can fo ⁇ n in the gasifier, wherein such mineral binder material (e.g., CaCO 3 ) can react with silica, alumina, and other mineral constituents present in the carbonaceous feed and prevent or inhibit some alkali catalyst loss and deactivation.
  • the mineral binder can combine with at least a portion of any reactive mineral constituents in the carbonaceous feed such as aluminum and silicon constituents, and thereby prevent or inhibit such reactive mineral constituents from reacting with the alkali catalysts.
  • the mineral binder material can thus be effective at stoichiometric quantities about equal to that of the reactive mineral constituents in the carbonaceous feed.
  • the carbonaceous feed material is Illinois #6 coal which contains on a dry basis about 10 to 11 wt% ash of which silica comprises about 51 wt% and alumina comprises about 18 wt%
  • 7.1 tons OfCaCO 3 or the equivalent amount of another mineral e.g., about 4.0 tons of CaO
  • the amount of CaO utilized can be in the range of about 2 to 6 wt% and is preferably highly dispersed with the feed; whereas to promote CO 2 trapping, higher amounts in the range of 50 to 200 wt%, which need not be highly dispersed with the feed can be utilized. It is expected that substantial amounts in the range of at least 60% to about 90% of the CO 2 trap material can be recovered in the CO 2 trap regenerator and recycled within the process, such that the amount of fresh CO 2 trap material can be about 5 to 80 wt% CaO.
  • the feed can include about 5% CaO highly dispersed within the feed and the balance as a separate stream.
  • the reactor is designed so that a solid purge can be periodically or continuously withdrawn.
  • the CO 2 trap material reacts with CO 2 in the reactor and is withdrawn in the "carbonated" form with the solid purge.
  • the CO 2 trap material is CaO or Ca(OH) 2
  • the solid purge can include particles OfCaCO 3 , as well as particles of unreacted carbon, the ash or mineral constituents of the carbonaceous feed, and some alkali catalyst in various forms.
  • the process of the invention can include a regeneration process of conventional design to recover and recycle active CO 2 trap material, if desired or necessary.
  • the CO 2 trap material is CaO
  • the CO 2 trap material regenerator can be a calciner.
  • CaCO 3 particles can be separated from said withdrawn solids by passing through a coarse sieve, or by elutriation of fine particles or other techniques, and can be directed to the calciner to recover the CaO.
  • the recovered CaO can be activated or its surface area increased by steam treatment or similar treatment, during or after calcination and prior to recycling.
  • the regenerated CaO recycled to the gasifier can constitute as much as about 90% of the calcium value withdrawn in the solid purge.
  • the calcined off-gas mostly CO 2 and possibly some CaCO 3 , CaS and CaSO 4 , as well as H 2 S and possibly SO 2 and O 2 , can be sequestered or otherwise properly disposed.
  • the solid purge fraction that passes through the sieve can include soluble alkali metal salts, and can also include insoluble alkali and/or calcium aluminosilicates. These can be treated in a catalyst recovery system for recovery and recycle of the catalyst.
  • the catalyst recovery system can comprise a water wash system and optionally can comprise a lime digestion system.
  • the hot carbon/ash particles can be contacted with water and soluble catalyst constituents of the particles can dissolve into solution. If the particles contain small amounts of alkali aluminosilicates, then the water contacting step can be sufficient to accomplish essentially complete catalyst recovery.
  • the washed solids can be digested in an alkaline solution or slurry to recover insoluble alkali moieties.
  • the washed solids can contain sufficient calcium or other alkaline compounds such that little or no additional lime or other alkaline solution is necessary for digestion.
  • the partial pressure and/or concentration of steam can be monitored and controlled to maximize conversion rates and maximize overall conversion to methane or other desired gaseous product such as syngas.
  • causing the reaction includes maintaining a molar ratio of steam to carbon in the range of about 1.5 to 3 and/or controlling partial pressure of the steam by addition of a non-reactive gas to the gasification environment.
  • the catalytic steam gasification process can produce a dry raw gaseous product that includes at least about 40% methane and can include at least about 50%, or at least about 60%, or even at least about 70% or higher, methane by volume, without the need for H 2 and CO recycling, or extensive recycling, and without the need for separate stage water-gas shift reactions.
  • Other embodiments produce a dry raw gaseous product that can include about 80% methane or higher.
  • the overall direct carbon conversion of carbonaceous material to methane can be at least about 50%, more particularly at least about 65%, still more particularly at least about 80%, and still more particularly at least about 90%.
  • the carbon conversion of the carbonaceous material can be at least about 50% or at least about 65% at less than about 55O 0 C. .
  • alkali metal salts compliment transition metal salts in that they keep them active for longer reaction times.
  • the active catalyst state may actually contain three metals (two outside catalysts and one from the mineral in coal).
  • coal can be gasified at low temperatures and elevated pressures to produce methane, and that lower temperatures help to minimize syngas formation.
  • Example 2 MCCG in Accordance with an Embodiment of the Invention
  • MCCG mild catalytic coal gasification
  • Particulate coal or other carbonaceous material, particles of CO 2 trap material and/or mineral binder material, and an alkali metal catalyst solution can be combined and mixed in mixer 100 to form a feed stream and fed to one or more lock hoppers shown generally as lock hopper 200.
  • Said particulate streams can be fed separately to mixer 100 or combined (not shown) before being fed to mixer 100.
  • the feed stream can be fed to gasifier 300 by a screw feeder 250, which alternatively can be a star feeder, or a mechanism that feeds the carbonaceous material as a liquid slurry, or any other feed mechanism known in the art which allows carbonaceous material to be fed to a gasifier at a rate, temperature and pressure necessary to achieve the desired gasification result.
  • a screw feeder 250 which alternatively can be a star feeder, or a mechanism that feeds the carbonaceous material as a liquid slurry, or any other feed mechanism known in the art which allows carbonaceous material to be fed to a gasifier at a rate, temperature and pressure necessary to achieve the desired gasification result.
  • Gasifier 300 can be operated in a fluid bed 400A or a moving bed 400B mode.
  • Advantages of fluid bed mode 400A include ease of design and easy tar control.
  • One disadvantage of the fluid bed is that fresh feed particles of coal and the CO 2 trap material may be removed with converted residue (solid purge).
  • the steam concentration in the outlet gas will be higher than in the moving bed.
  • the moving bed mode is more complex because solid recycle is needed to move partially gasified coal to the top of the bed to prevent tar from leaving the reactor with the product gas.
  • an advantage of the moving bed is that the steam concentration in the outlet gas will be substantially reduced and attrition of the CO 2 trap material is minimized. This mode also maximizes coal conversion.
  • such compounds can react with and tie up minerals in the coal or other carbonaceous material, preventing or inhibiting the minerals from reacting with the alkali metal salt catalysts so the alkali metal salt catalysts will remain active longer, increasing the carbon conversion efficiency and carbon conversion rate and improving catalytic recovery.
  • such compounds can react with alumina, silica, or other mineral constituents of the coal.
  • the coal or other carbonaceous feed can also be pretreated with CaO, Ca(OH) 2 , CaCO 3 , or other alkaline earth metal salts to tie up the minerals/ash in the coal.
  • Gasifier 300 is operated at about 55O 0 C or less and at an operating pressure of less than about 1000 psig (68 atm).
  • CaO, Ca(OH) 2 , or other compounds effective for regeneratively combining with CO 2 can be used as a trap for CO 2 and sulfur gases. This will enhance catalytic activity by driving the reaction forward and will also enhance production of methane by shifting the reaction kinetics toward increased production of methane.
  • Steam is fed to the bottom of gasifier 300. It can be beneficial to add a small quantity of O 2 /air to the steam to activate the catalyst.
  • oxygen or air is added to the steam to provide oxidized sites on the coal surface and provide complexes where catalyst can interact with the coal to produce higher gasification rates and carbon conversion.
  • Product gases will leave the top of gasifier 300 and pass through a condenser 500 to remove steam.
  • the condensed water can be used within the catalyst recovery system 600.
  • the product gases mostly CH 4 , with lesser amounts of H 2 and NH3 can be diverted for separation (not shown) using traditional methods, as needed. Gas separation will be dependent on target product end use.
  • syngas is produced by lowering pressure and reducing CaO feed (or other CO 2 trap) to control the H 2 /C0 ratio.
  • CO 2 trap material such as CaO or Ca(OH) 2 particles
  • an alkali metal catalyst solution are mixed in mixer 100, fed to lock hopper 200, and fed to gasifier 300 as described above.
  • Mixer 100 can comprise an impeller and means to heat the contents such that the carbonaceous particles can become impregnated with alkali catalyst therein.
  • Gasifier 300 can be operated in a fluid bed 400 A or a moving bed 400B mode, as described, and is operated at a temperature between about 300°C about 700°C and a pressure from about 12 to about 40 atm.
  • CaO or Ca(OH) 2 can be used as a trap for CO 2 and sulfur gases, and CaO, Ca(OH) 2 , CaCO 3 , or other alkaline earth metal salts can react with alumina, silica, or other mineral constituents of the coal.
  • Carbon conversion rate for steam gasification of petroleum coke was studied at 700 0 C and 650 0 C. Carbon conversion without catalyst at 700 0 C was about 35% after 15 minutes and only increased to about 45% after 60 minutes and about 55% after 90 minutes. With KOH catalyst, the conversion increased to about 45% after 15 minutes, and to about 55%, 60%, and 80% after 30, 60, and 90 minutes respectively. With KOH catalyst and CaO (again loaded at 1 :2 molar CaO/C), conversion increased to about 85% after 15 or 30 minutes and to about 95% after 60 or 90 minutes. The corresponding conversions at 65O 0 C and 60 minutes, were 15% for uncatalyzed petroleum coke, about 50% with KOH, and about 80% with the CO 2 trap. The increase in conversion with the CO 2 trap at 65O 0 C indicates that steam gasification of petroleum coke at 650°C can be economically feasible.
  • Example 5 Test Results of Steam Gasification using KOH. LiOH. NaOH. and Ca(OH) 2 .
  • Carbon conversion for catalytic steam gasification in the temperature range of 500°C and 700°C of Powder River Basin coal (PRB) in the presence of KOH, LiOH, NaOH, and Ca(OH) 2 was measured.
  • the conversion with KOH was about 90% and 85% respectively at 700°C and 65O 0 C, and decreased to about 70% at 600 0 C and to about 60% at 55O 0 C and 500 0 C.
  • NaOH showed significantly better performance of about 80% conversion at 600 0 C and 70% at 550 0 C, and performed about the same as KOH at 700 0 C, 650 0 C and 500 0 C. This suggests NaOH as a preferred low cost catalyst for low temperature steam gasification.
  • coal is mixed with an alkali metal catalyst, and calcium salts selected from CaO, Ca(OH) 2 , CaCO 3 and other alkaline earth metal salts as described above, and then mixed with petroleum residua.
  • the coal/residua mixture is heated to about 400 to 500 0 C for about 3 to 30 minutes to disperse the catalyst, and then is gasified and further processed as described above.
  • Dispersing the catalyst allows for better catalyst contact, allowing temperatures to be dropped to about 300 0 C to about 55O 0 C.
  • Such dispersal also provides better contact and reaction between reactive mineral components of the carbonaceous feed and such alkaline earth salts, thereby avoiding mineral/catalyst interactions and enhancing catalyst recovery. Dispersal also allows for more efficient sulfur removal, reduced catalyst quantities, and enables extensive gasification to result in only unreactive solids and minerals remaining after gasification is complete.
  • the coal to residua weight ratio is in the range of about 1:1 to about 1:10.
  • the four feed components can be combined first into two streams, one comprising coal and calcium salts, and the other comprising alkali catalyst and residua; and such combined streams can then be mixed together and heated, as above, to about 400 to 500 0 C for about 3 to 30 minutes to disperse the alkali catalyst onto the coal.
  • a small amount of residua can be combined with the coal, blended with the catalyst, and then blended with the balance of the residua.
  • the coal/residua/catalyst mixture is then introduced into a reactor at the dispersing temperature described above (400 to 500 0 C) for about 3 to 30 minutes as described, and the dispersed mixture is introduced into another reactor where steam is added. Gasification is then done with steam to produce gases (methane, ethane, propane and butane) and light distillate C5 to ClO fraction (gasoline fraction).
  • gases methane, ethane, propane and butane
  • light distillate C5 to ClO fraction gasoline fraction

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de gazéification à la vapeur à catalyseur de métal alcalin qui utilise un matériau piège de CO2 et/ou un matériau de liaison minéral à l'intérieur du gazogène. Le procédé réalise de manière optimale plus de 90 % de transformation du carbone avec plus de 80 % de rendement de méthane. Le produit gazeux brut peut être utilisé directement comme combustible. Le catalyseur peut être récupéré de la purge solide et recyclé vers le gazogène et/ou le piège de CO2 peut être régénéré et recyclé vers le gazogène.
PCT/US2006/024050 2005-07-01 2006-06-21 Procede de gazeification a la vapeur catalytique modere WO2007005284A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BRPI0612806A BRPI0612806A2 (pt) 2005-07-01 2006-06-21 método para gaseificação catalítica de material carbonáceo em gases combustíveis
EP06773644A EP1910500A2 (fr) 2005-07-01 2006-06-21 Procede de gazeification a la vapeur catalytique modere
CA002612249A CA2612249A1 (fr) 2005-07-01 2006-06-21 Procede de gazeification a la vapeur catalytique modere
JP2008519394A JP2009500471A (ja) 2005-07-01 2006-06-21 温和な接触水蒸気ガス化法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US69599405P 2005-07-01 2005-07-01
US60/695,994 2005-07-01
US11/421,507 US20070000177A1 (en) 2005-07-01 2006-06-01 Mild catalytic steam gasification process
US11/421,507 2006-06-01

Publications (2)

Publication Number Publication Date
WO2007005284A2 true WO2007005284A2 (fr) 2007-01-11
WO2007005284A3 WO2007005284A3 (fr) 2007-06-14

Family

ID=37587889

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/024050 WO2007005284A2 (fr) 2005-07-01 2006-06-21 Procede de gazeification a la vapeur catalytique modere

Country Status (7)

Country Link
US (1) US20070000177A1 (fr)
EP (1) EP1910500A2 (fr)
JP (1) JP2009500471A (fr)
KR (1) KR20080041635A (fr)
BR (1) BRPI0612806A2 (fr)
CA (1) CA2612249A1 (fr)
WO (1) WO2007005284A2 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009013320A (ja) * 2007-07-06 2009-01-22 National Institute Of Advanced Industrial & Technology 水素の製造方法
JP2011508066A (ja) * 2007-12-28 2011-03-10 グレイトポイント・エナジー・インコーポレイテッド 触媒ガス化のための石油コークス組成物
JP2011526325A (ja) * 2008-06-27 2011-10-06 グレイトポイント・エナジー・インコーポレイテッド ２系列触媒ガス化システム
JP2012503088A (ja) * 2008-09-19 2012-02-02 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックのガス化のための方法
DE102016219986A1 (de) 2016-10-13 2018-04-19 Marek Fulde Verfahren zur Herstellung von Methan
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

Families Citing this family (101)

* 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
KR101138096B1 (ko) * 2007-08-02 2012-04-25 그레이트포인트 에너지, 인크. 촉매-담지된 석탄 조성물, 제조 방법 및 용도
WO2009024880A2 (fr) * 2007-08-22 2009-02-26 Sasol Technology (Proprietary) Limited Gazéification
WO2009048724A2 (fr) * 2007-10-09 2009-04-16 Greatpoint Energy, Inc. Compositions pour la gazéification catalytique d'un coke de pétrole
US20090090055A1 (en) * 2007-10-09 2009-04-09 Greatpoint Energy, Inc. Compositions for Catalytic Gasification of a Petroleum Coke
US20090151253A1 (en) * 2007-12-17 2009-06-18 Range Fuels, Inc. Methods and apparatus for producing syngas and alcohols
WO2009086367A1 (fr) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Compositions de coke de pétrole pour gazéification catalytique et leurs procédés de préparation
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
WO2009086372A1 (fr) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Carburants carbonés et procédés de préparation et d'utilisation de ces derniers
WO2009086363A1 (fr) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Compositions de charbon pour gazéification catalytique et leur procédé de préparation
WO2009086366A1 (fr) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Procédés pour fabriquer du gaz de synthèse et produits dérivés de gaz de synthèse
WO2009086370A2 (fr) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Procédés de fabrication de produits dérivés de gaz synthétique
CA2713656C (fr) 2007-12-28 2014-07-08 Greatpoint Energy, Inc. Gazeificateur de boues a generation de vapeur pour la gazeification catalytique d'une charge carbonee
US20090165383A1 (en) * 2007-12-28 2009-07-02 Greatpoint Energy, Inc. Catalytic Gasification Process with Recovery of Alkali Metal from Char
US8608981B2 (en) 2008-01-31 2013-12-17 Battelle Memorial Institute Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass
US8241605B2 (en) * 2008-01-31 2012-08-14 Battelle Memorial Institute Methods and apparatus for catalytic hydrothermal gasification of biomass
US8114177B2 (en) 2008-02-29 2012-02-14 Greatpoint Energy, Inc. Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
CN101959996B (zh) * 2008-02-29 2013-10-30 格雷特波因特能源公司 用于气化作用的颗粒状组合物及其制备和连续转化
US7926750B2 (en) * 2008-02-29 2011-04-19 Greatpoint Energy, Inc. Compactor feeder
US20090220406A1 (en) * 2008-02-29 2009-09-03 Greatpoint Energy, Inc. Selective Removal and Recovery of Acid Gases from Gasification Products
US8286901B2 (en) * 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
WO2009111330A1 (fr) * 2008-02-29 2009-09-11 Greatpoint Energy, Inc. Procédés de fabrication d’adsorbants et procédés pour éliminer des contaminants de fluides en utilisant ceux-ci
US8297542B2 (en) * 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US20090260287A1 (en) * 2008-02-29 2009-10-22 Greatpoint Energy, Inc. Process and Apparatus for the Separation of Methane from a Gas Stream
WO2009111345A2 (fr) 2008-02-29 2009-09-11 Greatpoint Energy, Inc. Compositions particulaires de gazéification catalytique
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
WO2009111335A2 (fr) * 2008-02-29 2009-09-11 Greatpoint Energy, Inc. Compositions de charbon pour gazéification catalytique
US8709113B2 (en) * 2008-02-29 2014-04-29 Greatpoint Energy, Inc. Steam generation processes utilizing biomass feedstocks
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
RU2359006C1 (ru) * 2008-05-05 2009-06-20 Сергей Романович Исламов Способ переработки угля
US20090324461A1 (en) * 2008-06-27 2009-12-31 Greatpoint Energy, Inc. Four-Train Catalytic Gasification Systems
CN102112585B (zh) * 2008-06-27 2013-12-04 格雷特波因特能源公司 用于sng生产的三列催化气化系统
WO2009158583A2 (fr) * 2008-06-27 2009-12-30 Greatpoint Energy, Inc. Systèmes de gazéification catalytique à quatre lignes
CN102076828A (zh) * 2008-06-27 2011-05-25 格雷特波因特能源公司 用于合成气制备的四列催化气化体系
WO2010002792A2 (fr) 2008-06-30 2010-01-07 Kior, Inc. Co-traitement de biomasse solide dans une unité de traitement pour raffinage de pétrole classique
US9352329B2 (en) 2008-08-12 2016-05-31 4A Technologies, Llc Modularized system and method for urea production using a bio-mass feedstock
MX2011001680A (es) * 2008-08-12 2011-06-09 4A Technologies Llc Sistema modularizado y metodo para produccion de urea usando un material de alimentacion de biomasa.
JP4733792B2 (ja) * 2008-08-26 2011-07-27 株式会社豊田中央研究所 エネルギーガス製造方法及びエネルギーガス貯蔵材料
WO2010033848A2 (fr) * 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Processus de gazéification d’une charge carbonée
CN102159683B (zh) * 2008-09-19 2014-10-01 格雷特波因特能源公司 碳质原料的气化方法
CN102159687B (zh) * 2008-09-19 2016-06-08 格雷特波因特能源公司 使用炭甲烷化催化剂的气化方法
KR101275429B1 (ko) * 2008-10-23 2013-06-18 그레이트포인트 에너지, 인크. 탄소질 공급원료의 기체화 방법
KR101290453B1 (ko) 2008-12-30 2013-07-29 그레이트포인트 에너지, 인크. 촉매된 탄소질 미립자의 제조 방법
KR101290423B1 (ko) 2008-12-30 2013-07-29 그레이트포인트 에너지, 인크. 촉매된 석탄 미립자의 제조 방법
US8524959B1 (en) 2009-02-18 2013-09-03 Kior, Inc. Biomass catalytic conversion process and apparatus for use therein
US8558043B2 (en) * 2009-03-04 2013-10-15 Kior, Inc. Modular biomass treatment unit
US8562933B2 (en) * 2009-03-31 2013-10-22 Alstom Technology Ltd Hot solids process selectively operable based on its primary purpose
US20100281769A1 (en) * 2009-03-31 2010-11-11 Alstom Technology Ltd. Hot solids process selectively operable based on the type of application that is involved
US20100288678A1 (en) * 2009-03-31 2010-11-18 Andrus Jr Herbert E Hot solids process having an output suitable for the input to a petrochemical process
US20100290975A1 (en) * 2009-03-31 2010-11-18 Alstom Technology Ltd Hot solids process selectively operable for combustion purposes and gasification purposes
US8728182B2 (en) * 2009-05-13 2014-05-20 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US8268899B2 (en) * 2009-05-13 2012-09-18 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
EP2430126A2 (fr) * 2009-05-13 2012-03-21 Greatpoint Energy, Inc. Procédés d'hydrométhanation de charges d'alimentation carbonées
CA2759954A1 (fr) * 2009-05-22 2010-11-25 Robert Bartek Traitement d'une biomasse a l'aide d'une source d'hydrogene
US8623634B2 (en) * 2009-06-23 2014-01-07 Kior, Inc. Growing aquatic biomass, and producing biomass feedstock and biocrude therefrom
KR101042603B1 (ko) * 2009-07-02 2011-06-20 고등기술연구원연구조합 가스화 시스템
KR101570882B1 (ko) 2009-08-04 2015-11-23 에스케이이노베이션 주식회사 메탄의 열분해 및 이산화탄소 전환 반응을 포함하는 탄소 함유 물질의 가스화 방법
WO2011017630A1 (fr) 2009-08-06 2011-02-10 Greatpoint Energy, Inc. Procédés d'hydrométhanation d'une charge d'alimentation carbonée
CN102575181B (zh) 2009-09-16 2016-02-10 格雷特波因特能源公司 集成氢化甲烷化联合循环方法
WO2011034891A1 (fr) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Procédé à deux modes pour production d'hydrogène
AU2010295764B2 (en) 2009-09-16 2013-07-25 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
WO2011034889A1 (fr) 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Processus intégré d'hydrométhanation à cycle combiné
CN102667057B (zh) 2009-10-19 2014-10-22 格雷特波因特能源公司 整合的强化采油方法
AU2010310849B2 (en) * 2009-10-19 2013-05-02 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
EP2501788A4 (fr) 2009-11-18 2013-12-04 G4 Insights Inc Méthanisation de la biomasse améliorée par sorption
US20110146978A1 (en) * 2009-12-17 2011-06-23 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
CA2780375A1 (fr) 2009-12-17 2011-07-14 Greatpoint Energy, Inc. Processus integre de recuperation assistee des hydrocarbures
US8669013B2 (en) * 2010-02-23 2014-03-11 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
CN102858925B (zh) 2010-04-26 2014-05-07 格雷特波因特能源公司 碳质原料的加氢甲烷化与钒回收
CN102906230B (zh) 2010-05-28 2015-09-02 格雷特波因特能源公司 液体重烃进料向气态产物的转化
US8057641B2 (en) 2010-07-19 2011-11-15 Kior Inc. Method and apparatus for pyrolysis of a biomass
JP2013535565A (ja) * 2010-08-18 2013-09-12 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックのハイドロメタネーション
JP2013537248A (ja) 2010-09-10 2013-09-30 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックの水添メタン化
US8772556B2 (en) 2010-09-22 2014-07-08 Kior, Inc. Bio-oil production with optimal byproduct processing
US20120102837A1 (en) 2010-11-01 2012-05-03 Greatpoint Energy, Inc. Hydromethanation Of A Carbonaceous Feedstock
KR101543136B1 (ko) 2010-11-01 2015-08-07 그레이트포인트 에너지, 인크. 탄소질 공급원료의 히드로메탄화
US9017428B2 (en) 2010-11-16 2015-04-28 Kior, Inc. Two-stage reactor and process for conversion of solid biomass material
CN103391989B (zh) 2011-02-23 2015-03-25 格雷特波因特能源公司 伴有镍回收的碳质原料加氢甲烷化
US8236173B2 (en) 2011-03-10 2012-08-07 Kior, Inc. Biomass pretreatment for fast pyrolysis to liquids
WO2012145497A1 (fr) 2011-04-22 2012-10-26 Greatpoint Energy, Inc. Hydrométhanation d'une matière première carbonée avec valorisation des produits de carbonisation
WO2012151275A1 (fr) * 2011-05-02 2012-11-08 Virent, Inc. Appareil et procédé de conversion de biomasse en charge d'alimentation pour des processus de fabrication de biocarburant/biocombustible et de substances biochimiques
WO2012166879A1 (fr) 2011-06-03 2012-12-06 Greatpoint Energy, Inc. Hydrométhanation d'une charge d'alimentation carbonée
CN103890147A (zh) 2011-08-17 2014-06-25 格雷特波因特能源公司 碳质原料的加氢甲烷化
US20130046124A1 (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
EP2800799A4 (fr) 2012-01-06 2015-08-26 Kior Inc Réacteur à deux étages et procédé pour la conversion de matériau de biomasse solide
CN103484180B (zh) * 2012-06-15 2016-07-06 新奥科技发展有限公司 一种燃煤自供热的催化气化制天然气的工艺和系统
IN2014DN09147A (fr) * 2012-07-03 2015-05-22 Battelle Memorial Institute
WO2014055353A1 (fr) 2012-10-01 2014-04-10 Greatpoint Energy, Inc. Charge d'alimentation de charbon de rang bas à particules agglomérées et ses utilisations
IN2015DN02940A (fr) 2012-10-01 2015-09-18 Greatpoint Energy Inc
WO2014055365A1 (fr) 2012-10-01 2014-04-10 Greatpoint Energy, Inc. Utilisation d'un charbon de rang bas contaminé pour permettre une combustion
WO2014055349A1 (fr) 2012-10-01 2014-04-10 Greatpoint Energy, Inc. Charge d'alimentation de charbon de rang bas à particules agglomérées et ses utilisations
AU2013377372B2 (en) * 2013-02-05 2018-01-04 Reliance Industries Limited A process for catalytic gasification of carbonaceous feedstock
US20180162729A1 (en) * 2015-05-28 2018-06-14 Gas Technology Institute Power generation using hydrogen fuel with economical carbon dioxide capture
WO2017141186A1 (fr) 2016-02-18 2017-08-24 8 Rivers Capital, Llc Système et procédé de production d'électricité comprenant la méthanation
JP7280718B2 (ja) * 2018-03-09 2023-05-24 大阪瓦斯株式会社 炭素質材料のガス化方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3828474A (en) * 1973-02-01 1974-08-13 Pullman Inc Process for producing high strength reducing gas
US3847567A (en) * 1973-08-27 1974-11-12 Exxon Research Engineering Co Catalytic coal hydrogasification process
US3904386A (en) * 1973-10-26 1975-09-09 Us Interior Combined shift and methanation reaction process for the gasification of carbonaceous materials
US4720289A (en) * 1985-07-05 1988-01-19 Exxon Research And Engineering Company Process for gasifying solid carbonaceous materials
US20050137442A1 (en) * 2003-12-19 2005-06-23 Gajda Gregory J. Process for the removal of nitrogen compounds from a fluid stream

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689240A (en) * 1971-03-18 1972-09-05 Exxon Research Engineering Co Production of methane rich gases
JPS6039114B2 (ja) * 1977-02-24 1985-09-04 エクソン・リサ−チ・エンド・エンジニアリング・コンパニ− 中間Ｂｔｕガスの製造法
US5057294A (en) * 1989-10-13 1991-10-15 The University Of Tennessee Research Corporation Recovery and regeneration of spent MHD seed material by the formate process
JP4075281B2 (ja) * 2000-04-10 2008-04-16 三菱マテリアル株式会社 高カロリーガスの製造方法及びその装置
US6506361B1 (en) * 2000-05-18 2003-01-14 Air Products And Chemicals, Inc. Gas-liquid reaction process including ejector and monolith catalyst
JP2001354974A (ja) * 2000-06-13 2001-12-25 Toshiba Corp 燃料ガス化方法およびその装置
JP4395570B2 (ja) * 2002-07-30 2010-01-13 独立行政法人産業技術総合研究所 水の熱化学的分解による水素の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3828474A (en) * 1973-02-01 1974-08-13 Pullman Inc Process for producing high strength reducing gas
US3847567A (en) * 1973-08-27 1974-11-12 Exxon Research Engineering Co Catalytic coal hydrogasification process
US3904386A (en) * 1973-10-26 1975-09-09 Us Interior Combined shift and methanation reaction process for the gasification of carbonaceous materials
US4720289A (en) * 1985-07-05 1988-01-19 Exxon Research And Engineering Company Process for gasifying solid carbonaceous materials
US20050137442A1 (en) * 2003-12-19 2005-06-23 Gajda Gregory J. Process for the removal of nitrogen compounds from a fluid stream

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BROWN ET AL.: 'Biomass-Derived Hydrogen From A Thermally Ballasted Gasifier' DOE HYDROGEN PROGRAM CONTRACTORS' REVIEW MEETING August 2005, page 1 *
BROWN R.C. ET AL.: 'Biomass-Derived Hydrogen From A Thermally Ballasted Gasifier' DOE HYDROGEN PROGRAM CONTRACTORS' REVIEW MEETING 21 May 2003, pages 1 - 27, XP003014330 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009013320A (ja) * 2007-07-06 2009-01-22 National Institute Of Advanced Industrial & Technology 水素の製造方法
JP2011508066A (ja) * 2007-12-28 2011-03-10 グレイトポイント・エナジー・インコーポレイテッド 触媒ガス化のための石油コークス組成物
JP2011526325A (ja) * 2008-06-27 2011-10-06 グレイトポイント・エナジー・インコーポレイテッド ２系列触媒ガス化システム
JP2012503088A (ja) * 2008-09-19 2012-02-02 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックのガス化のための方法
DE102016219986A1 (de) 2016-10-13 2018-04-19 Marek Fulde Verfahren zur Herstellung von Methan
WO2018069503A2 (fr) 2016-10-13 2018-04-19 Marek Fulde Procédé pour la production de méthane
WO2018069503A3 (fr) * 2016-10-13 2018-06-07 Marek Fulde Procédé pour la production de méthane
DE102016219986B4 (de) 2016-10-13 2022-11-03 Fld Technologies Gmbh Verfahren zur Herstellung von Methan
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

Also Published As

Publication number Publication date
CA2612249A1 (fr) 2007-01-11
BRPI0612806A2 (pt) 2016-11-29
JP2009500471A (ja) 2009-01-08
KR20080041635A (ko) 2008-05-13
WO2007005284A3 (fr) 2007-06-14
EP1910500A2 (fr) 2008-04-16
US20070000177A1 (en) 2007-01-04

Similar Documents

Publication Publication Date Title
US20070000177A1 (en) Mild catalytic steam gasification process
Li et al. A review of CaO based catalysts for tar removal during biomass gasification
Dou et al. Hydrogen production from the thermochemical conversion of biomass: issues and challenges
Wu et al. Syngas production by chemical looping gasification of biomass with steam and CaO additive
Shen et al. Advances in in situ and ex situ tar reforming with biochar catalysts for clean energy production
KR100569120B1 (ko) 바이오메스 정제연료의 저온 촉매가스화 장치 및가스제조방법
CN102465047B (zh) 一种由煤催化气化制甲烷的方法
Fermoso et al. Sorption enhanced catalytic steam gasification process: a direct route from lignocellulosic biomass to high purity hydrogen
US8114177B2 (en) Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
TWI640471B (zh) 一種催化氣化含碳原料之工藝
Ramadhani et al. Catalytic tar conversion and the prospective use of iron-based catalyst in the future development of biomass gasification: a review
US20090165384A1 (en) Continuous Process for Converting Carbonaceous Feedstock into Gaseous Products
CN102159682A (zh) 碳质原料的气化方法
CA2490425A1 (fr) Procede de production de melanges gazeux hydrogenes
WO2010078297A1 (fr) Procédés de préparation d'une matière particulaire carbonée catalysée
KR20110102927A (ko) 촉매된 석탄 미립자의 제조 방법
AU2011320055A1 (en) Production of synthesis gas by heating oxidized biomass with a hot gas obtained from the oxidation of residual products
JP5659536B2 (ja) タール含有ガスの改質用触媒及びその製造方法、並びにタール含有ガスの改質方法
Wang et al. Sorption-enhanced steam gasification of biomass for H2-rich gas production and in-situ CO2 capture by CaO-based sorbents: a critical review
Kobayashi et al. Woody biomass and RPF gasification using reforming catalyst and calcium oxide
CN102159685A (zh) 由有机废料制备合成气和甲醇的方法
CN104804753B (zh) 原料预处理方法及催化气化方法
Liu et al. A green route for hydrogen production from alkaline thermal treatment (ATT) of biomass with carbon storage
CN101263214A (zh) 适度催化蒸汽气化方法
Gyrdymova et al. Production of Acetylene from Viable Feedstock: Promising Recent Approaches

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680031251.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2612249

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 10095/DELNP/2007

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2008519394

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006773644

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1020087002593

Country of ref document: KR

ENP Entry into the national phase

Ref document number: PI0612806

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20071228

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载