GB2512334A - Materials for use in chemical looping combustion - Google Patents
Materials for use in chemical looping combustion Download PDFInfo
- Publication number
- GB2512334A GB2512334A GB1305517.3A GB201305517A GB2512334A GB 2512334 A GB2512334 A GB 2512334A GB 201305517 A GB201305517 A GB 201305517A GB 2512334 A GB2512334 A GB 2512334A
- Authority
- GB
- United Kingdom
- Prior art keywords
- transition metal
- metal oxide
- particles
- inert
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 114
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004645 aluminates Chemical class 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000011230 binding agent Substances 0.000 claims abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 2
- 229940037003 alum Drugs 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- 238000005054 agglomeration Methods 0.000 description 14
- 230000002776 aggregation Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- -1 Mayenite Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 2
- 235000019854 cupric carbonate Nutrition 0.000 description 2
- 239000011646 cupric carbonate Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009483 freeze granulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C99/00—Subject-matter not provided for in other groups of this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
- F23C2900/99008—Unmixed combustion, i.e. without direct mixing of oxygen gas and fuel, but using the oxygen from a metal oxide, e.g. FeO
-
- 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
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
Abstract
An oxygen carrying material for use in a chemical looping combustion process comprises: a particulate transition metal oxide, in which individual particles of the transition metal oxide have thereon and oxide coating which is substantially inert during the chemical looping combustion process. A method of forming said oxygen carrying material comprises: calcining uncoated transition metal oxide particles; treating the calcined transition metal oxide particles with an inert oxide precursor at alkaline pH; and firing the result is coated particles the temperature of 500°C to 900°C. A second method of forming said oxygen carrying material is also disclosed and comprises: reducing uncoated transition metal oxide particles; treating the reduced transition metal oxide particles with an inert oxide powder and binding agent; and firing the resulting coated particles at a temperature of 500°C to 900°C. The transition metal oxide may be iron, copper, nickel, manganese and/or cobalt. The inert oxide coating may be alumina, silica, magnesium, zirconia, or a silicate or aluminate. The transition metal oxide particles may be prepared by wet impregnation of an inert refractory support with a soluble salt of the transition metal.
Description
Materials for use in chemical looping combustion process The present invention concerns materials for use in a chemical looping combustion process, the preparation of such materials, and the use thereof in a chemical looping combustion process.
In standard aerobic combustion of fuel in power plants and the like, carbon dioxide (C02) is produced, along with nitrogen, oxygen, nitrogen oxides (N0) and steam.
The steam can be easily separated by condensation, but in order to separate the CO2 from nitrogen and N0, costly and energy intensive separation techniques are generally required. With the aim of minimising the emissions of the greenhouse gas CO2 into the atmosphere, the chemical looping combustion (CLC) process has therefore been developed in order to permit cost effective capture of 002.
A known CLC process involves continuous re-circulation of oxygen carrier in the form of transition metal oxide particles between an air reactor and a fuel reactor. In the fuel reactor, fuel undergoes combustion with oxygen from thereby producing 002 and a stream containing H20. The reduced transition metal oxide particles are then fed to an air reactor, in which they are subjected to re-oxidation. Unused nitrogen and oxygen can be vented from the air reactor, while the re-oxidized transition metal oxide particles are again fed to the fuel reactor. Steam produced in the fuel reactor from the combustion of fuel is condensed and separated from 002. CO2 can thus be captured or sequestrated. All the process steps can be repeated for multiple reduction/oxidation (redox) cycles.
As will be apparent, combustion of fuel is not carried out aerobically in the CLO process, but instead transition metal oxides, in particulate form, are used as oxygen carriers to provide the oxygen for combustion of the gaseous fuel, thus producing 002 and steam. Formation of N0 is largely eliminated as the combustion takes place in the absence of nitrogen. After the combustion, steam is separated by condensation and 002 can be readily captured or sequestrated, and the transition metal oxide particles (which have been reduced while the gas has been oxidised) are then regenerated by oxidation.
However, after repeated reduction and oxidation cycles, it has been observed that the particulate transition metal oxides powderise, and undergo sintering (that is, they undergo loss of internal surface area), attrition and agglomeration into larger clumps.
All of these problems lower the oxygen-carrying capacity of the particles. In the case of agglomeration, large clumps of the transition metal oxide particles are formed, which thereby causes lowered total surface area, and thus lowered oxygen-carrying capacity for the transition metal oxide particles. At high temperatures, agglomeration may be caused by softening or melting of the material, and at low temperatures by the growing oxide layers on the outside of overlapping particles.
While in a fluidised bed, the transition metal oxide particles may not be in contact with one another for a sufficiently long time to result in the particles sticking together, but for a packed bed this sticking together can be significant.
There have been efforts to increase the oxygen-carrying efficiency of the transition metal oxide particles, to obtain optimum reactivity and stability during multi-redox cycles, for example, by modifying the preparation method or by using mixed oxides.
Various proposals have been published regarding methods to prevent agglomeration of transition metal oxide particles in a CLC process. For example, there are disclosures by Chuang, S Y, et al. 2008 Proc. Comb. Inst. Vol 32 pp2633-2640 and Chuang, S Y, et al. in "Combustion and Flame", Vol. 154, pp. 109-121, that at very high temperatures, the problem of lowering of oxygen-carrying capacity can be alleviated by diluting the transition metal oxide in a particle with an inert support material, either by impregnating the support with a metal precursor, or co-precipitating the transition metal oxide with a suitable inert material. However, the disparate materials employed tend to segregate and a large volume of the reactor is taken up by inert material, thereby leading to lower concentration of oxygen-carrying particles in the reactor. This in turn results in lower concentration of oxygen available for combustion of fuel in the reactor.
Thus, there is a need for a method to prevent or inhibit agglomeration of oxygen-carrying particles in a chemical looping combustion process.
The present invention therefore provides, for use in a CLC process, a particulate transition metal oxide capable of undergoing a reversible redox reaction so as to be suitable as an oxygen-carrying material in the CLC process, in which individual particles of the transition metal oxide are coated with an inert oxide (that is, an oxide which is substantially inert during the chemical looping combustion process).
It is preterred that the inert oxide coating covers at least 60% of the free surface of the individual particles (as can be determined micrographically), more preferably covering substantially the entire surface thereof The coated particulate transition metal oxide is intended for use in a chemical looping combustion process in which a reversible reduction/oxidation reaction is effected using particulate transition metal oxides as oxygen-carrying particles.
In one embodiment of the invention, the transition metal oxide particles are coated with the inert oxide using a method comprising (a) calcining uncoated transition metal oxide particles; (b) treating the calcined transition metal oxide particles with an inert oxide precursor at an alkaline pH (such as to avoid dissolution of the transition metal oxide) so as to precipitate the precursor on surfaces of the particles; and (c) firing the resulting coated particles at a temperature of from 500°C to 900°C to convert the precipitate to an inert oxide coating.
In another embodiment of the invention, the transition metal oxide particles are coated with the inert oxide using a method comprising (a) reducing uncoated transillon metal oxide partides; (b) treating the reduced transiflon metal oxide particles with an inert oxide powder and bndAng agent to adhere the powder to the surfaces of the partides; and (c)flring the resulting coated particles atatemperature of from 500°C to 900°C to reoxidise the transition metal oxide particles and bond the oxide coating.
The CLC process using such coated transition metal oxide particles according to the invention has improved efficiency, because the inert oxide coating prevents or inhibits agglomeration of the transition metal oxide particles during a CLC process.
The transition metal oxide particles generally comprise oxides of transition metals of Group VIIA, VIllA, lB or IIB of the Periodic Table of Elements, of which preferred oxides are those of the transition metals Fe (iron), Cu (copper), Ni (nickel), Mn (manganese) and/or Co (cobalt).
The transition metal is optionally on a refractory inert support of, for example, an oxide of Group IIA, IVA, IIIB or IVB of the Periodic Table of Elements, or an oxide of a Lanthanide metal. Especially preferred such supports are one or more of alumina (A1203), titanium dioxide (Ti02), silicon dioxide (SiC2), magnesium oxide (MgC), zirconium dioxide (7r02), and a mixed oxide such as a silicate or aluminate.
The transition metal oxide particles for use as oxygen-carrying particles are typically prepared by wet impregnation of such an inert support material with a soluble salt of the transition metal. A preferred example of such a salt is the nitrate.
The inert oxide coating on the transition metal oxide particles is typically also an oxide of a metal Group IIA, IVA, IIIB or IVB of the Periodic Table, or of a metal of the Lanthanide series. Alumina (A1203), titanium dioxide (Ti02), silica (SiC2), magnesia (MgO), zirconia (Zr02) or a mixed oxide such as a silicate or aluminate (e.g. Mayenite, which is a calcium aluminate of formula Ca12A114O33) are preferred such oxides.
The transition metal oxide particles may be prepared by a known preparation method such as by mechanical mixing, wet impregnation, co-precipitation, sol-gel, spray-drying, freeze granulation or mechanical mixing.
The precursor may be precipitated on the transition metal oxide particles in the form of a sol-gel, for example, using an alumina sol-gel.
The resulting inert oxide coating is porous and the coating acts as a barrier between adjacent transition metal oxide particles during a CLC process, which thereby prevents or inhibits the oxygen-carrying particles from agglomerating after continuous cycles of redox reaction. As a result of this, the oxygen-carrying capacity of the transition metal oxide particles can be maintained even after a large number of cycles of the redox reaction.
The transition metal oxide particles may prepared by a known preparation methods such as mechanical mixing, wet impregnation, co-precipitation, a sol-gel process, spray-drying, freeze granulation or mechanical mixing. Existing commercially avaflable transition metal oxide particles may also be used.
In one embodiment of the invention, the coating is applied as a sol-gel. A sol-gel with a pH value which is too low to cause decomposition of the transition metal oxide particles is applied thereto. The pH value of the sol-gel is then controlled and increased as necessary into the alkali range by the addition of an alkali (hydroxide or carbonate), for example, calcium hydroxide, so as to precipitate the coating on the surface of the particles.
In another embodiment of the invenfion, the supported metal oxide particles may be exposed to a reducing atmosphere at elevated temperatures, prior to the application of the metal oxide coating. Upon firing the coated particles at high temperature in air, the reoxidisation of the particle facilitates improved coating adherence and greater mechanical strength.
The coating applied to the transition metal oxide particles accoiding to the invention acts as a barrier between adjacent transition metal oxide particles to prevent agglomeration of the particles in a packed bed reactor or a fluidized reactor in a chemical looping combustion process. The active surface area of the oxygen-carrying particles is not inhibited or lowered by the coating.
The present invention furthei comprises a chemical looping combustion piocess in which a combustible gas is oxidised using a particulate transition metal oxide as an oxygen-carrying material, and the resulting reduced particulate transition metal oxide is then reoxidised for use in further oxidation of further combustible gas, in which the particulate transition metal oxide is as defined above or produced by a method as defined above.
The invention may be bettei undeistood with reference to the following examples, which illustrate advantageous featuies of the invention.
In the Examples, reference will be made to the accompanying drawings, which show conventional oxygen-carder particles befoie and after repeated CLC cycles, and also particles according to the invention after multiple cycles in a CLC process.
EXAMPLE I
(a) Preparation of oxygen-carrying particles Commercially available porous A1203 (Alumina) is crushed, so as to yield particles in the range of 500-700 micrometies. The crushed A1203 paiticles are then dipped in an aqueous solution of Cu(N03)2 (copper (II) nitrate) to impregnate the porous AbC3 particles with Cu(N03)2. The A1203 paiticles are filteied out. The filteied A1203 particles are calcined at a temperature above 500°C resulting in decomposition of Cu(N03)2 to CuO (Copper oxide) in the pores of A1203. The quantity of crushed A1203, concentration of Cu(N03)2 solution and quantity of the solution is taken in such a proportion that weight peicentage of Cu in the resulting oxygen cairying particles ranges from 50% to 90%.
(b) Coating Alumina sol-gel is used for coating of the oxygen-carrying particles prepared above.
Since alumina sol is too acidic, in order to prevent the dissolution of the CuO, the alumina gel is neutralized with calcium hydroxide (Ca(OH)2). Coating is done by introducing alumina sol-gel in a lotating drum containing the oxygen-cairying particles. The viscosity of alumina sol-gel can be altered by adding distilled water.
The resulting coated particles are then fired at a temperature of about 700°C.
Heating results in the formation of coating of a mixed oxide, calcium aluminate, on the oxygen-carrying particles. The resulting particles are coated over substantially the entire free surface thereof and are highly active at low temperatures (above 250°C), stable at high temperatures, and can be cycled more than 100 times, without significant agglomeration.
The above improved cycle life is demonstrated in the accompanying micrographs in which: Figure 1(a) shows extruded (non-coated) particles before cycling -coated particles will, however, have similar appearance; Figure 1(b) shows such an agglomerated mass after such particles have been subject to 100 cycles; and Figure 1(c) shows particles similar to those of Fig 1(c) but with a coating according to the invention, after 100 cycles.
The figures show that the oxide-coated particles retain their physical form, with little or no agglomeration, even after 100 cycles in a CLC process.
EXAMPLE 2
(a) Preparation of oxygen-carrying particles A solution of Cu(NJcJ3)2 and a solution of Al(N03)3 (aluminium nitrate) are mixed in a temperature controlled vessel along with excess of Na2CO3 (sodium carbonate) solution to maintain a pH value of 10.6. An appropriate volume of both the nitrates is added to get the desired weight percentage of copper in the final particles. The two metals precipitate as CuCO3 (copper (II) carbonate) and Al(OH)3 (aluminium hydroxide).
The resulting mixture is stirred and the precipitates are filtered. The filtered precipitates are mixed with distilled water in a vessel and stirred. Excess sodium ions are removed and the precipitate filtered and extruded to particles of size ranging from 500-700 micrometres. The particles thus formed are calcined at temperature above 550°C.
(b) Coating Alumina sol-gel is used for coating of the oxygen-carrying particles prepared above as described in Example 1(b). The resulting coated particles (after firing at about 700°C) are again coated over substantially the entire free surface thereof, are highly active at low temperatures (above 250°C), stable at high temperatures, and can be cycled more than 100 times, without significant agglomeration.
EXAMPLE 3
(a) Preparation of oxygen-carrying particles Commercially available Fe203 (iron oxide) is crushed to yield particles in the range 500-750 micrometres.
(b) Coating Alumina sol-gel is used for coating. Alumina sol-gel is first neutralised with ammonia.
The crushed iron oxide particles are then introduced in a rotating drum and neutralized alumina gel is mixed with the particles. The resulting coated particles are then fired at a temperature of about 700°C. The fired particles are again coated over substantially their entire free surface, are highly stable at high temperatures! are active at low temperatures (above 250°C) and show virtually no agglomeration even after 100 cycles of reduction and oxidation in a CLC process.
EXAMPLE 4
a) Preparation of oxygen-carrying particles Commerdally avaflable cylindhcal particles comprising about 70 wt. % CuC and about 30 wt. % Si02 are reduced in approx 5.1 vol. % hydrogen in nitrogen at 673°K, and then cooled in nitrogen.
b) Coating A suspension of bentonite (approx 1 wt. %) and water is used to wash-coat the reduced CuO!Si02 particles, before a coating of fine Ti02 powder (<5 micrometres) is applied via agglomeration in a rotating drum. The thickness of the TiC7 coating can be altered by changing the weight % of sodium bentonite in the initial wash-coat. The resulting coated particles are then fired at a temperature of 900°C.
Heating results in the reoxidation of the inner particles, which facilitates adherence to the outer coating. The resulting particles are coated over substantially the entire free surface thereof and are highly active at low temperatures (above 250°C), stable at high temperatures, and can be cycled more than 100 tImes, without sIgnificant agglomeration.
The above improved cycle life is demonstrated In the accompanying micrographs in which: Figure 2(a) shows non-coated commercial CuOISiO2 particles before cycling; Figure 2(b) shows such an agglomerated mass after such particles have been subject to 100 cycles; Figure 2(c) shows partIcles similar to those of Fig 2(a) but with a coating according to the invention; and Figure 2(d) partIcles similar to those of Fig 2(c) after 100 cycles.
These figures show that the oxide-coated particles retain their physical form, with little or no agglomeration, even after 100 cycles in a CLC process.
Claims (14)
- Claims 1 An oxygen-carrying material for use in a chemical looping combustion process, the material comprising particulate transition metal oxide, in which individual particles of the transition metal oxide have thereon an oxide coating which is substantially inert during the chemical looping combustion process.
- 2 An oxygen-carrying material according to claim 1, wherein the transition metal oxide is of Fe (iron), Cu (copper), Ni (nickel), Mn (manganese) and/or Co (cobalt).
- 3 An oxygen-carrying material according to claim 1 or 2, wherein the transition metal oxide is on a refractory inert support comprising an oxide of a metal of Group IIA, IVA, IIIB or IVB of the Periodic Table of Elements, or of the Lanthanide series.
- 4 An oxygen-carrying material according to claim 3, wherein the support is of alumina (A1203), titanium dioxide (hO2), silicon dioxide (Si02), magnesium oxide (MgO), zirconium dioxide (Zr02), or a silicate or aluminate.
- An oxygen-carrying material according to any of claims 1 to 4, wherein the inert oxide coating on the transition metal oxide particles is of alumina (A1203), titanium dioxide (hO2), silica (Si02), magnesia (MgO), zirconia (Zr02) or a silicate or aluminate.
- 6. A method of coating transition metal oxide particles for use as oxygen-carrying particles in a chemical looping combustion process, the method comprising the steps of: (a) calcining uncoated transition metal oxide particles; (b) treating the calcined transition metal oxide particles with an inert oxide precursor at an alkaline pH so as to avoid dissolution of the transition metal oxide and to precipitate the precursor on surfaces of the particles; and (c) firing the resulting coated particles at a temperature of from 500°C to 900°C to convert the precipitate to an inert oxide coating.
- 7. A method of coating transition metal oxide particles for use as oxygen-carrying particles in a chemical looping combustion process, the method comprising the steps of: (a) reducing uncoated transition metal oxide particles; (b) treating the reduced transition metal oxide particles with an inert oxide powder and binding agent to adhere the powder to the surfaces of the particles; and (c) firing the resulting coated particles at a temperature of from 500°C to 900°C to reoxidise the transition metal oxide particles and bond the oxide coating.
- 8. A method acccrding to claim 6 or 7, wherein the transition metal oxide particles are prepared by wet impregnation of an inert refractory support with a soluble salt of the transition metal.
- 9. A method according to claim 6 or 7, wherein the transition metal oxide particles are prepared by co-precipitation of the transition metal oxide and an inert refractory support.
- 10. A method according to claim 8 or 9, wherein the support comprises one or more of alumina (A1203), titanium dioxide (Ti02), silicon dioxide (Si02), magnesium oxide (MgO), zirconium dioxide (Zr02), and a silicate or alum in ate.
- 11. A method according to any of claims 6 to 10, wherein the inert oxide comprises one or more of alumina (A1203), titanium dioxide (Tic2), silicon dioxide (SiC2), magnesium oxide (MgO), zirconium dioxide (ZrC2), and a siiicate or aluminate.
- 12. A method according to any of claims 6 to 11, wherein step (b) is performed using a sol-gel process.
- 13. A method according to claim 12, wherein the pH of the sol-gel is maintained in the alkaii range.
- 14. A chemical looping combustion process in which a combustible gas is oxidised using a particulate fransition metal oxide as an oxygen-carrying material, and the resulting reduced particulate transition metal oxide Is then reoxidlsed for use In further oxidation of a combustible gas, In which the particulate transition metal oxide is as defined in any of claims I to 5 or produced by a method as defined in any of claims 6 to 13.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1305517.3A GB2512334A (en) | 2013-03-26 | 2013-03-26 | Materials for use in chemical looping combustion |
| PCT/GB2014/050967 WO2014155116A1 (en) | 2013-03-26 | 2014-03-26 | Materials for use in chemical looping combustion process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1305517.3A GB2512334A (en) | 2013-03-26 | 2013-03-26 | Materials for use in chemical looping combustion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB201305517D0 GB201305517D0 (en) | 2013-05-08 |
| GB2512334A true GB2512334A (en) | 2014-10-01 |
Family
ID=48326687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1305517.3A Withdrawn GB2512334A (en) | 2013-03-26 | 2013-03-26 | Materials for use in chemical looping combustion |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2512334A (en) |
| WO (1) | WO2014155116A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635245B (en) * | 2015-11-02 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of oxygen carrier for burning chemistry chains, its preparation method and application |
| CN108641288B (en) * | 2018-04-20 | 2019-06-25 | 大连理工大学 | A kind of nano zircite/epoxy resin composite material and preparation method thereof |
| TWI676600B (en) * | 2018-07-20 | 2019-11-11 | 財團法人工業技術研究院 | Composite oxygen carrier and method of manufacturing the same and oxidation-reduction reaction |
| EP3721992A1 (en) | 2019-04-09 | 2020-10-14 | Vito NV | Redox preparation process of an oxygen carrier for a chemical looping process |
| CN114073952A (en) * | 2020-08-14 | 2022-02-22 | 南京理工大学 | High-activity iron-based oxygen carrier suitable for efficiently removing ammonia gas from power plant flue gas chemical chain and preparation method thereof |
| CN111998335B (en) * | 2020-09-02 | 2022-11-18 | 中国石油化工股份有限公司 | Auxiliary combustion oxygen carrier composition and preparation method and application thereof |
| JPWO2022065339A1 (en) * | 2020-09-24 | 2022-03-31 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533391A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Novel iron-based oxygen carrier with interlayer shell structure, and preparation method for novel iron-based oxygen carrier |
| CN102533390A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Iron-based oxygen carrier with interlayer shell structure and capable of catalyzing direct combustion of coal, and preparation method for iron-based oxygen carrier |
| CN102585969A (en) * | 2012-02-16 | 2012-07-18 | 华北电力大学 | Novel iron-based oxygen carrier of nuclear-free cavity structure and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2948177B1 (en) * | 2009-07-16 | 2011-08-05 | Inst Francais Du Petrole | CHEMICAL LOOP COMBUSTION PROCESS WITH INDEPENDENT CONTROL OF SOLIDS CIRCULATION |
| GB2477322B (en) * | 2010-02-01 | 2015-10-21 | Gas Recovery & Recycle Ltd | Inert gas recovery system |
| US20130125462A1 (en) * | 2010-08-02 | 2013-05-23 | Horst Greiner | Chemical looping system |
-
2013
- 2013-03-26 GB GB1305517.3A patent/GB2512334A/en not_active Withdrawn
-
2014
- 2014-03-26 WO PCT/GB2014/050967 patent/WO2014155116A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533391A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Novel iron-based oxygen carrier with interlayer shell structure, and preparation method for novel iron-based oxygen carrier |
| CN102533390A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Iron-based oxygen carrier with interlayer shell structure and capable of catalyzing direct combustion of coal, and preparation method for iron-based oxygen carrier |
| CN102585969A (en) * | 2012-02-16 | 2012-07-18 | 华北电力大学 | Novel iron-based oxygen carrier of nuclear-free cavity structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201305517D0 (en) | 2013-05-08 |
| WO2014155116A1 (en) | 2014-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2512334A (en) | Materials for use in chemical looping combustion | |
| CA2302529C (en) | Sox additive systems based upon use of multiple particle species | |
| US8361925B2 (en) | Exhaust gas-purifying catalyst | |
| JP2006036576A (en) | Zirconia-based porous body and its production method | |
| JP2008512337A (en) | Multi-component metal oxide compound containing alkali metal and metal oxide compound produced thereby | |
| JP2014532559A (en) | Method for producing reforming catalyst and method for reforming methane | |
| JP7352487B2 (en) | Ammonia decomposition catalyst | |
| JPS59142847A (en) | Catalyst for oxidizing hydrogen sulfide | |
| Chang et al. | Fe 2 O 3@ SiTi core–shell catalyst for the selective catalytic reduction of NO x with NH 3: activity improvement and HCl tolerance | |
| CN106732647A (en) | A kind of perovskite type methyl hydride combustion catalyst and preparation method and application | |
| WO2009144472A2 (en) | Carbon dioxide acceptors | |
| JP2017533169A (en) | High temperature synthesis of aluminate by flame spray pyrolysis | |
| JP2013129554A (en) | Composite oxide, method for producing the same, and catalyst for exhaust gas purification | |
| DK164805B (en) | PREMIUM MATERIAL THAT CAN BE CONVERTED TO A METAL METAL IRON CATALYST BY REDUCTION AND PROCEDURE FOR THE MANUFACTURING OF THE MATERIAL | |
| WO2019003424A1 (en) | Alumina-based composite oxide and method for producing same | |
| TW201231386A (en) | Method and apparatus for producing double oxide | |
| US20110207069A1 (en) | REDOX MASSES HAVING A SPINEL TYPE STRUCTURE AxA'x,ByB'y,O4 AND USE IN A CHEMICAL LOOPING COMBUSTION PROCESS | |
| US20200274159A1 (en) | Process for making an electrode active material | |
| Jiaowen et al. | CO 2 decomposition using metal ferrites prepared by co-precipitation method | |
| CN106994346B (en) | The preparation method of load type metal Co catalysts | |
| CA1244814A (en) | Iron oxide containing precursor to a catalyst | |
| WO2015007895A2 (en) | A chemical-looping process with a supported metal-based oxygen carrier | |
| US20230415125A1 (en) | Oxygen-carrier solid with sub-stoichiometric spinel for a chemical-looping redox process | |
| JP2020083741A (en) | Shell burned product | |
| JP2004269296A (en) | Hydrogen producing method by decomposition of water and reaction medium used for the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |