EP3592459A2 - Matières de lit pour procédés de réaction en lit fluidisé et procédés de réaction en lit fluidisé - Google Patents

Matières de lit pour procédés de réaction en lit fluidisé et procédés de réaction en lit fluidisé

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Publication number
EP3592459A2
EP3592459A2 EP18708923.0A EP18708923A EP3592459A2 EP 3592459 A2 EP3592459 A2 EP 3592459A2 EP 18708923 A EP18708923 A EP 18708923A EP 3592459 A2 EP3592459 A2 EP 3592459A2
Authority
EP
European Patent Office
Prior art keywords
particle
catalyst
fluidised bed
particles
μιτι
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Withdrawn
Application number
EP18708923.0A
Other languages
German (de)
English (en)
Inventor
Bartlomiej PRUSISZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sibelco Nederland NV
Original Assignee
Sibelco Nederland NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sibelco Nederland NV filed Critical Sibelco Nederland NV
Publication of EP3592459A2 publication Critical patent/EP3592459A2/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • B01J23/755—Nickel
    • 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
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • 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 
    • F23C1/00—Combustion apparatus specially adapted for combustion of two or more kinds of fuel simultaneously or alternately, at least one kind of fuel being either a fluid fuel or a solid fuel suspended in a carrier gas or air
    • 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 
    • F23C10/00—Fluidised bed combustion apparatus
    • F23C10/01—Fluidised bed combustion apparatus in a fluidised bed of catalytic particles
    • 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 
    • F23C9/00—Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B15/00—Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C10J2300/092—Wood, cellulose
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0993—Inert particles, e.g. as heat exchange medium in a fluidized or moving bed, heat carriers, sand
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1853—Steam reforming, i.e. injection of steam only
    • 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 present invention relates to bed materials for fluidised bed reaction methods.
  • the present invention also relates to fluidised bed reaction methods.
  • Combustion is the high-temperature exothermic reaction between a fuel and an oxidant.
  • Gasification is a method that converts organic (for example biomass) or fossil fuel based carbonaceous materials (fuels) into carbon monoxide, hydrogen and/or carbon dioxide.
  • Fluidised bed combustion and fluidised bed gasification are both fluidised bed reaction methods. Combustion and gasification can be considered oxidation methods in the sense that the fuel is oxidised in both cases.
  • Fluidised bed technology is used in the combustion and gasification of fuels.
  • particles of fuel are suspended in a bed of particulate materials (for example ash, sand and/or limestone). Jets of oxygenated gas (for example air or oxygen depleted air) are blown through the bed to provide the oxygen required for the combustion of the fuel.
  • particulate materials for example ash, sand and/or limestone.
  • Jets of oxygenated gas for example air or oxygen depleted air
  • fluidised bed combustion occurs at a temperature of combustion of from 750 to 850°C. Fluidised bed combustion can occur at different temperatures, depending on the reactor design and the fuel.
  • fluidised bed gasification particles of fuel are suspended in a bed of particulate materials (for example ash, sand and/or limestone). Jets of oxygenated gas (for example air) and/or steam are blown through the bed to effect gasification of the fuel.
  • particulate materials for example ash, sand and/or limestone.
  • combustion and fluidised bed gasification is the amount of oxygen in the gas. Generally, less oxygen is required for fluidised bed gasification because the amount of oxidation of the fuel in gasification is less than in fluidised bed combustion.
  • Another difference between fluidised bed combustion and fluidised bed gasification is the temperature of the fluidised bed; combustion utilises higher temperatures than gasification, for any particular fuel.
  • fluidised bed gasification occurs at temperature of gasification of from 650 to 749°C. Fluidised bed gasification can occur at different
  • Fluidised bed combustion is an increasingly common source of energy because fluidised bed combustion can be used to burn fuels which prove difficult to burn using other technologies. Furthermore, SO x emissions can be precipitated out using limestone in a fluidised bed. Fluidised bed combustion releases lower levels of NO x emissions than other combustion methods because the temperatures of combustion are relatively low.
  • a fluidised bed used in either fluidised bed combustion or fluidised bed gasification, can be formed by introducing pressurised gas (pressurised higher than atmospheric pressure) through a bed material.
  • the bed material is formed of a plurality of solid particles.
  • the solid particles are typically formed of ash, sand and/or limestone.
  • a fluidised bed consists of a gas-solid mixture (the gas being the pressurised gas; the solid being the solid particles) that exhibits fluid-like properties.
  • a fluidised bed can be considered a
  • a fluidised bed can be used to promote contact between gases and solids and enhance reactions between gases and solids.
  • a particle for a fluidised bed reaction method comprising:
  • the particle consists essentially of:
  • bed material and the catalyst combined make up at least 98% of the particle by weight, the balance being unavoidable impurities.
  • the bed material is any one or more of: ash, sand (optionally quartz sand or feldspatic sand), olivine, limestone, ilmenite, feldspar, crushed ceramics, calcined bauxite, Chamotte and/or calcined clays.
  • the bed material is Chamotte.
  • the catalyst is any one or more of: elements from groups 1 or 2 of the periodic table; and/or mixtures and/or alloys from any one, two or three of groups 1 , 2 and/or 3 of the periodic table; optionally selected from: Group 1 : Ti, V, Cr, Mo, Fe
  • Group 2 Ni, Co, Mn, Cu
  • Group 3 CaO, MgO, ZnO.
  • the catalyst is: a mixture of Ni and Cr; or, a mixture of Ni, Cr and ZnO.
  • the particle has a particle size of: from 100 ⁇ to 2mm; or, from 250 ⁇ to 1 .5 mm; or, from 250 ⁇ to 500 ⁇ ; or, from 0.5 mm to 1 .5 mm; or, from 0.2 mm to 0.6 mm.
  • the catalyst within the particles comprising a bed material and a catalyst, is formed of catalyst particles with a particle size of: 250 ⁇ or lower; or, 100 ⁇ or lower; or, 50 ⁇ or lower; or, from 0.1 ⁇ to 50 ⁇ .
  • the particle size is the maximum dimension of the particle.
  • particle size is measured on a MalvernTM Mastersizer 3000.
  • the particle comprises, consists essentially of or consists of:
  • catalyst to 1 % catalyst by weight
  • 30% catalyst to 5% catalyst by weight
  • 20% catalyst to 5% catalyst by weight
  • 10% catalyst to 5% catalyst by weight
  • 30% catalyst to 8% catalyst by weight
  • the balance is the bed material and, optionally, unavoidable impurities.
  • the particle is refractory.
  • the particle is refractory because it is stable up to at least 1 ,100°C.
  • the particle has a Mohs hardness of at least 6.
  • a method of forming a particle for a fluidised bed reaction method comprising: a bed material; and, a catalyst;
  • the method comprising the steps of:
  • step of calcining occurs at: from 1 ,200°C to 1 ,675°C; or, from 1 ,550°C to 1 ,675°C; optionally, at 1 ,600°C.
  • the product is ground and/or sieved.
  • the product is ground and/or sieved into particles with particle sizes of: from 100 ⁇ to 2mm; or, from 250 ⁇ to 1 .5 mm; or, from 250 ⁇ to 500 ⁇ ; or, from 0.5 mm to 1 .5 mm; or, from 0.2 mm to 0.6 mm.
  • particle sizes of: from 100 ⁇ to 2mm; or, from 250 ⁇ to 1 .5 mm; or, from 250 ⁇ to 500 ⁇ ; or, from 0.5 mm to 1 .5 mm; or, from 0.2 mm to 0.6 mm.
  • a plurality of particles comprising a plurality of particles according to the above particles.
  • the plurality of particles consists of a plurality of particles according to the above particles.
  • a method of oxidising fuel in a fluidised bed comprising the steps of:
  • the method of oxidising fuel is a method of fluidised bed combustion or fluidised bed gasification.
  • the fuel is any one or more of: fossil fuels (for example coal, peat or natural gas); wood (for example untreated wood, treated wood, recycled wood or wood pellets); char; torrefied biomass; energy crops (for example Miscanthus, Switchgrass, Giant Reed, Reed Canary Grass, Cardoon, Willow, Poplar or Eucalyptus); animal manure (for example cow, horse, pig or poultry manure); organic residues/products (for example agricultural waste, horticultural waste, bagasse, black liquor, food industry products, food industry waste, grain, meal, organic domestic waste, paper, paper pulp, slaughterhouse residue, textile waste or organic residue); municipal solid waste; refuse-derived fuel; plastic; sludge (for example drainage culvert, food industry sludge, paper sludge or sewage); straw (for example stalk, cob or ear straw); a mixture of virgin wood (90% by weight) and grass (10% by weight); or any combination of any one, two, three, four, five,
  • the gas is an oxidising gas; optionally, wherein the gas comprises oxygen; and/or wherein the gas is any one or more of air, steam or a mixture of air and steam; and/or, wherein the gas is at atmospheric pressure (101 ,325 Pa) or at a pressure higher than atmospheric pressure.
  • the heat of the method of oxidising fuel is: from 100 to 1 ,000°C; or, from 200 to 900°C; or, from 500 to 850°C; or, from 750 to 850°C; or, from 650 to 750°C.
  • the fuel is a mixture of wood (90% by weight) and straw (10% by weight).
  • Figure 1 is a schematic diagram of a fluidised bed reactor, which can be used in either fluidised bed combustion or fluidised bed gasification.
  • Fluidised bed combustion refers to the combustion of fuel, typically solid fuel, in a hot, bubbling bed, or circulating bed, of bed materials.
  • Fluidised bed gasification refers to the gasification of fuel, typically solid fuel, (forming carbon monoxide, hydrogen and carbon dioxide) in a hot, bubbling bed, or circulating bed, of bed materials.
  • Fluidised bed reactor refers to a reactor that can be used in fluidised bed combustion and/or fluidised bed gasification methods.
  • fluidised bed reactors are lined with a ceramic material.
  • suitable ceramic materials include C71 refractories according to the ASTM standard ("non- metallic materials having those chemical and physical properties to make them applicable for structures, or as components of systems, that are exposed to environments above 538°C”: see “Circulating Fluidized Bed Boilers: Design, Operation and Maintenance", Prabir Basu, Springer, 2015, the contents of which are hereby incorporated by reference).
  • Bench scale fluidised bed reactors typically generate power of from 2kW to 10kW.
  • Industrial fluidised bed reactors typically generate power of from 18MW to 50MW.
  • Fuel refers to a material that can react with other materials to release chemical energy as heat through oxidation of the fuel.
  • fuel include: fossil fuels (for example coal, peat or natural gas); wood (for example untreated wood, treated wood, recycled wood or wood pellets); char; torrefied biomass; energy crops (for example Miscanthus, Switchgrass, Giant Reed, Reed Canary Grass, Cardoon, Willow, Poplar or Eucalyptus); animal manure (for example cow, horse, pig or poultry manure); organic
  • Wastes/products for example agricultural waste, horticultural waste, bagasse, black liquor, food industry products, food industry waste, grain, meal, organic domestic waste, paper, paper pulp, slaughterhouse residue, textile waste or organic residue); municipal solid waste; refuse-derived fuel; plastic; sludge (for example drainage culvert, food industry sludge, paper sludge or sewage); straw (for example stalk, cob or ear straw); a mixture of virgin wood (90% by weight) and grass (10% by weight); or any combination of any one, two, three, four, five, six, seven, eight, nine, ten or more of these examples of fuel.
  • "Bed materials” refers to the materials making up the bed in a fluidised bed reactor. Bed materials are typically solid particulate materials.
  • bed materials examples include ash, sand (for example quartz sand or feldspatic sand), olivine, limestone, ilmenite, feldspar, crushed ceramics, calcined bauxite, Chamotte and calcined clays.
  • Bed materials are typically inert but can agglomerate with fuel ash under high temperatures and/or pressures.
  • Catalyst refers to a substance that increases the rate of a chemical reaction without itself undergoing any permanent chemical change.
  • Examples of catalysts used to catalyse oxidation of fuel in fluidised bed combustion or fluidised bed gasification include metals, metal oxides and metal carbonates.
  • iron (metallic Fe) iron oxides
  • Chamotte has a high percentage of silica and alumina, with 95% of the total mass of Chamotte being either silica (SiO 2 ) or alumina (AI 2 O 3 ), in different proportions.
  • Chamotte can be produced by heating fire clay to high temperature (typically greater than 1500°C) before grinding and screening to different particle sizes.
  • particle size refers to the maximum dimension of a particle. In the example of generally spherical particles, particle size refers to the diameter of the particles. Particle size is measured by whether the particles fit through a suitably sized filter, for example particles of 250 ⁇ or lower fit through a filter with a mesh size of 250 ⁇ . Alternatively or additionally, particle size can be measured by laser diffraction (for example using a MalvernTM Mastersizer 3000). In some examples, particles of the presently claimed invention have a particle size of: from 100 ⁇ to 2mm; or, from 250 ⁇ to 1 .5 mm; or, from 250 ⁇ to 500 ⁇ ; or, from 0.5 mm to 1 .5 mm; or, from 0.2 mm to 0.6 mm.
  • Figure 1 is a schematic diagram of a fluidised bed reactor 1 , which can be used in either fluidised bed combustion or fluidised bed gasification.
  • a fluidised bed reactor 1 of Figure 1 there is an input 2 for solid materials 7 and an input 3 for gas materials 6.
  • the solid materials 7 sit on a porous plate 4, sometimes referred to as a distributor.
  • the gas materials 6 enter the reactor 1 though the input 3 and then through the porous plate 4, in an upwards direction as shown schematically by arrow 5.
  • the solid materials 7 are illustrated schematically by the circles 7; this is a simplification, there are in fact many millions of particles of solid material in a charged fluidised bed reactor.
  • the gas materials 6 are illustrated
  • the gas materials 6 are forced into the input 3 and then through the porous plate 4.
  • the solid materials 7 remain in place as the gas materials 6 pass through the voids between the solid materials 7 (the fluidised bed reactor at this stage is sometimes called a packed bed reactor).
  • the reactor 1 reaches a stage where the force of the gas materials 6 on the solid materials 7 balances the weight of the solid materials 7 (this stage is sometimes called incipient fluidisation).
  • the solid materials 7 act like a fluid, for example like water in a boiling receptacle of water (the bed in the fluidised bed reactor at this stage is now called a fluidised bed).
  • solid materials 7 are introduced through input 2.
  • Typical examples of solid materials 7 added to a fluidised bed reactor for fluidised bed combustion or fluidised bed gasification include bed materials.
  • Fuel is also introduced through input 2, either in one shot or in a number of shots over time as the fuel is depleted.
  • Gas materials 6 are introduced through input 3.
  • gas materials 6 include air (in the case of fluidised bed combustion) and steam optionally mixed with air (in the case of fluidised bed gasification).
  • Waste gas materials are taken out of the reactor 1 through output (flue) 8.
  • Some components of the waste gas materials can be used in refining processes, particularly in the case of waste gas materials from fluidised bed gasification. Waste solid materials are taken out of the reactor 1 through output 9, or through other outputs (not shown).
  • the solid materials 7 include particles comprising a bed material and a catalyst.
  • catalysts which can be added to a fluidised bed reactor in particles comprising a bed material and a catalyst, and some reactions they catalyse in fluidised bed reactors include:
  • the nickel-chromium catalyst increases the reaction rate and prevents emission of unburned hydrocarbons.
  • reaction 2 The gaseous mixture containing carbon monoxide, obtained from biomass containing an excess of steam, over an iron catalyst (for example iron metal or an iron oxide), reacts according to reaction 2:
  • an iron catalyst for example iron metal or an iron oxide
  • iron catalyst shifts the CO/H 2 equilibrium in the favor of hydrogen gas.
  • Hydrogen gas is a preferable product because it can be used as a fuel in other methods.
  • Reactions 1 and 2 do occur in combustion and gasification. In combustion, the gases will combust in the fluidised bed reactor. In
  • Another catalyst, and a reaction that it catalyses in a fluidised bed reactor, is:
  • the substrate of the first reaction is FeTiOs.
  • one product is FeTiO 3 ; therefore FeTiO 3 is acting as a catalyst because it increases the rate of the overall chemical reaction (depleting carbon monoxide and methane and producing carbon dioxide and water) without itself undergoing any permanent chemical change.
  • This set of reactions was proposed in, "Using an oxygen-carrier as bed material for combustion of biomass in a 12-MW th circulating fluidized-bed boiler", Henrik Thunman, Fredrik Lind, Claes Breitholtz, Nicolas Berguerand, Martin Seemann, Fuel, 1 13 (2013), 300-309; the disclosure of which hereby incorporated by reference).
  • catalysts and some methods they catalyse in fluidised bed reactors, include: 4. Ilmenite (FeTiOs) as a catalyst for fluidised bed combustion of agricultural waste or sludge and their mixes with wood.
  • Ilmenite FeTiOs
  • Nickel oxide NiO
  • minerals containing nickel oxide for example olivine
  • Nickel oxide NiO
  • minerals containing nickel oxide for example olivine
  • Nickel enriched olivine as a catalyst in catalytic tar reduction in fluidised bed biomass steam gasification.
  • Copper oxide (CuO) as a catalyst in fluidised bed combustion of coal.
  • Calcium oxide (CaO) as a catalyst in cracking tar formed by rice husk fluidised bed gasification.
  • Olivine (Mg, Fe) 2 SiO 4 ) as a catalyst in fluidised bed gasification of biomass.
  • Nickel-chromium compounds of the formula: Ni 2- xCr x AI 3 where x 0.07 or 0.1 1 as a catalyst for fluidised bed gasification or fluidised bed combustion.
  • catalysts include, but are not limited to elements from groups 1 and 2 of the periodic table, as well as mixtures and/or alloys from any one, two or three of groups 1 , 2 and/or 3 of the periodic table, including:
  • Group 1 Ti, V, Cr, Mo, Fe
  • Group 2 Ni, Co, Mn, Cu
  • the size of the catalyst particles within the particles comprising a bed material and a catalyst are 250 ⁇ or lower.
  • the size of the catalyst particles within the particles comprising a bed material and a catalyst are from 0.1 to 50 ⁇ .
  • the particle sizes are measured by whether the particles fit through a suitably sized filter, for example catalyst particles of 250 ⁇ or lower fit through a filter with a mesh size of 250 ⁇ .
  • the particle sizes can be measured by laser diffraction (for example using a MalvernTM Mastersizer 3000).
  • the particles comprising a bed material and a catalyst according to the present invention have particle sizes from 0.3 mm to 2 mm, or from 0.5 mm to 1 .2 mm.
  • the particle sizes are measured by whether the particles fit through a suitably sized filter, for example particles of 1 .2 mm or lower fit through a filter with a mesh size of 1 .2 mm.
  • a suitably sized filter for example particles of 1 .2 mm or lower fit through a filter with a mesh size of 1 .2 mm.
  • the particle sizes can be measured by laser diffraction (for example using a MalvernTM Mastersizer 3000).
  • the particles comprising a bed material and a catalyst are added to a fluidised bed reactor in the form of powders, pellets, granules or slurry.
  • particles comprising a bed material and a catalyst By adding particles comprising a bed material and a catalyst to a fluidised bed reactor, it is possible to increase the efficiency of fluidised bed reaction methods (for example fluidised bed combustion or fluidised bed gasification) because the catalyst is combined with the bed material.
  • fluidised bed reaction methods for example fluidised bed combustion or fluidised bed gasification
  • the particles act as a bed material and also provide catalyst at their surfaces such that the fluidised bed reaction method is catalysed.
  • the particles comprising a bed material and a catalyst are also controllable.
  • the particles can be designed to include particular bed material and catalyst combinations to increase the efficiency of combustion or gasification of any particular fuel.
  • the fuel consumption is 1 .2 kg per hour (plus or minus 10 percent). These values can be scaled up to fluidised bed reaction methods where around 20,000 kg of fuel is consumed per hour. Fuel consumption can reach 100,000 kg per hour in large fluidised bed reactors.
  • the amount of catalyst in a particle comprising bed materials and catalyst added to fluidised bed reactors ranges from: 50% catalyst to 1 % catalyst (by weight); or 30% catalyst to 5% catalyst (by weight); or 20% catalyst to 5% catalyst (by weight); or 10% catalyst to 5% catalyst (by weight); or 30% catalyst to 8% catalyst (by weight).
  • the particles comprising bed materials and catalyst do not provide high levels of catalyst at their surfaces and do not provide a strong catalytic effect.
  • too much catalyst for example more than 50%, or 30%, by weight the particles comprising bed materials and catalyst become heavier and more energy is needed to form a fluidised bed using the particles.
  • the particles comprising bed materials and catalyst according to the present invention are refractory, i.e. they are stable up to at least 1 ,100°C.
  • the particles comprising bed materials and catalyst according to the present invention are also hard, i.e. they have a Mohs hardness of at least 6. These properties are the result of at least the calcining method at from 1 ,550°C to 1 ,675°C for from 4 hours to 6 hours. If the particles comprising bed materials and catalyst according to the present invention were not refractory and/or hard, they would disintegrate during fluidised bed reaction methods. Examples
  • Chamotte either on its own or mixed with catalyst, was heated so that it was calcined at 1 ,600°C in a rotary kiln, with rotation, for five hours.
  • the Chamotte or the mixture can be heated, so that the mixture is calcined, at: from 1 ,200°C to 1 ,675°C for from 4 hours to 6 hours; or, from 1 ,550°C to 1 ,675°C for from 4 hours to 6 hours.
  • the calcined Chamotte or the calcined mixture of Chamotte and catalyst was cooled in air at 20°C, then ground and sieved.
  • the starting material was a mixture of Chamotte and catalyst
  • the resulting material was a plurality of particles, each particle formed of Chamotte and catalyst.
  • the particles were ground and sieved to have particle sizes of from 250 ⁇ to 500 ⁇ .
  • the particle sizes were measured by a MalvernTM Mastersizer 3000.
  • Particle sizes of from 250 ⁇ to 500 ⁇ were suitable for a bench scale fluidised bed reactor as used in the present examples.
  • Table 1 shows the chemical composition of some example particles
  • the resulting particles (of F1 , F2 and F3) comprising bed material, or bed material and catalyst, were tested in a fluidised bed reactor.
  • the bench scale fluidised bed reactor used in the present examples generated power of 5kW.
  • the fluidised bed reactor was loaded with 1 ,000 grams of the particles (of F1 , F2 and F3) comprising bed material and catalyst.
  • the temperature of the fluidised bed reactor was 850°C with an oxygen concentration of 6%.
  • the fuel was a mixture of straw and wood in a weight ratio of wood 90% to straw 10%.
  • the fuel was added over 4 hours to the fluidised bed reactor and combusted.
  • the rate of fuel consumption was 1 .2 kg per hour (plus or minus 10%).
  • THC 58 32 26 In Table 2, THC refers to total hydrocarbons. The lower the THC level, the more efficient the fluidised bed combustion method is because more hydrocarbons have been combusted and do not exit in the flue gases.
  • the CO and NOx levels were measured by an infrared detector on the flue. The infrared detector was the same, and was set up in the same way, for each CO measurement and for each NOx measurement, respectively.
  • the THC level was measured by a flame ionization detector. The flame ionization detector was the same, and was set up in the same way, for each THC measurement.
  • F1 was mixed with the loose catalyst mixtures from F2 and F3 (i.e. bed material F1 loosely mixed with catalyst mixtures).
  • bed material F1 loosely mixed with catalyst mixtures On using these mixtures as the bed materials in the fluidised bed combustion shown with reference to Table 2, the loose catalyst rapidly left the fluidised bed reactor through the flue and did not participate in the fluidised bed combustion reaction. Put another way, the loose catalyst was too light on its own to catalyse the fluidised bed combustion reaction.
  • the particles were ground and sieved to have different particle sizes.

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Abstract

La présente invention concerne des matières de lit pour procédés de réaction en lit fluidisé et des procédés de réaction en lit fluidisé.
EP18708923.0A 2017-03-06 2018-02-16 Matières de lit pour procédés de réaction en lit fluidisé et procédés de réaction en lit fluidisé Withdrawn EP3592459A2 (fr)

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CN109764331B (zh) * 2019-01-10 2021-01-01 嘉兴圣斯顿金属制品有限公司 一种高效燃烧的生物质能粉末燃烧机
EP4139418A1 (fr) * 2020-04-20 2023-03-01 Teknologian Tutkimuskeskus VTT OY Procédé et appareil de production d'hydrocarbures et utilisation
CN112354516B (zh) * 2020-10-26 2021-10-29 哈尔滨工业大学 一种污泥制备磁性污泥基生物炭材料的方法及其应用
WO2023007315A1 (fr) * 2021-07-26 2023-02-02 The Trustees For The Time Being Of The Kmn Fulfilment Trust Composition de carburant pour combustion
CN115337874A (zh) * 2022-09-15 2022-11-15 南京理工大学 一种金属燃料颗粒流化床破膜反应方法

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