EP2699517A1 - The method of obtaining ternary chemical compounds based on iron oxide and copper oxide - Google Patents
The method of obtaining ternary chemical compounds based on iron oxide and copper oxideInfo
- Publication number
- EP2699517A1 EP2699517A1 EP11781865.8A EP11781865A EP2699517A1 EP 2699517 A1 EP2699517 A1 EP 2699517A1 EP 11781865 A EP11781865 A EP 11781865A EP 2699517 A1 EP2699517 A1 EP 2699517A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- temperature
- cuo
- calcination
- oxide
- inert
- 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.)
- Ceased
Links
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 48
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 9
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 40
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000000969 carrier Substances 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000001502 supplementing effect Effects 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000004113 Sepiolite Substances 0.000 claims description 14
- 229910052624 sepiolite Inorganic materials 0.000 claims description 14
- 235000019355 sepiolite Nutrition 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 11
- 229910000278 bentonite Inorganic materials 0.000 claims description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000003077 lignite Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 235000012216 bentonite Nutrition 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000003415 peat Substances 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 74
- 239000001301 oxygen Substances 0.000 description 74
- 229910052760 oxygen Inorganic materials 0.000 description 74
- 238000002485 combustion reaction Methods 0.000 description 30
- 230000002349 favourable effect Effects 0.000 description 25
- 239000003245 coal Substances 0.000 description 20
- 239000000446 fuel Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000009467 reduction Effects 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000008929 regeneration Effects 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 11
- 238000002309 gasification Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004449 solid propellant Substances 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C10J3/72—Other features
- C10J3/725—Redox processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1606—Combustion processes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the subject of the invention consists of the method of obtaining ternary chemical compounds based on iron oxide and copper oxide used in the processes of chemical oxygen transport in chemical looping fuels combustion or gasification.
- oxygen carriers including various compositions of copper, cobalt, manganese, iron or nickel oxides used as active materials and aluminium oxide, titanium oxide, zirconium oxide, silicon oxide, zirconium-stabilised yttrium used as an inert material. Inert materials are added at the amount from a few to a few dozen wt.% in relation to the active material, due to which the oxide carriers life is extended, inter alia via the reduction of their abrasion.
- the chemical looping was initially used for the process of gaseous fuels combustion; later on it was expanded onto solid fuels combustion (including biomass and coal).
- Patent application No P-389853 and additional patent P-391770 present a method for producing ternary chemical compounds based on iron oxide and manganese oxide used in the processes of chemical oxygen transport for chemical looping fuels combustion or gasification.
- the invention is aimed at the method of obtaining ternary chemical compounds based on iron oxide and copper oxide, useful for the process of oxygen transport in chemical looping, of more favourable reactivity parameters and primarily of improved oxygen transport capacity and of lower agglomeration tendency.
- the input components with a carbon carrier are
- the inert material consists of sepiolite and/or bentonite and/or kaolin and/or Zr0 2 and/or Ti0 2 and/or A1 2 0 3 and/or Si0 2 or any mixture of them.
- X assumes values of 20, 30, 40, 60 wt.% and Y assumes values of 60, 50, 40, 20 wt.%.
- powdered graphite is the carbon carrier.
- powdered active carbon peat, hard and brown coal, graphite, anthracite, petroleum coke, pitch-derived carbon materials, fullerene or any mixture of them are the carbon carrier.
- the inert material consists of inorganic heat-resistant minerals or their mixture.
- bentonite or sepiolite or kaolin or any mixture of them is the inert material.
- the input components consist of chemical compounds containing iron and copper, from which iron and copper oxides are obtained as a result of calcination in an oxidising or inert atmosphere.
- the basic merit of the invention is the fact that from metal oxides due to the mechanical mixing and calcination of the oxide materials are obtained, which are oxygen carriers featuring better capacity of oxygen transport, more favourable parameters of reactivity with fuel (in the combustion/gasification reaction) and with oxygen from the air (at the stage of carrier regeneration) as compared with the solutions known from the state of the art.
- an oxygen transfer capacity at the amount of 4 - 20 wt.% was obtained as well as the melting point in a reducing atmosphere above 1300 °C.
- the obtained oxide materials are used as solid oxygen carriers in chemical looping processes.
- the obtained oxide materials may be used for fuels conversion in chemical looping, inter alia in the process of combustion and gasification of: gaseous fuels, including e.g. hydrocarbon fuels, natural gas; hydrocarbon liquid fuels; solid fuels, e.g. hard coal, lignite, plastic waste, biomass and biodegradable waste; and may be intended as a structural material of membranes applicable in 0 2 separation from N 2 in the temperature range of 400 - 1500 °C; and applicable in processes of solid and liquid fuels conversion by partial oxidation in membrane reactors.
- gaseous fuels including e.g. hydrocarbon fuels, natural gas; hydrocarbon liquid fuels; solid fuels, e.g. hard coal, lignite, plastic waste, biomass and biodegradable waste; and may be intended as a structural material of membranes applicable in 0 2 separation from N 2 in the temperature range of 400 - 1500 °C; and applicable in processes of solid and liquid fuels conversion by partial oxidation in membrane reactors.
- thermochemical reactions in lower temperature ranges.
- complex oxygen carriers feature a better reactivity.
- the method of manufacturing acc. to the invention is simple in the practical application and gives repeatable results, enables obtaining oxygen carriers for chemical looping purposes with a possibility of free mixing of active and inert components of the input products, which is not ensured by other methods, e.g. impregnation, because in this respect they are very limited by the amount of active component fed, frequently up to the amount of ca. 20 wt.%.
- the selection of components' proportions is related to the obtaining of valuable, for chemical looping, oxides properties taking into account the reduction of their production costs.
- oxygen carriers Fe 2 0 3 (purity > 99%), CuO (purity > 99%), bentonite, sepiolite, A1 2 0 3 (purity > 99.7%), Ti0 2 (purity 99%), Zr0 2 (purity 99%), Si0 2 (purity 99%), synthetic graphite.
- the method of obtaining ternary chemical compounds consists in mixing 60 g of Fe 2 0 3 , 20 g of CuO, 20 g of sepiolite and 10 g of graphite. The components were rubbed with distilled water till obtaining the grain size below 100 ⁇ . After drying the blend was calcined. The calcination was carried out during 24 hours at the temperature of 850 °C. Then the blend obtained was milled again and calcined at the temperature of 850 °C during 24 hours. As a result, a sample was obtained of composition of 60 wt.%> of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of sepiolite.
- the oxygen carriers obtained in this way feature:
- the method of obtaining ternary chemical compounds consists in mixing 60 g of Fe 2 0 3 , 20 g of CuO, 20 g of bentonite and 10 g of graphite. After the components mixing the blend was twice calcined during 24 hours, where the calcination temperature amounted to 1050 °C. As a result, a sample was obtained of chemical composition 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of bentonite.
- thermogravimetry coupled with a quadrupole mass spectrometer
- X- ray diffraction on powder specimens
- melting points melting points
- abrasion tests using a fluidised bed reactor grain size distribution measurements
- BET specific surface and pore size distribution measurements
- the manufacture methods specified guarantee that the conversion of substrates used ranges from 80 to 100%.
- the oxygen transport capacity as a characteristic parameter of an oxygen carrier, is defined as the mass difference between oxidised and reduced form of solid oxygen carrier. In practice it stands for the amount of oxygen released by the carrier from its structure and transferred to the fuel.
- Fig. 1 gives results of cyclical thermogravimetric examinations for a sample of 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of sepiolite, performed versus temperature from the range of 700 - 950 °C.
- Table 1 presents the oxygen transport capacity versus the composition and temperature for selected ternary oxygen carriers based on iron and copper oxide.
- Table 2 includes examples of estimated, at the temperature of 950 °C, both regeneration and reduction periods for oxygen carrier examples.
- the method of obtaining ternary chemical compounds consists in mixing 60 g of Fe 2 03, 20 g of CuO, 20 g of Ti0 2 and 10 g of graphite. The components were rubbed with distilled water till obtaining the grain size below 100 ⁇ . After drying the blend was calcined. The calcination was carried out during 20 hours at the temperature of 850°C. Then the blend obtained was milled again with 10 g of graphite and calcined at the temperature of 850°C during 24 hours. As a result, a sample was obtained of composition of 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of Ti0 2 .
- the oxygen carriers obtained in this way feature:
- the method of obtaining ternary chemical compounds consists in mixing 60 g of Fe 2 03, 20 g of CuO, 20 g of AI 2 O 3 and 10 g of graphite. The components were rubbed with distilled water till obtaining the grain size below 100 ⁇ . After drying the blend was calcined. The calcination was carried out during 8 hours at the temperature of 850 °C. Next the blend obtained was milled again with 10 g of graphite and calcined at the temperature of 850 °C during 24 hours. Then the blend obtained was milled again with 10 g of graphite and calcined at the temperature of 850 °C during 24 hours. As a result, a sample was obtained of composition of 60 wt.%> of Fe 2 03, 20 wt.%> of CuO, 20 wt.%> ofAl 2 0 3 .
- the oxygen carriers obtained in this way feature:
- Fig. 1 Results of cyclic thermogravimetric examinations 60 wt.% of Fe 2 0 3 , 20 wt.% CuO, 20%) wt.%) of sepiolite, using hydrogen as the fuel,
- Fig. 4 Oxidation ability (regeneration) of examples of oxygen carriers based on iron oxide and copper oxide
- Fig. 5 Reduction ability of examples of oxygen carriers based on iron oxide and copper oxide, depending on the inert material used
- Fig. 6 Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following composition: 60 wt.% of Fe 2 0 3 , 20 wt.% CuO, 20 wt.% of AI 2 O 3 and 80 wt.% of Fe 2 0 3 , 20 wt.% of A1 2 0 3 ,
- Fig. 7 Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of bentonite and 80 wt.% of Fe 2 0 3 , 20 wt.% of bentonite,
- Fig. 8 Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of sepiolite and 80 wt.% of Fe 2 0 3 , 20 wt.% of sepiolite,
- Fig. 9 Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe 2 0 3 , 20 wt.% CuO, 20 wt.% of Si0 2 and 80 wt.% of Fe 2 0 3 , 20 wt.% of Si0 2 ,
- Fig. 10 Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of Ti0 2 and 80 wt.% of Fe 2 0 3 , 20 wt.% of Ti0 2 ,
- Dash lines were used to mark the reaction rate, where the black colour was used for a ternary system and grey for a binary oxygen carrier.
- solid lines mean a change of mass versus temperature or time, where the grey colour was used for a binary system, e.g. 80 wt.%), 20 wt.%) of Ti0 2
- the black colour for a ternary system e.g. samples of the composition: 60 wt.% of Fe 2 0 3 , 20 wt.% of CuO, 20 wt.% of Ti0 2 .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Chemically Coating (AREA)
Abstract
The method of obtaining ternary chemical compounds based on iron oxide and copper oxide The method of obtaining ternary chemical compounds based on iron oxide and reactive oxide carriers as well as inert materials and carbon carriers, consisting in mixing the initial components, calcination of the mixture at a high temperature, acc. to the invention is characterised by the fact that powdered carbon carrier at the amount of to 25 wt.% in relation to the initial mix is added to the initial components in the form ok Fe2O3 and CuO and an inert material, used in proportions resulting from a general chemical formula ∑(X Fe2O3 + Y CuO + Z inert material ) = 100 wt.%, where X and Y are within the ranges 1£x£99, 1£y£99 and the inert material is used at the amount supplementing to 100 wt.%, and the whole after blending is subject to at least one-stage calcination in an oxidising or inert atmosphere at a temperature of 400 –1100 °C during 3 to 24 hours.
Description
The method of obtaining ternary chemical compounds based on iron oxide and copper oxide
The subject of the invention consists of the method of obtaining ternary chemical compounds based on iron oxide and copper oxide used in the processes of chemical oxygen transport in chemical looping fuels combustion or gasification.
Requirements related to carbon dioxide and nitrogen oxides emission reduction cause a significant intensification of research on the application of chemical looping combustion and gasification processes. The application of solid oxygen carriers in processes of chemical looping combustion or gasification enables carrying out the process with the use of pure oxygen, which transfer proceeds due to a permanently circulating bed of an oxygen carrier obtained on the basis of metal oxides. Because of the application of chemical looping combustion or gasification there is no nitrogen in the flue gas, contrary to conventional methods of energy generation from fossil fuels; this results in the lack of nitrogen oxides emission, substantially facilitates carbon dioxide capture and considerably reduces the flue gas volume.
Many possible oxygen carriers are known, including various compositions of copper, cobalt, manganese, iron or nickel oxides used as active materials and aluminium oxide, titanium oxide, zirconium oxide, silicon oxide, zirconium-stabilised yttrium used as an inert material. Inert materials are added at the amount from a few to a few dozen wt.% in relation to the active material, due to which the oxide carriers life is extended, inter alia via the reduction of their abrasion.
The chemical looping was initially used for the process of gaseous fuels combustion; later on it was expanded onto solid fuels combustion (including biomass and coal).
The paper "Characterisation of oxygen carriers for chemical looping combustion" published during the Seventh International Conference in Vancouver, Canada in 2004 shows that the use of oxygen carriers consisting of one active and one inert component is known. While the known methods of oxygen carriers obtaining for chemical looping are based on one-stage process of calcination most often not exceeding the period of 6 hours.
French patent description No FR 2 923 035 presents a preparation, which is an oxygen carrier consisting of one active and one inert oxide. This preparation contains from 5 to 20% of graphite; moreover, the process of calcination is performed in one stage at a temperature between 650 and 1050 °C during 3 to 9 hours.
Patent application No P-389853 and additional patent P-391770 present a method for producing ternary chemical compounds based on iron oxide and manganese oxide used in the processes of chemical oxygen transport for chemical looping fuels combustion or gasification. The method of obtaining ternary chemical compounds based on iron oxide and manganese oxide, consisting in mixing the initial components, calcination of the mixture at a high temperature, acc. to the invention is characterised by the fact that powdered graphite at the amount of 1 to 25 wt.% in relation to the initial mixture is added to the initial components in the form of Fe203 and Mn02 and an inert material, used in proportions resulting from a general chemical formula∑ (¾e203 + Ϊ Μηθ2 + -Zinert material) = 100 wt.%, where X and Y are within the ranges l≤x<99, l≤y<99 and the inert material is used at the amount supplementing to 100 wt.%, and the whole is subject to at least one-stage calcination in an oxidising atmosphere at a temperature of 600 - 1500 °C during 3 to 24 hours.
The invention is aimed at the method of obtaining ternary chemical compounds based on iron oxide and copper oxide, useful for the process of oxygen transport in chemical looping, of more favourable reactivity parameters and primarily of improved oxygen transport capacity and of lower agglomeration tendency.
The method of obtaining ternary chemical compounds based on iron oxide and reactive oxide carriers as well as inert materials and carbon carriers, consisting in mixing the initial components, calcination of the mixture at a high temperature, acc. to the invention is characterised by the fact that powdered carbon carrier at the amount of 1 to 25 wt.% in relation to the initial mix is added to the initial components in the form of Fe203 and CuO and an inert material, used in proportions resulting from a general chemical formula∑ (¾e203 + FCuo + -Zinert material) = 100 wt.%), where X and Y are within the ranges l≤x<99, l≤y<99 and the inert material is used at the amount supplementing
to 100 wt.%, and the whole after blending is subject to at least one-stage calcination in an oxidising or inert atmosphere at a temperature of 400 - 1100 °C during 3 to 24 hours. What is favourable, the input components with a carbon carrier are subject to at least two-stage calcination in an oxidising or inert atmosphere at the temperature of 850 °C during 24 hours.
What is favourable, the inert material consists of sepiolite and/or bentonite and/or kaolin and/or Zr02 and/or Ti02 and/or A1203 and/or Si02 or any mixture of them.
What is favourable, X assumes values of 20, 30, 40, 60 wt.% and Y assumes values of 60, 50, 40, 20 wt.%.
What is favourable, powdered graphite is the carbon carrier.
What is favourable, 10 wt.% of powdered graphite are added to the mix.
What is favourable, powdered active carbon, peat, hard and brown coal, graphite, anthracite, petroleum coke, pitch-derived carbon materials, fullerene or any mixture of them are the carbon carrier.
What is favourable, the inert material consists of inorganic heat-resistant minerals or their mixture.
What is favourable, bentonite or sepiolite or kaolin or any mixture of them is the inert material.
What is favourable, once the process of high-temperature calcination is completed the process of controlled cooling at a temperature decrease rate from 1 °C/minute to 1000 °C/minute is carried out.
What is favourable, the input components consist of chemical compounds containing iron and copper, from which iron and copper oxides are obtained as a result of calcination in an oxidising or inert atmosphere.
The basic merit of the invention is the fact that from metal oxides due to the mechanical mixing and calcination of the oxide materials are obtained, which are oxygen carriers featuring better capacity of oxygen transport, more favourable parameters of reactivity with fuel (in the combustion/gasification reaction) and with oxygen from the air (at the stage of carrier regeneration) as compared with the solutions known from the state of the art.
Using the method of the invention an oxygen transfer capacity at the amount of 4 - 20 wt.% was obtained as well as the melting point in a reducing atmosphere above 1300 °C.
This was achieved because of using two active components and one inert component, which are the basic components of the oxygen carrier. The use of such system enabled primarily the obtaining of more perfect oxide materials by increasing their reactivity with fuel (in the combustion/gasification reaction) and increasing their life due to reducing their abrasion and weakening their tendency to agglomerate.
The obtained oxide materials are used as solid oxygen carriers in chemical looping processes.
The obtained oxide materials may be used for fuels conversion in chemical looping, inter alia in the process of combustion and gasification of: gaseous fuels, including e.g. hydrocarbon fuels, natural gas; hydrocarbon liquid fuels; solid fuels, e.g. hard coal, lignite, plastic waste, biomass and biodegradable waste; and may be intended as a structural material of membranes applicable in 02 separation from N2 in the temperature range of 400 - 1500 °C; and applicable in processes of solid and liquid fuels conversion by partial oxidation in membrane reactors.
Moreover, they enable carrying out thermochemical reactions in lower temperature ranges. In general, complex oxygen carriers feature a better reactivity.
The method of manufacturing acc. to the invention is simple in the practical application and gives repeatable results, enables obtaining oxygen carriers for chemical looping purposes with a possibility of free mixing of active and inert components of the input products, which is not ensured by other methods, e.g. impregnation, because in this respect they are very limited by the amount of active component fed, frequently up to the amount of ca. 20 wt.%.
Appropriate calcination, with adequately chosen calcination time and temperature, enables increasing the oxide product life due to reducing its abrasion and favourable weakening its tendency to agglomerate and increasing the homogeneity of the end product obtained. Thereby this has a favourable impact on the costs of fuels combustion or gasification processes, which are reduced due to their increased reactivity and life. In addition, the use of inorganic heat-resistant minerals and chemical compounds containing iron and/or copper ensured the improvement to the economic efficiency.
The graphite addition to the blend caused that during calcination at the temperature of 850 °C in the air atmosphere it is subject to oxidation to carbon dioxide, which release results in an increase in: the specific surface, the conversion and the reaction rate.
The selection of components' proportions is related to the obtaining of valuable, for chemical looping, oxides properties taking into account the reduction of their production costs.
The method acc. to the invention has been described in non-restrictive examples of implementation.
The following components have been used as raw materials to obtain oxygen carriers: Fe203 (purity > 99%), CuO (purity > 99%), bentonite, sepiolite, A1203 (purity > 99.7%), Ti02 (purity 99%), Zr02 (purity 99%), Si02 (purity 99%), synthetic graphite.
Example 1
The method of obtaining ternary chemical compounds consists in mixing 60 g of Fe203, 20 g of CuO, 20 g of sepiolite and 10 g of graphite. The components were rubbed with distilled water till obtaining the grain size below 100 μιη. After drying the blend was calcined. The calcination was carried out during 24 hours at the temperature of 850 °C. Then the blend obtained was milled again and calcined at the temperature of 850 °C during 24 hours. As a result, a sample was obtained of composition of 60 wt.%> of Fe203, 20 wt.% of CuO, 20 wt.% of sepiolite.
The oxygen carriers obtained in this way feature:
- high oxygen transport capacity of 19.03% at the temperature of 950 °C (Table 1),
- specific surface BET of 7.4 m2/g and mean value of pores diameter equal to 8.8 nm,
- low abrasion index, AI = 3.5%,
- good regeneration capacity (Fig. 1),
- repeatability of results,
- the fact that the optimum range of preparation action falls within the temperature range of 400 - 1300 °C, where the application of mineral in the form of sepiolite has especially favourable impact on increasing the oxygen transport capacity at lower temperatures in relation to commonly used inert materials, e.g. in the form of A1203 (Table 1),
- high thermal resistance; the melting point in a reducing atmosphere amounted to 1440 °C,
- low tendency to agglomerate, because 90% of the material produced was a fraction < 616 μιη and 50% was a fraction < 237 μιη,
- short oxidation and reduction time, where 80% of fraction is oxidised during 2.46 minutes, reduced during 8.56 minutes for hydrogen and oxidised during 4.3 minutes after previous reduction with carbon (Table 2),
- higher and hence more favourable oxygen transport capacity as compared to adequate binary oxygen carrier (Fig. 8),
- more favourable kinetics of the combustion reaction e.g. of carbon than in the case of using adequate binary oxygen carrier (Fig. 8), where the reaction of coal combustion in oxygen released from the oxygen carrier structures, with the applied 20%> CuO addition, proceeds approx. 1.7 times faster,
- 100% regeneration capacity after the reaction of gaseous and solid fuels combustion, e.g. hydrogen and coal (Fig. 4, Fig. 8)
- using coal as fuel no problems of oxygen carrier deactivation with soot was observed,
- application of a system, at least ternary, as compared with conventionally used binary, had a favourable impact on increasing the fuel combustion reaction rate (Fig. 8)
Example 2
The method of obtaining ternary chemical compounds consists in mixing 60 g of Fe203, 20 g of CuO, 20 g of bentonite and 10 g of graphite. After the components mixing the blend was twice calcined during 24 hours, where the calcination temperature amounted to 1050 °C. As a result, a sample was obtained of chemical composition 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of bentonite.
The oxygen carriers obtained feature:
- high oxygen transport capacity of 18.61% at the temperature of 950 °C (Table 1),
- higher and hence more favourable oxygen transport capacity as compared to adequate binary oxygen carrier (Fig. 7.),
- more favourable kinetics of the combustion reaction e.g. of coal than in the case of using adequate binary oxygen carrier (Fig. 7), where the reaction of coal combustion in oxygen released from the oxygen carrier structures, with the applied 20% CuO addition, proceeds approx. 1.2 times faster,
- specific surface BET of 1.4 m2/g and mean value of pores diameter equal to 7.2 nm,
- short oxidation and reduction time, where 80% of fraction is oxidised during 2.6 minutes, reduced during 7.88 minutes for hydrogen and oxidised during 3.88 minutes after previous reduction with carbon (Table 2),
- 100% regeneration capacity after the reaction of gaseous and solid fuels combustion, e.g. hydrogen and coal (Fig. 4., Fig. 7),
- high thermal resistance; where the melting point in a reducing atmosphere amounted to 1430 °C,
- the scope of the compound use is optimal in the temperature range of 400 - 1300 °C,
- low tendency to agglomerate, where 90% of the material produced was a fraction < 642 μιη and 50% was a fraction < 200 μιη,
- repeatability of results.
These advantages have been confirmed by product analyses, including investigations of: thermogravimetry coupled with a quadrupole mass spectrometer, X- ray diffraction on powder specimens, melting points, abrasion tests using a fluidised bed reactor, grain size distribution measurements, BET specific surface and pore size distribution measurements.
The manufacture methods specified guarantee that the conversion of substrates used ranges from 80 to 100%.
The oxygen transport capacity, as a characteristic parameter of an oxygen carrier, is defined as the mass difference between oxidised and reduced form of solid oxygen carrier. In practice it stands for the amount of oxygen released by the carrier from its structure and transferred to the fuel.
To determine the oxygen transport capacity of the obtained solid oxygen carriers (Table 1) based on transition metals cyclic tests in oxidising (synthetic air) and
reducing (3% hydrogen, hard coal from Janina colliery featuring favourable physicochemical parameters) conditions were carried out by means of coupled TG-MS technique using a Netzsch STA 409 PC Luxx thermobalance coupled with an Aeolos QMS 403C quadrupole mass spectrometer, where the mass spectrometry was used to control substrates and to identify the flue gases.
The process of chemical looping was simulated this way using a thermogravimetric analysis. What's more, the reactivity tests were carried out versus temperature.
For example, Fig. 1 gives results of cyclical thermogravimetric examinations for a sample of 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of sepiolite, performed versus temperature from the range of 700 - 950 °C.
Table 1 presents the oxygen transport capacity versus the composition and temperature for selected ternary oxygen carriers based on iron and copper oxide. Table 2 includes examples of estimated, at the temperature of 950 °C, both regeneration and reduction periods for oxygen carrier examples.
Table 1. Oxygen transport capacity versus the chemical composition of solid oxygen carriers
Oxygen carrier Temperature (°C)
700 800 900 950
Oxygen transport capacity (wt.%>)
60 wt.% of Fe203, 20 wt.% CuO, 20 wt.% Si02 15.40 15.45 18.21 18.52
60 wt.% Fe203, 20 wt.% CuO, 20 wt.% A1203 15.25 14.28 18.46 19.31
60 wt.% of Fe203, 20 wt.% CuO, 20 wt.% Ti02 16.54 16.44 19.25 19.94
60 wt.% Fe203, 20 wt.% CuO, 20 wt.% sepiolite 16.19 16.13 18.59 19.03
60 wt.% Fe203, 20 wt.% CuO, 20 wt.% bentonite 16.96 17.09 18.94 18.61
Table 2. Time necessary to reach preset conversion at the temperature of 950°C
Conversion Regeneration time Reduction time
(%) (min) (min)
Fe203 - Cu0 / Sepiolite
50 2.07 4.02
80 2.46 8.56
100 4.7 19.88
Fe203 - CuO / Si02
50 2.14 5.00
80 2.81 10.45
100 4.79 22.71
Fe203 - CuO / Al203
50 2.11 5.00
80 2.79 9.54
100 5.0 22.66
Fe203 - CuO / Bentonite
50 1.92 3.87
80 2.6 7.88
100 4.18 19.49
Fe203 - CuO / Ti02
50 1.87 4.73
80 2.54 11.66
100 4.15 25
Example 3
The method of obtaining ternary chemical compounds consists in mixing 60 g of Fe203, 20 g of CuO, 20 g of Ti02 and 10 g of graphite. The components were rubbed with distilled water till obtaining the grain size below 100 μιη. After drying the blend was calcined. The calcination was carried out during 20 hours at the temperature of 850°C. Then the blend obtained was milled again with 10 g of graphite and calcined at the temperature of 850°C during 24 hours. As a result, a sample was obtained of composition of 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of Ti02.
The oxygen carriers obtained in this way feature:
- high oxygen transport capacity of 19.94% (at the temperature of 950 °C),
- higher and hence more favourable oxygen transport capacity as compared to adequate binary oxygen carrier (Fig. 10),
- more favourable kinetics of the fuel combustion reaction e.g. of coal than in the case of using adequate binary oxygen carrier (Fig. 10), where the reaction of coal combustion using oxygen released from oxygen carrier structures, with the applied addition of 20% of CuO proceeds slightly faster,
- specific surface BET of 0.4 m2/g and mean value of pores diameter equal to 6.2 nm,
- good capacity of regeneration,
- repeatability of results,
- the fact that the optimum range of preparation action falls within the temperature range of 600 - 1350 °C,
- high thermal resistance; the melting point in a reducing atmosphere amounted to:
1440 °C,
- low agglomeration tendency, because 90% of the material produced was a fraction < 772 μιη and 50%> was a fraction < 212 μιη,
- short oxidation and reduction time, where 80% of fraction is oxidised during 2.54 minute, reduced during 11.66 minutes for hydrogen and oxidised during 4.02 minutes after previous reduction with carbon (Table 2),
- 100%) regeneration capacity after the combustion reaction of gaseous fuels (e.g. hydrogen) (Fig. 4) and of solid fuels (e.g. coal) (Fig. 10)
Example 4
The method of obtaining ternary chemical compounds consists in mixing 60 g of Fe203, 20 g of CuO, 20 g of AI2O3 and 10 g of graphite. The components were rubbed with distilled water till obtaining the grain size below 100 μιη. After drying the blend was calcined. The calcination was carried out during 8 hours at the temperature of 850 °C. Next the blend obtained was milled again with 10 g of graphite and calcined at the temperature of 850 °C during 24 hours. Then the blend obtained was milled again with 10 g of graphite and calcined at the temperature of 850 °C during 24 hours. As a result, a sample was obtained of composition of 60 wt.%> of Fe203, 20 wt.%> of CuO, 20 wt.%> ofAl203.
The oxygen carriers obtained in this way feature:
- high oxygen transport capacity of 19.31% (at the temperature of 950 °C),
- higher and hence more favourable oxygen transport capacity as compared to adequate binary oxygen carrier (Fig. 6),
- more favourable kinetics of the combustion reaction e.g. of coal than in the case of using adequate binary oxygen carrier (Fig. 6) where the reaction of coal combustion with the applied 20% addition of CuO proceeds approx. 1.7 times faster,
- specific surface BET of 0.5 m2/g and mean value of pores diameter equal to 6.3 nm,
- good regeneration capacity (Fig. 2.),
- repeatability of results,
- the fact that the optimum range of the preparation action falls within the temperature range of 600 - 1600 °C,
- high thermal resistance; the melting point in a reducing atmosphere amounted to: > 1650 °C,
- low agglomeration tendency, because 90% of the material produced was a fraction < 608 μιη and 50%> was a fraction < 189 μιη,
- short oxidation and reduction time, where 80%> of fraction is oxidised during 2.79 minutes, reduced during 9.54 minutes for hydrogen and oxidised during 4.64 minutes after previous reduction with carbon,
- 100% capacity of regeneration, after the combustion reaction of hydrogen (Fig. 4) and coal, no problem of deactivation with soot was observed (Fig. 6).
The following graphs present the obtained results of examinations, of which:
Fig. 1 - Results of cyclic thermogravimetric examinations 60 wt.% of Fe203, 20 wt.% CuO, 20%) wt.%) of sepiolite, using hydrogen as the fuel,
Fig. 2 - Results of cyclic thermogravimetric examinations 60 wt.% of Fe203, 20 wt.% CuO, 20 wt.%) of A1203, using hydrogen as the fuel,
Fig. 3 - Results of cyclic thermogravimetric examinations 60 wt.% of Fe203, 20 wt.% CuO, 20 wt.%) of Si02, using hydrogen as the fuel,
Fig. 4 - Oxidation ability (regeneration) of examples of oxygen carriers based on iron oxide and copper oxide,
Fig. 5 - Reduction ability of examples of oxygen carriers based on iron oxide and copper oxide, depending on the inert material used,
Fig. 6 - Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following composition: 60 wt.% of Fe203, 20 wt.% CuO, 20 wt.% of AI2O3 and 80 wt.% of Fe203, 20 wt.% of A1203,
Fig. 7 - Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of bentonite and 80 wt.% of Fe203, 20 wt.% of bentonite,
Fig. 8 - Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of sepiolite and 80 wt.% of Fe203, 20 wt.% of sepiolite,
Fig. 9 - Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe203, 20 wt.% CuO, 20 wt.% of Si02 and 80 wt.% of Fe203, 20 wt.% of Si02,
Fig. 10 - Results of thermogravimetric examinations of coal combustion in oxygen released from oxygen carriers of the following compositions: 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of Ti02 and 80 wt.% of Fe203, 20 wt.% of Ti02,
Marking:
Symbols + used in Fig. 1-3. and Fig. 6-10 stand for temperature.
Dash lines were used to mark the reaction rate, where the black colour was used for a ternary system and grey for a binary oxygen carrier. In turn, solid lines mean a change of mass versus temperature or time, where the grey colour was used for a binary system, e.g. 80 wt.%), 20 wt.%) of Ti02, and the black colour for a ternary system, e.g. samples of the composition: 60 wt.% of Fe203, 20 wt.% of CuO, 20 wt.% of Ti02.
Claims
1. The method of obtaining ternary chemical compounds based on iron oxide and reactive oxide carriers as well as inert materials and carbon carriers, consisting in mixing the initial components, calcination of the mixture at a high temperature, is characterised in that powdered carbon carrier at the amount of 1 to 25 wt.% in relation to the initial mix is added to the initial components in the form of Fe203 and CuO and an inert material, used in proportions resulting from a general chemical formula∑ (¾¾2θ3 + i cuo + Zinert material) = 100 wt.%, where X and Y are within the ranges l≤x<99, l≤y<99 and the inert material is used at the amount supplementing to 100 wt.%, and the whole is subject to at least one- stage calcination in an oxidising or inert atmosphere at a temperature of 400 - 1100 °C during 3 to 24 hours.
2. The method according to claim 1 is characterised in that input components with a carbon carrier are subject to at least two-stage calcination in an oxidising or inert atmosphere at the temperature of 850 °C during 24 hours.
3. The method according to claim 1 and 2 is characterised in that the inert material consists of sepiolite and/or bentonite and/or kaolin and/or Zr02 and/or Ti02 and/or A1203 and/or Si02 or any mixture of them.
4. The method according, to claim 1 and 2 is characterised in that X assumes values of 20, 30, 40, 60 wt.% and Y assumes values of 60, 50, 40, 20 wt.%.
5. The method according to claim 1 is characterised in that powdered graphite is the carbon carrier.
6. The method according to claim 5 is characterised in that 10 wt.% of powdered graphite are added to the mix.
7. The method according to claim 1 is characterised in that powdered active carbon, peat, hard and brown coal, graphite, anthracite, petroleum coke, pitch- derived carbon materials, fullerene or any mixture of them are the carbon carrier.
8. The method according to claim 1 is characterised in that inorganic heat- resistant minerals or their mixture is the inert material.
9. The method according, to claim 6 is characterised in that bentonite or sepiolite or kaolin or any mixture of them is the inert material.
10. The method according, to claim 1 and 2 is characterised in that once the process of high-temperature calcination is completed the process of controlled cooling at a temperature decrease rate from l°C/minute to 1000°C/minute is carried out.
11. The method according to claim 1 is characterised in that the input components consist of chemical compounds containing iron and copper, from which iron and copper oxides are obtained as a result of calcination in an oxidising or inert atmosphere.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL394620A PL224039B1 (en) | 2011-04-20 | 2011-04-20 | Method for obtaining ternary chemical compounds based on iron oxide and copper oxide |
| PCT/IB2011/054347 WO2012143766A1 (en) | 2011-04-20 | 2011-10-04 | The method of obtaining ternary chemical compounds based on iron oxide and copper oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2699517A1 true EP2699517A1 (en) | 2014-02-26 |
Family
ID=44936317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11781865.8A Ceased EP2699517A1 (en) | 2011-04-20 | 2011-10-04 | The method of obtaining ternary chemical compounds based on iron oxide and copper oxide |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2699517A1 (en) |
| PL (1) | PL224039B1 (en) |
| WO (1) | WO2012143766A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043615B (en) * | 2012-12-26 | 2014-07-23 | 东北大学 | Device and method for preparing oxygen through taking hot gas as heat source by chemical chain air technology |
| JP6326982B2 (en) * | 2013-06-21 | 2018-05-23 | 東京瓦斯株式会社 | Chemical loop combustion method and oxygen carrier |
| CN111362310A (en) * | 2020-02-21 | 2020-07-03 | 深圳大学 | Multi-element heterostructure nanocomposite, controllable preparation method and lithium ion battery |
| CN115888737A (en) * | 2022-08-22 | 2023-04-04 | 西北大学 | Cerium-cobalt composite oxygen carrier and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2923035B1 (en) | 2007-10-25 | 2009-11-27 | Hopi | METHOD FOR CONSTRUCTING AT LEAST ONE IDENTIFIER AND SECURING ITS READING BY A DIGITAL PEN ASSOCIATED WITH A TRAMEE SHEET AND MEANS FOR CARRYING IT OUT. |
| FR2924035B1 (en) * | 2007-11-23 | 2010-09-03 | Sebatien Roux | FORMULATION OF OXIDES, ITS OBTAINING AND ITS USE AS OXYGEN CARRIER IN A PROCESS FOR OXIDATION AND / OR DEOXIDATION OF A GASEOUS FLOW |
| PL222499B1 (en) | 2010-07-07 | 2016-08-31 | Inst Chemicznej Przeróbki Węgla | Method for obtaining ternary chemical compounds based on iron oxide and manganese oxide |
| PL218481B1 (en) | 2009-12-10 | 2014-12-31 | Inst Chemicznej Przeróbki Węgla | Method for obtaining ternary chemical compounds based on iron oxide and manganese oxide |
| EP2509921B1 (en) * | 2009-12-10 | 2017-09-06 | Instytut Chemicznej Przeróbki Wegla | The method of obtaining ternary chemical compounds based on iron oxide and manganese oxide |
-
2011
- 2011-04-20 PL PL394620A patent/PL224039B1/en unknown
- 2011-10-04 WO PCT/IB2011/054347 patent/WO2012143766A1/en active Application Filing
- 2011-10-04 EP EP11781865.8A patent/EP2699517A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012143766A1 (en) | 2012-10-26 |
| PL224039B1 (en) | 2016-11-30 |
| PL394620A1 (en) | 2012-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Effects of supports on hydrogen production and carbon deposition of Fe-based oxygen carriers in chemical looping hydrogen generation | |
| Siriwardane et al. | Synergetic effects of mixed copper–iron oxides oxygen carriers in chemical looping combustion | |
| US20190003704A1 (en) | Sustainable Oxygen Carriers for Chemical Looping Combustion with Oxygen Uncoupling and Methods for Their Manufacture | |
| EP1445018A1 (en) | Catalytic system and process for the production of hydrogen | |
| Skulimowska et al. | Chemical looping with oxygen uncoupling (CLOU) and chemical looping combustion (CLC) using copper-enriched oxygen carriers supported on fly ash | |
| US20130130032A1 (en) | Fe-ni compound oxide for chemical looping combustion process and method of manufacturing the same | |
| Kun et al. | Preparation of double perovskite-type oxide LaSrFeCoO6 for chemical looping steam methane reforming to produce syngas and hydrogen | |
| EP2699517A1 (en) | The method of obtaining ternary chemical compounds based on iron oxide and copper oxide | |
| Xu et al. | Chemical looping hydrogen production with modified iron ore as oxygen carriers using biomass pyrolysis gas as fuel | |
| Cheng et al. | Thermal decomposition mechanism of Co–ANPyO/CNTs nanocomposites and their application to the thermal decomposition of ammonium perchlorate | |
| Mohammad Pour et al. | Investigation of manganese–iron oxide materials based on manganese ores as oxygen carriers for chemical looping with oxygen uncoupling (CLOU) | |
| Ran et al. | Evaluation of CuO/MgAl2O4 in biomass chemical looping gasification with oxygen uncoupling | |
| US10030204B1 (en) | Metal ferrite oxygen carriers for gasification of solid carbonaceous fuel | |
| EP2509921B1 (en) | The method of obtaining ternary chemical compounds based on iron oxide and manganese oxide | |
| Chiron et al. | Steam carbon gasification of a nickel based oxygen carrier | |
| WO2005030391A1 (en) | Catalyst and method for the generation of co-free hydrogen from methane | |
| SE438160B (en) | METHOD OF REDUCING METAL ORE | |
| CN110721691B (en) | CFAN catalyst, preparation thereof and application thereof in methane hydrogen production | |
| PL218481B1 (en) | Method for obtaining ternary chemical compounds based on iron oxide and manganese oxide | |
| CN112705234B (en) | Oxygen-doped carbon-based nickel carbide nanocomposite and preparation method and application thereof | |
| TWI625305B (en) | Preparing method of complex oxygen carrier | |
| CN112705237B (en) | Carbon-coated nickel carbide and nickel nanocomposite as well as preparation method and application thereof | |
| CN111689464A (en) | Method for preparing hydrogen and elemental sulfur by oxidizing, catalytically decomposing and hydrogen sulfide under trace oxygen atmosphere | |
| KR102531947B1 (en) | Catalyst for methane synthesis and preparation method thereof | |
| CN112569995B (en) | Composition containing epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20130215 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| DAX | Request for extension of the european patent (deleted) | ||
| 17Q | First examination report despatched |
Effective date: 20141016 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R003 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
| 18R | Application refused |
Effective date: 20161103 |