U.S. Department of Energy

The United States of America as Represented by the Department of Energy

The United States of America as Represented by the United States

Ranjani V Siriwardane

Yueying Fan

Hanjing Tian

Jarrett Riley

James C Fisher

Robert W Stevens, Jr

Shira Rosencwaig

William Benincosa

David A Berry

George Alan Richards

Duane D Miller

Justin M Weber

Materials, methods to prepare, and methods of use for producing an Hrich synthesis gas stream from coal free of nitrogen is described. One embodiment of the method comprises. The method includes an oxygen carrier at least partially reduced using a fuel in a reactor forming a reduced metal oxide comprised of first series—3d block-transition metals or mixture thereof. The reduced metal oxide is reacted with the solid fuel/steam to produce Hand CO/CO in the reactor; and the reduced metal oxide is added separately or simultaneously with a solid fuel while not impregnating the solid fuel with the reduced metal oxide.

Process for production of Hrich synthesis gas from coal/steam with Cu—Fe-alumina based catalysts

This disclosure provides a method to produce highly attrition resistant pellets by encapsulating reactive components in a vitrified clay outer layer. The reactive component mixture is present relative to the clay substrate in a weight ratio of part per 60-100 part to about 60 parts of the clay substrate. The reactive components are agglomerated first, and clay substrate is added to form the outer layer of the pellet. The pellets are calcined at temperatures above 1200 C to form a vitrified clay semi porous outer layer providing high strength to the pellet while facilitating the gas transfer for the reaction with the encapsulated reactive components. Pellets containing CuO&#x2014;FeO-alumina oxygen carrier for chemical looping combustion of fuel demonstrated high attrition resistance and high reactivity with methane.

Encapsulation method for preparation of pellets with high attrition resistance

The invention provides a calcined Fe&#x2014;Al&#x2014;Obased catalyst for the decomposition of hydrocarbons such as methane to produce hydrogen and carbon. The catalyst comprises iron oxide mixed with aluminum oxide and calcined at temperatures above 1100&#xb0; C., where Fe&#x2014;Al&#x2014;Ois a chemical composition with x&#x3e;0.1, y&#x3e;0.1, z&#x2265;0 and 0&#x3c;x/y&#x3c;200. Reaction of the calcined Fe&#x2014;Al&#x2014;Ocatalyst with methane generates a product stream comprising at least 40 vol. % Hand carbon. In an embodiment, carbon is separated from the catalyst and the catalyst is reused for continuous methane decomposition to produce H.

Iron based catalysts for production of carbon and hydrogen from decomposition of methane

Materials, methods of making, and methods of providing a trimetallic oxygen carrier for converting methane containing fuel to synthesis gas. The trimetallic oxygen carrier comprises CuFeMnO, where CuFeMnOis a chemical composition with 0&#x3c;x&#x2264;3 and 0&#x3c;y&#x2264;3 and 0&#x3c;z&#x2264;3 and, 0&#x3c;t&#x2264;5. For example, CuFeMnOmay be one of CuMnFeO, CuFeMnO, CuFeMnO, CuFeMnO, or Cu impregnated on FerMnsOu, Fe impregnated on CurMnsOu, Mn impregnated on CurFesOu where r&#x3e;0, s&#x3e;0 and u&#x3e;0 and combinations thereof. Reaction of trimetallic CuFeMnOwith methane generates a product stream comprising at least 50 vol. % CO and H.

Production of synthesis gas from natural gas with copper&#x2014;iron&#x2014;manganese oxide oxygen carriers/catalysts via partial oxidation and dry reforming processes

The invention provides a use of metal ferrite oxygen carrier for converting carbon dioxide to carbon monoxide or synthesis gas via three processes: catalytic dry reforming of methane, chemical looping dry reforming of fuel and promoting coal gasification with CO. The metal ferrite oxygen carrier comprises MFeO, where MFeOis a chemical composition with 0&#x3c;x&#x2264;4, z&#x3e;0 and 0&#x3c;y&#x2264;6 and M is one of Ca, Ba, and/or combinations thereof. For example, MFeOmay be one of CaFeO, BaFeO, MgFeO, SrFeOand/or combinations thereof. In catalytic dry reforming, methane and carbon dioxide react in the presence of metal ferrites generating a product stream comprising at least 50 vol. % CO and H. In another embodiment, chemical looping dry reforming process where metal ferrite is reduced with a fuel and then oxidized with carbon dioxide is used for production of CO from carbon dioxide. In another embodiment, the metal ferrite is used as a promoter to produce CO continuously from coal gasification with CO.

Metal ferrite oxygen carriers for conversion of CO2 to CO and fuel to syngas or CO

Methods, systems and apparatus relate to producing synthesis gas or carbon and hydrogen utilizing a reduced catalyst CuO&#x2014;FeO. The method comprises introducing CH; reducing the CuO&#x2014;FeOwith the introduced CH, yielding at least a reduced metal catalyst; oxidizing the reduced metal with Oyielding CuO&#x2014;FeO; and generating heat that would be used for the hydrogen and carbon or syngas production with the reduced catalyst CuO&#x2014;FeO.

Production of pure hydrogen and synthesis gas or carbon with CUO-Fe2O3 oxygen carriers using chemical looping combustion and methane decomposition/reforming

Metal ferrite catalyst for conversion of CO2 and methane to synthesis gas via reforming

Materials, methods to prepare, and methods of use for partial oxidation of methane. Embodiments include delivering a metal ferrite oxygen carrier to a fuel reactor, wherein the metal ferrite oxygen carrier comprises MFexOy where 1&#x2264;x&#x2264;3 and 3&#x2264;y&#x2264;5, and where M comprise a Group II alkali earth metals; and delivering a gaseous stream that contains methane to the metal ferrite oxygen carrier in the fuel reactor and maintaining the fuel reactor at a reducing temperature sufficient to reduce some portion of the metal ferrite oxygen carrier and oxidize some portion of the methane containing gas stream. Embodiments further include generating gaseous products containing Hand CO gas in the fuel reactor; withdrawing a product stream from the fuel reactor, where the gaseous products comprise the product stream, and where at least &#x3e;50 vol. % of the product stream includes CO and H; oxidizing the reduced carrier in an oxidizing reactor by contacting the reduced carrier and an oxidizing gas at an oxidizing temperature, where the oxidizing gas is comprised of oxygen, and where the oxidizing temperature is sufficient to generate an oxidizing reaction, where the reactants of the oxidizing reaction comprise some portion of the oxygen, some portion of the M component, and some portion of the FecOd component, and further wherein the product of the oxidizing reaction is a re-oxidized carrier that comprises some portion of the MFexOy; and delivering heat generated in the oxidizing reactor to the fuel reactor for the reaction of metal ferrite with methane.

Metal ferrite oxygen carriers/catalyst for partial oxidation of methane for production of synthesis gas

The disclosure provides a metal ferrite oxygen carrier for the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The metal ferrite oxygen carrier comprises MFeO, where MFeOis a chemical composition with 1.5&#x2264;x&#x2264;2.5 and 3.5&#x2264;y&#x2264;4.5 and M is one of Ca, Ba, and combinations thereof. For example, MFeOmay be one of CaFeO, BaFeO, MgFeO. SrFeOand combinations thereof. Mixing of the metal ferrite oxygen carrier and the solid carbonaceous fuel generates a product stream comprising at least 50 vol. % CO and H. The MFeOmay be supported on an inert support. In an embodiment, the MFeOcomprises at least 30 wt. % of the metal ferrite oxygen carrier the inert support when present comprises from about 5 wt. % to about 60 wt. % of the metal ferrite oxygen carrier.

Metal ferrite oxygen carriers for gasification of solid carbonaceous fuel

The disclosure provides a tri-metallic ferrite oxygen carrier for the chemical looping combustion of carbonaceous fuels. The tri-metallic ferrite oxygen carrier comprises CuFeMnO, where CuFeMnOis a chemical composition. Generally, 0.5&#x2266;x&#x2266;2.0, 0.2&#x2266;y&#x2266;2.5, and 0.2&#x2266;z&#x2266;2.5, and in some embodiments, 0.8&#x2266;x&#x2266;1.2, y&#x2266;1.2, and z&#x2267;0.8. The tri-metallic ferrite oxygen carrier may be used in various applications for the combustion of carbonaceous fuels, including as an oxygen carrier for chemical looping combustion.

Tri-metallic ferrite oxygen carriers for chemical looping combustion

The disclosure provides a metal ferrite oxygen carrier for the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The metal ferrite oxygen carrier comprises MFeOon an inert support, where MFeOis a chemical composition and M is one of Mg, Ca, Sr, Ba, Co, Mn, and combinations thereof. For example, MFeOmay be one of MgFeO, CaFeO, SrFeO, BaFeO, CoFeO, MnFeO, and combinations thereof. The MFeOis supported on an inert support. The inert support disperses the MFeOoxides to avoid agglomeration and improve performance stability. In an embodiment, the inert support comprises from about 5 wt. % to about 60 wt. % of the metal ferrite oxygen carrier and the MFeOcomprises at least 30 wt. % of the metal ferrite oxygen carrier. The metal ferrite oxygen carriers disclosed display improved reduction rates over FeO, and improved oxidation rates over CuO.

Metal ferrite oxygen carriers for chemical looping combustion of solid fuels

The disclosure provides an oxygen carrier for a chemical looping cycle, such as the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The oxygen carrier is comprised of at least 24 weight % (wt %) CuO, at least 10 wt % Fe2O3, and an inert support, and is typically a calcine. The oxygen carrier exhibits a CuO crystalline structure and an absence of iron oxide crystalline structures under XRD crystallography, and provides an improved and sustained combustion reactivity in the temperature range of 600&#xb0; C.-1000&#xb0; C. particularly for solid fuels such as carbon and coal.

Regenerable mixed copper-iron-inert support oxygen carriers for solid fuel chemical looping combustion process

Method for the production of a COsorbent prepared by integrating a clay substrate, basic alkali salt, amine liquid, hydraulic binder, and a liquid binder. The basic alkali salt is present relative to the clay substrate in a weight ratio of from about 1 part to about 50 parts per 100 parts of the clay substrate. The amine liquid is present relative to a clay-alkali combination in a weight ratio of from about 1 part to about 10 parts per 10 parts of the clay-alkali combination. The clay substrate and basic alkali salt may be combined in a solid-solid heterogeneous mixture and followed by introduction of the amine liquid. Alternatively, an alkaline solution may be blended with the amine solution prior to contacting the clay substrate. The clay-alkali-amine COsorbent is particularly advantageous for low temperature COremoval cycles in a gas stream having a COconcentration less than around 2000 ppm and an oxygen concentration around 21%, such as air.

[object Object]

Disclosed herein is a clay-alkali-amine COsorbent composition prepared by integrating a clay substrate, basic alkali salt, and amine liquid. The basic alkali salt is present relative to the clay substrate in a weight ratio of from about 1 part to about 50 parts per 100 parts of the clay substrate. The amine liquid is present relative to a clay-alkali combination in a weight ratio of from about 1 part to about 10 parts per 10 parts of the clay-alkali combination. The clay-alkali-amine C02 sorbent is particularly advantageous for low temperature COremoval cycles in a gas stream having a C02 concentration less than around 2000 ppm and an oxygen concentration around 21%, such as air.

Method for the production of a clay-alkali-amine COsorbent prepared by integrating a clay substrate, basic alkali salt, and amine liquid. The basic alkali salt is present relative to the clay substrate in a weight ratio of from about 1 part to about 50 parts per 100 parts of the clay substrate. The amine liquid is present relative to a clay-alkali combination in a weight ratio of from about 1 part to about 10 parts per 10 parts of the clay-alkali combination. The clay substrate and basic alkali salt may be combined in a solid-solid heterogeneous mixture and followed by introduction of the amine liquid. Alternatively, an alkaline solution may be blended with the amine solution prior to contacting the clay substrate. The clay-alkali-amine COsorbent is particularly advantageous for low temperature COremoval cycles in a gas stream having a COconcentration less than around 2000 ppm and an oxygen concentration around 21%, such as air. Results are presented illustrating the performance of the clay-alkali-amine COsorbent compared to a clay-amine sorbent lacking the alkali inclusion.

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Morgantown, WV, United States of America

Ranjani V Siriwardane