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 .

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