WO2024028540A1 - Method and apparatus for producing a product from recycled material - Google Patents

Method and apparatus for producing a product from recycled material Download PDF

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Publication number
WO2024028540A1
WO2024028540A1 PCT/FI2023/050452 FI2023050452W WO2024028540A1 WO 2024028540 A1 WO2024028540 A1 WO 2024028540A1 FI 2023050452 W FI2023050452 W FI 2023050452W WO 2024028540 A1 WO2024028540 A1 WO 2024028540A1
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WO
WIPO (PCT)
Prior art keywords
gas
pyrolysis
pyrolysis gas
fluidized bed
production unit
Prior art date
Application number
PCT/FI2023/050452
Other languages
French (fr)
Inventor
Pasi Makkonen
Antti Leinonen
Ilkka Hämäläinen
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Takaisin Technologies Oy
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Publication date
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Publication of WO2024028540A1 publication Critical patent/WO2024028540A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/48Carbon black
    • C09C1/482Preparation from used rubber products, e.g. tyres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B47/00Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/18Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge
    • C10B47/22Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge in dispersed form
    • C10B47/24Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge in dispersed form according to the "fluidised bed" technique
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • C10B49/04Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
    • C10B49/08Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
    • C10B49/10Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/14Features of low-temperature carbonising processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/024Dust removal by filtration
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/028Dust removal by electrostatic precipitation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/026Dust removal by centrifugal forces

Definitions

  • the application relates to a method defined in claim 1 and an apparatus defined in claim 11 for producing at least one product from recycled material . Further, the application relates to a use of the method defined in claim 18 .
  • Tire waste and tire-derived rubber waste are classified as end-of-life tyre (ELT ) derived products . It is known that the tire and rubber wastes can be recycled as such or as a rubber/tire material , they can be treated mechanically, and/or they can be treated by a thermal treatment .
  • ELT end-of-life tyre
  • the obj ective is to disclose a new method and apparatus for producing at least one high-value product from recycled material , especially tire waste , tire- derived rubber waste , waste rubber and asphalt felt . Further , the obj ective i s to di sclose a method and apparatus for treating recycled material comprising rubber material and/or bituminous material . Further, the obj ective is to improve recycling of tire waste , tire- derived rubber waste , waste rubber and asphalt felt .
  • recycled material comprising at least rubber material and/or bituminous material is fed to a fluidi zed bed reactor and a gaseous fluidi zing agent is supplied to a reactor .
  • the recycled material is fluidi zed by the fluidi z ing agent , and the recycled material is treated by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas .
  • Coarse particles and/or solid material are separated from the pyrolysis gas , and after that a product comprising carbon black is formed by separating carbon black particles from the pyrolysis gas .
  • Fig . 1 i s a flow chart illustration of a process according to one embodiment
  • Fig . 2 i s a flow chart i llustration of a process according to another embodiment
  • Figs . 3 and 4 show testing results .
  • At least one product is produced from recycled material .
  • the recycled material comprising at least rubber material and/or bituminous material is fed to a fluidi zed bed reactor which is a vertical reactor .
  • a gaseous fluidi zing agent is formed and heated, and the heated gaseous fucidi zing agent i s supplied to a lower part of the reactor, preferably under the inlet of the recycled material .
  • the recycled material is fluidi zed by the fluidi zing agent , and the recycled material is treated by a pyrolysis in the fluidi zed bed reactor to form a pyrolysis gas , such as a burnable gas or combustible gas .
  • the pyrolysis gas is discharged from a top of the fluidi zed bed reactor, and coarse particles and/or solid material are separated from the pyrolysis gas in a solids separator, e.g. a cyclone, arranged after the fluidized bed reactor.
  • the pyrolysis gas is supplied to a separation device, and a product comprising carbon black is formed by separating, e.g. filtrating, carbon black particles from the pyrolysis gas in the separation device. Then a gas product consisting of the pyrolysis gas is formed.
  • the recycled material forms a bed in the reactor and the fluidizing agent is supplied through the bed.
  • the object is to form a gaseous pyrolysis product, not a liquid product, in the present fluidized bed reactor.
  • An apparatus for producing at least one product from recycled material comprises at least one fluidized bed reactor which is a vertical reactor and in which the recycled material is treated, at least one recycled material inlet for feeding the recycled material comprising at least rubber material and/or bituminous material to the fluidized bed reactor and at least one fluidizing agent inlet for supplying a heated gaseous fluidizing agent to a lower part of the reactor such that the recycled material is fluidized by the fluidizing agent and treated by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas.
  • the apparatus comprises at least one pyrolysis gas outlet for discharging the pyrolysis gas from a top of the fluidized bed reactor, at least one solids separator, e.g.
  • cyclone or other separator arranged after the fluidized bed reactor for separating coarse particles and/or solid material from the pyrolysis gas, and at least one separation device for forming a product comprising carbon black by separating, e.g. filtrating, carbon black particles from the pyrolysis gas.
  • the recycled material means any recycled material, recyclable material, re-used material, reusable material, waste material, circular material, residue material, hazardous waste, material recovered from its first or primary use or from first or previous use phase, or the like, or their combinations, which comprises at least rubber material and/or bituminous material and which can be reused.
  • the recycled material can comprise other components or compounds.
  • the recycled material can contain one or more components. At least one component of the recycled material comprises carbon black.
  • tire waste or tire-derived rubber waste e.g. end-of-life tyre (ELT) derived products, contains significant amounts carbon black.
  • the recycled material is selected from the group consisting of waste rubber, tire waste, tire-derived rubber waste, polymer waste, plastic waste, asphalt felt and their combinations. In one embodiment, the recycled material consists of waste rubber, tire waste, tire-derived rubber waste, asphalt felt or their combinations. In one embodiment, the recycled material consists of waste rubber, tire waste, tire-derived rubber waste, or their combinations. In one embodiment, the recycled material consists of asphalt felt.
  • the recycled material comprises carbon black. Further the recycled material comprises a binding material, e.g. polymer, for binding carbon black, i.e. the carbon black is bound by the binding material.
  • the tire waste or tire-derived rubber waste may contain significant amounts, even up to 50 % , carbon black.
  • tire-derived rubber waste or waste rubber polymers e.g. rubber bind carbon black.
  • tire-derived rubber waste or waste rubber sulphur may be used as a binding agent, e.g. in a vulcanization.
  • the recycled material may be pre-treated before the pyrolysis process, e.g. by sorting, crushing, grinding, sieving, pre-heating and/or by other way.
  • raw material is crushed and/or grinded to form the recycled material which is used in the present process.
  • the recycled material is in the form of crushed aggregate, chips, breaker product, granulars, granules, powder, or the like or their combinations.
  • the recycled material is in the form of crushed aggregate, chips, granules, powder, or their combinations. In one embodiment, the recycled material is in the form of crushed aggregate for the pyrolysis. In one embodiment, the recycled material is in the form of granules for the pyrolysis. In one embodiment, the recycled material is in the form of powder for the pyrolysis.
  • the recycled material consists of solid material.
  • the recycled material contains rubber 0.1 - 10 % by weight and other solid material 99.9 - 90 % by weight, in one embodiment rubber 2 - 8 % and 98 - 92 % other solid material, in one embodiment rubber 4 - 6 % and 96 - 94 % other solid material, and in one embodiment rubber about 5 % and other solid material about 95 % .
  • an additional solid material e.g. sand or another material, is fed to the fluidized bed reactor.
  • the recycled material and the additional solid material are fed to the fluidized bed reactor to form a feed
  • the feed contains rubber 0.1 - 10 % by weight and other solid material 99.9 - 90 % by weight, in one embodiment rubber 2 - 8 % and 98 - 92 % other solid material, in one embodiment rubber 4 - 6 % and 96 - 94 % other solid material, and in one embodiment rubber about 5 % and other solid material about 95 % .
  • the fluidizing agent means any gaseous fluidizing agent which can be used for fluidizing the recycled material in the fluidized bed reactor.
  • the fluidizing agent can be formed and heated in a device in which the fluidizing agent is heated or heat is produced in connection with forming of the fluidizing agent, and the heated fluidizing agent is supplied to the lower part of the fluidized bed reactor.
  • the fluidizing agent is formed and heated by means of a heat source device.
  • the gaseous fluidizing agent is formed from starting material, e.g. gaseous substance, in the heat source device in which the starting material is burned to form the gaseous fluidizing agent.
  • the gaseous fluidizing agent is formed from methane, LNG (liquified natural gas) , flue gas, process gas or their combinations. In one embodiment, the gaseous fluidizing agent is formed from the methane, LNG, flue gas or process gas. In one embodiment, the gaseous fluidizing agent is formed from the methane, LNG, flue gas and/or process gas in the heat source device in which the methane, LNG, flue gas and/or process gas is burned to form the gaseous fluidizing agent.
  • the starting material comprises oxygen, and in one embodiment the starting material comprises an optimum amount of oxygen for burning, e.g. in the heat source device. In one embodiment, an oxygen content of the fluidizing agent is 3 - 5 % by volume.
  • the heat source device comprises at least a burner in which the gaseous fluidizing agent is formed and heated by burning.
  • the gaseous fluidizing agent is a hot gas.
  • the fluidizing agent is heated to a temperature which is 250 - 400 °C, in one embodiment 250 - 350 °C, and in one embodiment 270 - 320 °C. In one embodiment, the temperature of the heated fluidizing agent is less than 350 °C.
  • pressure of the fluidizing agent is arranged to pressure up to 0.5 bar (g) in the heating device, e.g. in the heat source device .
  • the fluidized bed reactor can be any fluidized reactor comprising a fluidized bed in which a heat treatment and/or pyrolysis can be carried out and pyrolysis gas can be formed.
  • the fluidized bed reactor is a fast fluidized bed reactor.
  • the fluidized bed reactor is a circulating fluidized bed reactor, e.g. CFB-reactor.
  • the fluidized bed reactor is a vertical reactor, and the fluidizing agent is used for fluidizing the recycled material in the reactor.
  • the fluidizing agent is used simultaneously for fluidization, pyrolysis and attrition, e.g. grinding, of the recycled material in the reactor.
  • the apparatus comprises at least one feeder for feeding the recycled material via the recycled material inlet to the fluidized bed reactor to form a bed in the reactor.
  • the feeder can be any feeder, feed equipment or other suitable feed device.
  • the feeder is selected from the group comprising pump, screw, tube, pipe, other suitable feeder and their combinations.
  • the feeder is a screw conveyor, dual-screw conveyor or their combinations.
  • the feeder comprises a lock hopper.
  • the heated gaseous fluidizing agent is supplied to a lower part of the reactor and under the recycled material inlet.
  • the recycled material is fed above the fluidizing agent inlet in the reactor.
  • the fluidizing agent is supplied to the reactor, e.g. to a wind box, in which the fluidizing agent is distributed, for example through a grate, into a reaction vessel or chamber of the fluidized bed reactor.
  • the recycled material is fluidized by means of the fluidizing agent such that the fluidizing agent flows through a bed of the recycled material and the recycled material is fluidized by fluiding agent flow. The fluidization improves a heat transfer from the fluidizing agent into particles of the recycled material.
  • particles of the recycled material form a dense fluidized bed which becomes less dense when at least a part of the particles, e.g. fine particles, are fluidized into an upper part of the reactor by the fluidizing agent.
  • the fluidization, pyrolysis and attrition of the recycled material may be performed simultaneously.
  • the recycled material is treated by heat such that bonds which are formed by the binding material, e.g. polymer or rubber polymer, and which bind carbon black are broken down during the pyrolysis. However, carbon black is not broken during the pyrolysis.
  • pyrolysis temperature is 250 - 350 °C, and in one embodiment 270 - 320 °C, and in one embodiment about 300 °C.
  • the pyrolysis is carried out under vacuum.
  • the pyrolysis is carried out under light vacuum, e.g. under vacuum between -100 mbar and -1 mbar or in one embodiment under vacuum of about -10 mbar.
  • the fluidizing gas has a velocity of 3 - 6 m/ s .
  • the pyrolysis gas comprising carbon black is formed by the pyrolysis in the fluidized bed reactor.
  • the pyrolysis gas means any pyrolysis gas comprising gaseous component or components, i.e. gaseous pyrolysis product.
  • the gaseous pyrolysis product contains hydrogen and hydrocarbons, in one embodiment high amounts of hydrogen and hydrocarbons.
  • the gaseous pyrolysis product comprises at least fine particles.
  • the gaseous pyrolysis product may contain most of the sulphur of the recycled material.
  • the pyrolysis gas may comprise several components.
  • the pyrolysis gas comprises at least gaseous pyrolysis product and carbon black.
  • the pyrolysis gas may comprise also coarse particles and/or solid material.
  • the gaseous pyrolysis product comprises burnable components, e.g. polymer based burnable components and/or hydrocarbon based burnable components.
  • the pyrolysis gas together with particles is discharged from the fluidized bed reactor through an opening at the top side wall of the reactor and lead to the solids separator.
  • the solids separator means any separator, separating device, cyclone or similar device in which any solids, solid material, solid matter, dry substance, particles, or the like can be separated from the pyrolysis gas.
  • the solids separator is integrated with the fluidized bed reactor.
  • the solids separator is adjustable.
  • coarse particles and/or solid material is separated from the pyrolysis gas.
  • particles of the coarse particles and/or solid material with desired particle sizes are separated from the pyrolysis gas.
  • the coarse material or solid material is fractionated in connection with the separation.
  • the coarse material and/or solid material may comprise any solid particles, over-size particles, metals, solid material with melting point which is higher than temperature in the pyrolysis, or their combinations.
  • the solid material comprises at least metal particles.
  • the solids separator is a cyclone. Any suitable cyclone, e.g. gas cyclone, cyclone separator, or their combination, can be used as the cyclone.
  • the solids separator e.g. cyclone, acts as a pre-separator .
  • the coarse particles and/or solid material e.g. over-size particles
  • the coarse particles and/or solid material is recirculated from the solids separator to the fluidized bed reactor.
  • the coarse particles and/or solid material is recirculated from the solids separator to a reactor chamber of the fluidized bed reactor, e.g. to a bottom part or lower part of the reactor chamber in the reactor.
  • at least the solid material e.g. metals
  • the coarse particles and/or solid material is recirculated from the solids separator to the fluidized bed reactor and again with the pyrolysis gas from the fluidized bed reactor to the solids separator.
  • Attrition, e.g. grinding, of the particles of the recycled material is performed during the fluidization and pyrolysis in the fluidized bed reactor.
  • the coarse particles, and/or also the solid material is recirculated in a combination of the fluidized bed reactor and solids separator so long that particles have a particle size which is sufficient small to move along with the pyrolysis gas out from the solids separator, i.e. over-size particles stay in the circulation.
  • the apparatus comprises at least one circulating device for recirculating the coarse particles and/or solid material from the solids separator to the fluidized bed reactor.
  • the apparatus comprises a loop seal after the solids separator, and the coarse particles and/or solid material are recirculated to the fluidized bed reactor through the loop seal.
  • the coarse particles and/or solid material can be taken out from the loop seal.
  • the loop seal prevents the gases leaving the reactor at the bottom or lower part of the reactor and entering into the solids separator.
  • the loop seal is integrated with the reactor, and the coarse particles and/or solid material may be taken out before the reactor, e.g. reactor chamber or vessel.
  • a desired part of the coarse particles and/or solid material is recovered as a solid product, e.g. a semifinished product, from the loop seal and/or after the solids separator.
  • the solid product may be used as a filler in a final product or as a binding material in pellets or in other purposes.
  • the solid product may be upgraded or reprocessed to form final products or new materials.
  • the pyrolysis gas comprising particles, e.g. fine particles such as carbon black particles, is supplied to the separation device, e.g. directly from the solids separator to the separation device or via cooling or heating to the separation device.
  • the pyrolysis gas leaves the solids separator via a central tube, e.g. a vortex finder.
  • the pyrolysis gas is cooled between the solids separator and the separation device.
  • the pyrolysis gas is heated between the solids separator and the separation device.
  • the apparatus comprises at least one cooling device and/or heating device after the solids separator and/or before the separation device for cooling and/or heating the pyrolysis gas. Any suitable cooling device may be used for cooling the pyrolysis gas. Any suitable heating device may be used for heating the pyrolysis gas.
  • the pyrolysis gas is heated in a heating device before the separation device.
  • the apparatus comprises at least one heating device for heating the pyrolysis gas.
  • the heating device comprises a ball mill in which the pyrolysis gas is heated and particles of the pyrolysis gas are treated.
  • the apparatus comprises the heating device and at least one ball mill which are arranged sequentially and wherein the pyrolysis gas is heated in the heating device and particles of the pyrolysis gas are treated in at least one ball mill.
  • the apparatus comprises more than one ball mill, the each ball mill may comprise different-sized balls.
  • the particles comprising carbon black particles are separated from the pyrolysis gas. Simultaneously a purified pyrolysis gas is formed.
  • Any suitable separation device e.g. filter, bag filter, multicyclone, classifier, their combination or the like, may be used as the separation device in the present method or apparatus for separating at least carbon black particles from the pyrolysis gas.
  • the filter is selected from the group consisting of a fabric filter, electrostatic filter, bag filter baghouse filter, and their combinations.
  • the filter is a fabric filter.
  • the filter is an electrostatic filter.
  • the filter is a bag filter.
  • the separation device is a multicyclone.
  • the apparatus comprises more than one separation devices which are arranged sequentially.
  • the pyrolysis gas may comprise also other particles than the carbon black particles, and different particles are separated in the sequential separation steps or devices such that the carbon black particles with high purity are separated in the last separation step or device.
  • a basic fraction is separated in the first separation step or device and a pure carbon black fraction, i.e. primary fraction, is separated in the last separation step or device, and optionally at least one another fraction is separated between the first and last separation steps or devices.
  • the basic fraction comprising carbon black and other particles may be used in tire material.
  • the pure carbon black fraction may be used as the carbon black product, e.g. printing ink.
  • the product comprising carbon black is recovered by separating from the pyrolysis gas in the separation device.
  • the product comprises at least carbon black particles.
  • the product consists mainly of carbon black particles.
  • the product consists of carbon black particles.
  • the product is pelletized for facilitating transport, storage and use.
  • the purified pyrolysis gas e.g. burnable gas
  • the pyrolysis gas can be utilized, e.g. in energy production and/or power production, or as a starting material for forming a final product.
  • the purified pyrolysis gas may be supplied to a power production unit.
  • polymers which bind the carbon black in the recycled material can be pyrolyzed into burnable gas, which is a good source of energy, and the burnable gas can be recovered, and the burnable gas may be supplied to a power production unit.
  • the pyrolysis gas is treated under vacuum, for example under low vacuum, e.g. between -100 mbar and -1 mbar, and then all pyrolysis gas components operate in low vacuum after the pyrolysis.
  • low vacuum e.g. between -100 mbar and -1 mbar
  • an in-built odor control can be achieved when all pyrolysis gas components operate in low vacuum.
  • the pyrolysis gas is supplied to a power production unit, such as after the separation and/or after the separation of the product in the separation device, to form an energy.
  • the apparatus comprises a power production unit to which the pyrolysis gas is supplied, e.g. after the separation device .
  • the power production unit comprises at least one energy production unit, and the pyrolysis gas, e.g. burnable gas, is supplied, e.g. directly from the separation device, to the energy production unit where the pyrolysis gas is burned to form flue gas and energy, and energy of the energy production unit is recovered, e . g . in the form of steam.
  • the power production unit comprises an energy production unit , and the energy production unit comprises at least one burner and/or steam boiler .
  • the power production unit comprises at least one energy production unit and at least one power production device , and the energy, e . g . steam, is supplied from the energy production unit to the power production device for producing electricity and/or heat .
  • the power production unit comprises at least one energy production unit and at least one power production device , and the energy is supplied from the energy production unit comprising a burner and/or steam boiler to the power production device comprising a steam turbine, gas engine , gas turbine, generator, condenser or their combinations .
  • the power production unit comprises the energy production unit and the power production device for producing electricity and/or heat
  • the power production device is selected from the group consisting of a steam turbine , gas engine , gas turbine, generator, condenser or their combinations .
  • the power production device comprises a steam turbine , gas engine , gas turbine and/or generator to form at least electricity .
  • the power production device comprises also a condenser in which heat is formed and/or in which the steam or a part of the steam may be condensed into water .
  • the condensed water is recirculated to the energy production unit , or the water may be removed from the process .
  • the energy production unit and power production device are combined to form a single power production unit for producing electricity and/or heat from the pyrolysis gas .
  • the sulphur used as a binding agent in the recycled material e . g . in a vulcanization, is collected from the pyrolysis gas or from flue gas produced in the energy production process.
  • flue gas of the power production unit e.g. flue gas of the energy production unit
  • the apparatus comprises at least one gas cleaning device for gas cleaning and sulphur capture.
  • the apparatus comprises at least one scrubber for cleaning flue gas of the power production unit, e.g. flue gas of the energy production unit, and/or for sulphur capturing from the flue gas.
  • the gas cleaning device e.g. the scrubber
  • sulphur can be removed from the flue gas.
  • at least one chemical is added to the gas cleaning device, e.g. the scrubber, for facilitating sulphur capture from the flue gas. The sulphur can be removed without added chemicals or with added chemicals, depending on the process and process conditions.
  • the method and apparatus are based on a continuous process.
  • the apparatus is a mobile apparatus, which can be transported to a desired place for treating the recycled material.
  • the apparatus is arranged into a container, and then a transport of the apparatus can be facilitated.
  • the product comprising carbon black is formed. Also a gas product comprising the pyrolysis gas is formed. In one embodiment, the present method and apparatus is based on a co-production of carbon black and energy. In one embodiment, the product comprising carbon black is porous and have high specific surface area.
  • the method and the apparatus are used and/or utilized in a production of carbon black, in a treatment of waste rubber, tire waste and/or tire-derived rubber waste, in a treatment of asphalt felt waste, in a production of tires, in a production of fillers, plastic fillers, colorants, pigments, inks, printing inks, additives, paints, coatings, rubber goods, films or other substances, or their combinations.
  • the product comprising carbon black obtained by the method is used in tires, fillers, inks, printing inks, colorants, additive agents, pigments, rubber goods, paints, coatings, plastics, films, other substances, or their combinations.
  • the high- quality carbon black and the pyrolysis gas with high heating value can be produced. Further, significant amount of energy in form of electricity and heat can be generated by burning the burnable pyrolysis gas. Further, sulphur as a side product can be produced. Further, by means of the method and process, the apparatus has a simple construction, and there are no moving parts in the reactor. Further, the integrated grinding and separation of the carbon black particles can be achieved, desired particle size of the carbon black and classification of the carbon black into desired particle size distribution can be achieved, and several particle sizes can be produced in one process. Further, the particle size can be reduced by attrition in the fluidized bed. Further, thanks to the process high separation efficiency of the carbon black product and the pyrolysis gas can be achieved. Further, energy such as power and heat can be produced by combusting the pyrolysis gas which has high heating value. An efficiency of the process is excellent, and all fractions can be recovered and recycled, and energy can be utilized.
  • a long residence time for the raw material can be achieved in a small reactor volume. Further, good heat transfer and mass transfer for the raw material can be achieved in a small reactor volume. Further, small footprint can be achieved when at least the fluidized bed reactor and the separation device are installed in vertical position.
  • the method and apparatus offer a possibility to form products with good properties easily, and energy- and cost-effectively.
  • the present invention provides an industrially applicable, simple and affordable way to treat the recycled materials, and further simultaneously to produce desired products and energy. For example, different tire waste materials, tire-derived rubber waste, waste rubbers, asphalt felts and other hazardous wastes and their fractions can be treated easily and effectively in the process to form new products. Further, the process allows parallel production of different products.
  • the method and apparatus are easy and simple to realize in connection with production processes. Further, the present apparatus can be used as a transportable process arrangement.
  • Fig. 1 presents the process and the apparatus for producing carbon black from recycled waste material, e.g. tire waste powder.
  • the apparatus of Fig. 1 comprises a fluidized bed reactor (1) , a cyclone (7) and a filter (12) , and optionally an energy production unit (15) , a power production device (18) and a gas cleaning device (22) .
  • the fluidized bed reactor (1) is a vertical circulating fluidized bed reactor in which the waste material (2) is treated.
  • the waste material comprising at least rubber material and/or bituminous material is fed by a feeder via a waste material inlet to the fluidized bed reactor.
  • the waste material forms a bed in the reactor.
  • a heated gaseous fluidizing agent (5) is supplied via a fluidizing agent inlet to a lower part of the reactor (1) .
  • the fluidizing agent may be formed by heating in a heating device (3) , e.g. in a heat source device, for example from LNG or flue gas (4) .
  • the fluidizing agent (5) is supplied into the bed of the waste material and through the bed such that the waste material is fluidized by the fluidizing agent and treated by a pyrolysis in the fluidized bed reactor. Then a pyrolysis gas (6) is formed.
  • the pyrolysis gas (6) is discharged via a pyrolysis gas outlet from a top of the fluidized bed reactor.
  • the pyrolysis gas is supplied to a cyclone (7) arranged after the fluidized bed reactor and integrated with the fluidized bed reactor in order to separate coarse particles and/or solid material (8) from the pyrolysis gas.
  • the coarse particles and/or solid material are recirculated to the fluidized bed reactor (1) , preferably to a bottom part in a reactor chamber in which the pyrolysis is carried out.
  • the coarse particles and/or solid material may be recirculated to a loop seal (9) and from the loop seal to the reactor (1) .
  • the pyrolysis gas (11) from the cyclone (7) is supplied to a filter (12) .
  • the pyrolysis gas (11) may be cooled by means of a cooling device or heated by means of a heating device before the filter (12) .
  • a product (14) comprising carbon black is formed by filtrating carbon black particles from the pyrolysis gas (11) .
  • the carbon black product (14) comprising carbon black particles is recovered.
  • a purified pyrolysis gas (13) which is a combustible gas, is recovered.
  • the pyrolysis gas (13) is supplied to a power production unit comprising at least the energy production unit (15) and optionally also the power production device (18) .
  • the energy production unit (15) comprises a burner and/or a steam boiler for forming flue gas (16) and steam (17) .
  • the steam may be supplied to the power production device (18) .
  • the power production device comprises a steam turbine, or a steam turbine and a generator, or a gas engine, or a gas turbine, or a gas turbine and a generator in order to produce electricity (21) and/or heat (20) .
  • the power production device may comprise also a condenser (19) for condensing the steam or a part of the steam into water (26) .
  • the water may be recirculated to the energy production unit (15) .
  • the energy production unit and power production device are combined to form a power production unit in which electricity and/or heat can be produced.
  • the flue gas (16) from the energy production unit (15) may be supplied to a gas cleaning device (22) , e.g. a scubber, for gas cleaning and sulphur capture.
  • a gas cleaning device e.g. a scubber
  • sulphur (23) can be removed from the flue gas, and a purified flue gas (24) can be achieved.
  • the sulphur can be removed without added chemicals or with added chemicals (25) , depending on the process and process conditions.
  • the apparatus of Fig. 1 may be a mobile apparatus.
  • the apparatus may be arranged into a container, and then the apparatus is easy to transport.
  • Fig. 2 presents the process arrangement according to example 1.
  • the process arrangement (Fig. 2) , i.e. the apparatus, is for pyrolysis of rubber tire waste aiming for co-production of carbon black and energy.
  • the tire waste contains significant amounts (up to 50 %) carbon black, which can be recycled as a material component.
  • the polymers, e.g. rubber, binding the carbon black can be pyrolyzed into burnable gas, which is a good source of energy.
  • the sulphur used as a binding agent (vulcanization) may be collected from the gas or from the flue gas produced in the energy production process.
  • the process arrangement comprises a heat source (3) , a fluidized bed reactor (1) , a cyclone separator (7) , a filter (12) , an energy production unit (15) , a power production device (18) and a gas cleaning device (22) .
  • the heat source (3) produces a hot fluidizing gas (5) , for example 350 °C with pressure up to 0.5 bar (g) , for the pyrolysis and fluidization of the tire waste powder (2) .
  • the fluidizing gas can be formed from a suitable starting material (4) , e.g. from methane, LNG or flue gas.
  • the hot fluidizing gas (5) is supplied to the fluidized bed reactor (1) .
  • the fluidizing gas enters a wind box, from which it is distributed through a special grate into a reaction chamber of the fluidized bed reactor ( 1 ) .
  • the fluidized bed reactor (1) which is a vertical reactor, uses the hot gas (5) for fluidization, pyrolysis and attrition (grinding of the material) .
  • the tire waste (2) is fed above the fluidizing gas inlet in the reactor, and a bed of tire waste powder is formed in the reactor.
  • the tire waste powder is fluidized by the fluidizing gas to flow through the bed of reactor. This fluidization helps to gain maximal heat transfer from the hot gas into the particles of the tire waste.
  • the polymers binding the carbon particles are broken down by the heat in the reactor, and pyrolysis gas comprising carbon black is formed.
  • the hot pyrolysis gas (6) leaves the vertical reactor together with solid particles through an opening at the top side wall of the reactor.
  • the pyrolysis gas is supplied to a gas cyclone separator ( 7 ) .
  • the cyclone separator (7) which is integrated with the fluidized bed reactor (1) is adjustable.
  • solid material (8) with desired particle sizes are separated from the pyrolysis gas. Further, the solid material may be fractionated of smaller particles. Then desired particle size and reduction of size in large particles can be achieved. Over-size particles (8) are returned to a bottom part of the reactor (1) .
  • material can be taken also from a loop seal (9) after the cyclone.
  • a "water lock" called loop seal prevents the gases from leaving the reactor into the cyclone.
  • the pyrolysis gas (11) together with the finest particles leave the cyclone (7) via a central tube called vortex finder, and the pyrolysis gas (11) is supplied to the filter (12) .
  • the pyrolysis gas may be cooled before the filter.
  • the filter (12) which is a fabric filter, alternatively an electrostatic filter, separates carbon black particles from the pyrolysis gas.
  • a carbon black product (14) comprising carbon black particles is recovered, and the purified pyrolysis gas (13) , i.e. burnable gas, is supplied to an energy production unit (15) .
  • the carbon black product (14) consisting of mainly carbon black particles can be pelletized or treated in other way for facilitating transport, storage and use.
  • the energy production unit (15) comprises a burner and a steam boiler for forming flue gas (16) and steam (17) .
  • the steam is supplied to a power production device (18) .
  • the power production device comprises a steam turbine, or a steam turbine and a generator, or a gas engine, or a gas turbine, or a gas turbine and a generator in order to produce electricity (21) and/or heat (20) .
  • the power production device can comprise also a condenser (19) in which the steam or a part of the steam is condensed into water (26) .
  • the energy production unit and power production device are combined to form a power production unit in which electricity and/or heat can be produced.
  • the flue gas (16) from the energy production unit is supplied to a scubber (22) for gas cleaning and sulphur capture.
  • scubber (22) sulphur (23) can be removed from the flue gas (24) .
  • the sulphur can be removed without added chemicals or with added chemicals ( 25 ) , depending on the process and process conditions .
  • the benefits of the present process arrangement are a simple construction , no moving parts in the reactor, integrated grinding and separation of the carbon black particles , possibility to produce several particle si zes in one process because the particle material can be taken also from a loop seal after the cyclone , desired particle si ze distribution due to the adj ustable cyclone separator, high efficiency separation of the carbon black product , the pyrolysis gas with a high heating value , in-built odor control where all pyrolysis gas components operate in low vacuum, and small footprint as at least the fluidi zed bed reactor and the filter are installed in vertical position .
  • the tire waste material is treated according to example 1 .
  • Table 1 shows an example chemical composition of pyrolysis gas formed from tire waste .
  • the process arrangement is capable of handling 16 000 ton/a tire waste and then it may be able to produce more than 5000 ton/a carbon black, more than 20 GWh electricity and 40 GWh heat.
  • the estimated HHV (Higher Heating Value) of such a pyrolysis gas is over 30 MJ/kg.
  • the first test was run with the laboratory oven so that the pulverized sample was set on a mesh inside a crucible at 275 °C for two (2) hours. In the first tests, it was observed that there is no liquid at the bottom of the crucible. Testing results are shown in Fig. 3.
  • Fig . 4 Testing results with larger tire particles are shown in Fig . 4 in which left side comprises large particle and right side comprises hard ceramic-like structure which is mostly carbon black .
  • the tire rubber can be pyrolyzed easily into pyrolysis gas .
  • the fluidi zed bed reactors , heat source devices , solids separators and separation devices , and energy and power production devices and gas cleaning devices , and other devices used in these examples are known per se , and therefore they are not described in any more detail in this context .
  • the method and apparatus are suitable in different embodiments for producing products , e . g . carbon black products and combustible gases , from different kinds of recycled materials . Further, the method and apparatus are suitable in different embodiments for treating different recycled materials comprising rubber material and/or bituminous material, e.g. different haz- ardous materials.

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Abstract

The invention relates to a method and an apparatus for producing at least one product from recycled material. The recycled material (2) comprising at least rubber material and/or bituminous material is fed to a fluidized bed reactor (1) which is a vertical reactor, and a gaseous fluidizing agent is formed and heated, and the heated gaseous fluidizing agent (5) is supplied to a lower part of the reactor. The recycled material is fluidized by the fluidizing agent, and the recycled material is treated by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas (6). The pyrolysis gas (6) is discharged from a top of the fluidized bed reactor. Coarse particles and/or solid material (8) are separated from the pyrolysis gas (6) in a solids separator (7) arranged after the fluidized bed reactor, and the pyrolysis gas is supplied to a separation device (12) and a product (14) comprising carbon black is formed by separating carbon black particles from the pyrolysis gas in the separation device. Further, the invention relates to the use of the method.

Description

METHOD AND APPARATUS FOR PRODUCING A PRODUCT FROM RECYCLED MATERIAL
FIELD
The application relates to a method defined in claim 1 and an apparatus defined in claim 11 for producing at least one product from recycled material . Further, the application relates to a use of the method defined in claim 18 .
BACKGROUND
Tire waste and tire-derived rubber waste are classified as end-of-life tyre (ELT ) derived products . It is known that the tire and rubber wastes can be recycled as such or as a rubber/tire material , they can be treated mechanically, and/or they can be treated by a thermal treatment .
OBJECTIVE
The obj ective is to disclose a new method and apparatus for producing at least one high-value product from recycled material , especially tire waste , tire- derived rubber waste , waste rubber and asphalt felt . Further , the obj ective i s to di sclose a method and apparatus for treating recycled material comprising rubber material and/or bituminous material . Further, the obj ective is to improve recycling of tire waste , tire- derived rubber waste , waste rubber and asphalt felt .
SUMMARY
The method and apparatus and use are characteri zed by what are presented in the claims .
In the method and apparatus , recycled material comprising at least rubber material and/or bituminous material is fed to a fluidi zed bed reactor and a gaseous fluidi zing agent is supplied to a reactor . The recycled material is fluidi zed by the fluidi z ing agent , and the recycled material is treated by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas . Coarse particles and/or solid material are separated from the pyrolysis gas , and after that a product comprising carbon black is formed by separating carbon black particles from the pyrolysis gas .
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings , which are included to provide a further understanding of the invention and constitute a part of this specification, illustrate some embodiments of the invention and together with the description help to explain the principles of the invention . In the drawings :
Fig . 1 i s a flow chart illustration of a process according to one embodiment ,
Fig . 2 i s a flow chart i llustration of a process according to another embodiment , and
Figs . 3 and 4 show testing results .
DETAILED DESCRIPTION
In a method at least one product is produced from recycled material . The recycled material comprising at least rubber material and/or bituminous material is fed to a fluidi zed bed reactor which is a vertical reactor . A gaseous fluidi zing agent is formed and heated, and the heated gaseous f luidi zing agent i s supplied to a lower part of the reactor, preferably under the inlet of the recycled material . The recycled material is fluidi zed by the fluidi zing agent , and the recycled material is treated by a pyrolysis in the fluidi zed bed reactor to form a pyrolysis gas , such as a burnable gas or combustible gas . The pyrolysis gas is discharged from a top of the fluidi zed bed reactor, and coarse particles and/or solid material are separated from the pyrolysis gas in a solids separator, e.g. a cyclone, arranged after the fluidized bed reactor. The pyrolysis gas is supplied to a separation device, and a product comprising carbon black is formed by separating, e.g. filtrating, carbon black particles from the pyrolysis gas in the separation device. Then a gas product consisting of the pyrolysis gas is formed. The recycled material forms a bed in the reactor and the fluidizing agent is supplied through the bed. The object is to form a gaseous pyrolysis product, not a liquid product, in the present fluidized bed reactor.
An apparatus for producing at least one product from recycled material comprises at least one fluidized bed reactor which is a vertical reactor and in which the recycled material is treated, at least one recycled material inlet for feeding the recycled material comprising at least rubber material and/or bituminous material to the fluidized bed reactor and at least one fluidizing agent inlet for supplying a heated gaseous fluidizing agent to a lower part of the reactor such that the recycled material is fluidized by the fluidizing agent and treated by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas. Further, the apparatus comprises at least one pyrolysis gas outlet for discharging the pyrolysis gas from a top of the fluidized bed reactor, at least one solids separator, e.g. cyclone or other separator, arranged after the fluidized bed reactor for separating coarse particles and/or solid material from the pyrolysis gas, and at least one separation device for forming a product comprising carbon black by separating, e.g. filtrating, carbon black particles from the pyrolysis gas.
One embodiment of the method and the apparatus is shown in Fig. 1. Another embodiment of the method and the apparatus is shown in Fig. 2. In this context, the recycled material means any recycled material, recyclable material, re-used material, reusable material, waste material, circular material, residue material, hazardous waste, material recovered from its first or primary use or from first or previous use phase, or the like, or their combinations, which comprises at least rubber material and/or bituminous material and which can be reused. Further, the recycled material can comprise other components or compounds. The recycled material can contain one or more components. At least one component of the recycled material comprises carbon black. For example, tire waste or tire-derived rubber waste, e.g. end-of-life tyre (ELT) derived products, contains significant amounts carbon black. In one embodiment, the recycled material is selected from the group consisting of waste rubber, tire waste, tire-derived rubber waste, polymer waste, plastic waste, asphalt felt and their combinations. In one embodiment, the recycled material consists of waste rubber, tire waste, tire-derived rubber waste, asphalt felt or their combinations. In one embodiment, the recycled material consists of waste rubber, tire waste, tire-derived rubber waste, or their combinations. In one embodiment, the recycled material consists of asphalt felt. The recycled material comprises carbon black. Further the recycled material comprises a binding material, e.g. polymer, for binding carbon black, i.e. the carbon black is bound by the binding material. For example, the tire waste or tire-derived rubber waste may contain significant amounts, even up to 50 % , carbon black. In the tire waste, tire-derived rubber waste or waste rubber, polymers e.g. rubber bind carbon black. Further, in the tire waste, tire-derived rubber waste or waste rubber, sulphur may be used as a binding agent, e.g. in a vulcanization. The recycled material may be pre-treated before the pyrolysis process, e.g. by sorting, crushing, grinding, sieving, pre-heating and/or by other way. In one embodiment, raw material is crushed and/or grinded to form the recycled material which is used in the present process. In one embodiment, the recycled material is in the form of crushed aggregate, chips, breaker product, granulars, granules, powder, or the like or their combinations. In one embodiment, the recycled material is in the form of crushed aggregate, chips, granules, powder, or their combinations. In one embodiment, the recycled material is in the form of crushed aggregate for the pyrolysis. In one embodiment, the recycled material is in the form of granules for the pyrolysis. In one embodiment, the recycled material is in the form of powder for the pyrolysis.
In one embodiment, the recycled material consists of solid material. In one embodiment, the recycled material contains rubber 0.1 - 10 % by weight and other solid material 99.9 - 90 % by weight, in one embodiment rubber 2 - 8 % and 98 - 92 % other solid material, in one embodiment rubber 4 - 6 % and 96 - 94 % other solid material, and in one embodiment rubber about 5 % and other solid material about 95 % . In one embodiment, in addition to the recycled material, an additional solid material, e.g. sand or another material, is fed to the fluidized bed reactor. In one embodiment, the recycled material and the additional solid material are fed to the fluidized bed reactor to form a feed, and the feed contains rubber 0.1 - 10 % by weight and other solid material 99.9 - 90 % by weight, in one embodiment rubber 2 - 8 % and 98 - 92 % other solid material, in one embodiment rubber 4 - 6 % and 96 - 94 % other solid material, and in one embodiment rubber about 5 % and other solid material about 95 % .
In this context, the fluidizing agent means any gaseous fluidizing agent which can be used for fluidizing the recycled material in the fluidized bed reactor. In one embodiment, the fluidizing agent can be formed and heated in a device in which the fluidizing agent is heated or heat is produced in connection with forming of the fluidizing agent, and the heated fluidizing agent is supplied to the lower part of the fluidized bed reactor. In one embodiment, the fluidizing agent is formed and heated by means of a heat source device. In one embodiment, the gaseous fluidizing agent is formed from starting material, e.g. gaseous substance, in the heat source device in which the starting material is burned to form the gaseous fluidizing agent. In one embodiment, the gaseous fluidizing agent is formed from methane, LNG (liquified natural gas) , flue gas, process gas or their combinations. In one embodiment, the gaseous fluidizing agent is formed from the methane, LNG, flue gas or process gas. In one embodiment, the gaseous fluidizing agent is formed from the methane, LNG, flue gas and/or process gas in the heat source device in which the methane, LNG, flue gas and/or process gas is burned to form the gaseous fluidizing agent. In one embodiment, the starting material comprises oxygen, and in one embodiment the starting material comprises an optimum amount of oxygen for burning, e.g. in the heat source device. In one embodiment, an oxygen content of the fluidizing agent is 3 - 5 % by volume. In one embodiment, the heat source device comprises at least a burner in which the gaseous fluidizing agent is formed and heated by burning. In one embodiment, the gaseous fluidizing agent is a hot gas. In one embodiment, the fluidizing agent is heated to a temperature which is 250 - 400 °C, in one embodiment 250 - 350 °C, and in one embodiment 270 - 320 °C. In one embodiment, the temperature of the heated fluidizing agent is less than 350 °C. In one embodiment, pressure of the fluidizing agent is arranged to pressure up to 0.5 bar (g) in the heating device, e.g. in the heat source device . In this context, the fluidized bed reactor can be any fluidized reactor comprising a fluidized bed in which a heat treatment and/or pyrolysis can be carried out and pyrolysis gas can be formed. In one embodiment, the fluidized bed reactor is a fast fluidized bed reactor. In one embodiment, the fluidized bed reactor is a circulating fluidized bed reactor, e.g. CFB-reactor. The fluidized bed reactor is a vertical reactor, and the fluidizing agent is used for fluidizing the recycled material in the reactor. In one embodiment, the fluidizing agent is used simultaneously for fluidization, pyrolysis and attrition, e.g. grinding, of the recycled material in the reactor.
In one embodiment, the apparatus comprises at least one feeder for feeding the recycled material via the recycled material inlet to the fluidized bed reactor to form a bed in the reactor. In this context, the feeder can be any feeder, feed equipment or other suitable feed device. In one embodiment, the feeder is selected from the group comprising pump, screw, tube, pipe, other suitable feeder and their combinations. In one embodiment, the feeder is a screw conveyor, dual-screw conveyor or their combinations. In one embodiment, the feeder comprises a lock hopper.
In one embodiment, the heated gaseous fluidizing agent is supplied to a lower part of the reactor and under the recycled material inlet. In one embodiment, the recycled material is fed above the fluidizing agent inlet in the reactor. In one embodiment, the fluidizing agent is supplied to the reactor, e.g. to a wind box, in which the fluidizing agent is distributed, for example through a grate, into a reaction vessel or chamber of the fluidized bed reactor. The recycled material is fluidized by means of the fluidizing agent such that the fluidizing agent flows through a bed of the recycled material and the recycled material is fluidized by fluiding agent flow. The fluidization improves a heat transfer from the fluidizing agent into particles of the recycled material. In one embodiment, particles of the recycled material form a dense fluidized bed which becomes less dense when at least a part of the particles, e.g. fine particles, are fluidized into an upper part of the reactor by the fluidizing agent. In the fluidized bed reactor, the fluidization, pyrolysis and attrition of the recycled material may be performed simultaneously.
In the pyrolysis, the recycled material is treated by heat such that bonds which are formed by the binding material, e.g. polymer or rubber polymer, and which bind carbon black are broken down during the pyrolysis. However, carbon black is not broken during the pyrolysis. In one embodiment, pyrolysis temperature is 250 - 350 °C, and in one embodiment 270 - 320 °C, and in one embodiment about 300 °C. In one embodiment, the pyrolysis is carried out under vacuum. In one embodiment, the pyrolysis is carried out under light vacuum, e.g. under vacuum between -100 mbar and -1 mbar or in one embodiment under vacuum of about -10 mbar. In one embodiment, the fluidizing gas has a velocity of 3 - 6 m/ s . The pyrolysis gas comprising carbon black is formed by the pyrolysis in the fluidized bed reactor.
In this context, the pyrolysis gas means any pyrolysis gas comprising gaseous component or components, i.e. gaseous pyrolysis product. In one embodiment, the gaseous pyrolysis product contains hydrogen and hydrocarbons, in one embodiment high amounts of hydrogen and hydrocarbons. Further, the gaseous pyrolysis product comprises at least fine particles. Further, the gaseous pyrolysis product may contain most of the sulphur of the recycled material. The pyrolysis gas may comprise several components. The pyrolysis gas comprises at least gaseous pyrolysis product and carbon black. The pyrolysis gas may comprise also coarse particles and/or solid material. In one embodiment, the gaseous pyrolysis product comprises burnable components, e.g. polymer based burnable components and/or hydrocarbon based burnable components.
In one embodiment, the pyrolysis gas together with particles is discharged from the fluidized bed reactor through an opening at the top side wall of the reactor and lead to the solids separator.
In this context, the solids separator means any separator, separating device, cyclone or similar device in which any solids, solid material, solid matter, dry substance, particles, or the like can be separated from the pyrolysis gas. In one embodiment, the solids separator is integrated with the fluidized bed reactor. In one embodiment, the solids separator is adjustable. In the solids separator, coarse particles and/or solid material is separated from the pyrolysis gas. In one embodiment, particles of the coarse particles and/or solid material with desired particle sizes are separated from the pyrolysis gas. In one embodiment, the coarse material or solid material is fractionated in connection with the separation. The coarse material and/or solid material may comprise any solid particles, over-size particles, metals, solid material with melting point which is higher than temperature in the pyrolysis, or their combinations. In one embodiment, the solid material comprises at least metal particles. In one embodiment, the solids separator is a cyclone. Any suitable cyclone, e.g. gas cyclone, cyclone separator, or their combination, can be used as the cyclone. The solids separator, e.g. cyclone, acts as a pre-separator .
In one embodiment, the coarse particles and/or solid material, e.g. over-size particles, is recirculated from the solids separator to the fluidized bed reactor. In one embodiment, the coarse particles and/or solid material is recirculated from the solids separator to a reactor chamber of the fluidized bed reactor, e.g. to a bottom part or lower part of the reactor chamber in the reactor. In one embodiment, at least the solid material, e.g. metals, is recirculated from the solids separator to the fluidized bed reactor. In one embodiment, the coarse particles and/or solid material is recirculated from the solids separator to the fluidized bed reactor and again with the pyrolysis gas from the fluidized bed reactor to the solids separator. In one embodiment, attrition, e.g. grinding, of the particles of the recycled material is performed during the fluidization and pyrolysis in the fluidized bed reactor. In one embodiment, the coarse particles, and/or also the solid material is recirculated in a combination of the fluidized bed reactor and solids separator so long that particles have a particle size which is sufficient small to move along with the pyrolysis gas out from the solids separator, i.e. over-size particles stay in the circulation. In one embodiment, the apparatus comprises at least one circulating device for recirculating the coarse particles and/or solid material from the solids separator to the fluidized bed reactor. In one embodiment, the apparatus comprises a loop seal after the solids separator, and the coarse particles and/or solid material are recirculated to the fluidized bed reactor through the loop seal. In one embodiment, the coarse particles and/or solid material can be taken out from the loop seal. In one embodiment, the loop seal prevents the gases leaving the reactor at the bottom or lower part of the reactor and entering into the solids separator. In one embodiment, the loop seal is integrated with the reactor, and the coarse particles and/or solid material may be taken out before the reactor, e.g. reactor chamber or vessel. In one embodiment, a desired part of the coarse particles and/or solid material is recovered as a solid product, e.g. a semifinished product, from the loop seal and/or after the solids separator. In one embodiment, the solid product may be used as a filler in a final product or as a binding material in pellets or in other purposes. In one embodiment, the solid product may be upgraded or reprocessed to form final products or new materials.
The pyrolysis gas comprising particles, e.g. fine particles such as carbon black particles, is supplied to the separation device, e.g. directly from the solids separator to the separation device or via cooling or heating to the separation device. In one embodiment, the pyrolysis gas leaves the solids separator via a central tube, e.g. a vortex finder. In one embodiment, the pyrolysis gas is cooled between the solids separator and the separation device. In one embodiment, the pyrolysis gas is heated between the solids separator and the separation device. In one embodiment, the apparatus comprises at least one cooling device and/or heating device after the solids separator and/or before the separation device for cooling and/or heating the pyrolysis gas. Any suitable cooling device may be used for cooling the pyrolysis gas. Any suitable heating device may be used for heating the pyrolysis gas.
In one embodiment, the pyrolysis gas is heated in a heating device before the separation device. In one embodiment, the apparatus comprises at least one heating device for heating the pyrolysis gas. In one embodiment, the heating device comprises a ball mill in which the pyrolysis gas is heated and particles of the pyrolysis gas are treated. In one embodiment, the apparatus comprises the heating device and at least one ball mill which are arranged sequentially and wherein the pyrolysis gas is heated in the heating device and particles of the pyrolysis gas are treated in at least one ball mill. In one embodiment, if the apparatus comprises more than one ball mill, the each ball mill may comprise different-sized balls.
In the separation device, the particles comprising carbon black particles are separated from the pyrolysis gas. Simultaneously a purified pyrolysis gas is formed. Any suitable separation device, e.g. filter, bag filter, multicyclone, classifier, their combination or the like, may be used as the separation device in the present method or apparatus for separating at least carbon black particles from the pyrolysis gas. In one embodiment, the filter is selected from the group consisting of a fabric filter, electrostatic filter, bag filter baghouse filter, and their combinations. In one embodiment, the filter is a fabric filter. In one embodiment, the filter is an electrostatic filter. In one embodiment, the filter is a bag filter. In one embodiment, the separation device is a multicyclone. In one embodiment, the apparatus comprises more than one separation devices which are arranged sequentially. In one embodiment, the pyrolysis gas may comprise also other particles than the carbon black particles, and different particles are separated in the sequential separation steps or devices such that the carbon black particles with high purity are separated in the last separation step or device. In one embodiment, a basic fraction is separated in the first separation step or device and a pure carbon black fraction, i.e. primary fraction, is separated in the last separation step or device, and optionally at least one another fraction is separated between the first and last separation steps or devices. For example, the basic fraction comprising carbon black and other particles may be used in tire material. For example, the pure carbon black fraction may be used as the carbon black product, e.g. printing ink.
The product comprising carbon black is recovered by separating from the pyrolysis gas in the separation device. The product comprises at least carbon black particles. In one embodiment, the product consists mainly of carbon black particles. In one embodiment, the product consists of carbon black particles. In one embodiment, the product is pelletized for facilitating transport, storage and use.
In the separation device, the purified pyrolysis gas, e.g. burnable gas, is formed, and is recovered. The pyrolysis gas can be utilized, e.g. in energy production and/or power production, or as a starting material for forming a final product. For example, the purified pyrolysis gas may be supplied to a power production unit. In one embodiment, polymers which bind the carbon black in the recycled material can be pyrolyzed into burnable gas, which is a good source of energy, and the burnable gas can be recovered, and the burnable gas may be supplied to a power production unit.
In one embodiment, the pyrolysis gas is treated under vacuum, for example under low vacuum, e.g. between -100 mbar and -1 mbar, and then all pyrolysis gas components operate in low vacuum after the pyrolysis. Thus, an in-built odor control can be achieved when all pyrolysis gas components operate in low vacuum.
In one embodiment, the pyrolysis gas is supplied to a power production unit, such as after the separation and/or after the separation of the product in the separation device, to form an energy. In one embodiment, the apparatus comprises a power production unit to which the pyrolysis gas is supplied, e.g. after the separation device .
In one embodiment, the power production unit comprises at least one energy production unit, and the pyrolysis gas, e.g. burnable gas, is supplied, e.g. directly from the separation device, to the energy production unit where the pyrolysis gas is burned to form flue gas and energy, and energy of the energy production unit is recovered, e . g . in the form of steam. In one embodiment , the power production unit comprises an energy production unit , and the energy production unit comprises at least one burner and/or steam boiler .
In one embodiment , the power production unit comprises at least one energy production unit and at least one power production device , and the energy, e . g . steam, is supplied from the energy production unit to the power production device for producing electricity and/or heat . In one embodiment , the power production unit comprises at least one energy production unit and at least one power production device , and the energy is supplied from the energy production unit comprising a burner and/or steam boiler to the power production device comprising a steam turbine, gas engine , gas turbine, generator, condenser or their combinations . In one embodiment, the power production unit comprises the energy production unit and the power production device for producing electricity and/or heat, and the power production device is selected from the group consisting of a steam turbine , gas engine , gas turbine, generator, condenser or their combinations . In one embodiment , the power production device comprises a steam turbine , gas engine , gas turbine and/or generator to form at least electricity . In one embodiment , the power production device comprises also a condenser in which heat is formed and/or in which the steam or a part of the steam may be condensed into water . In one embodiment , the condensed water is recirculated to the energy production unit , or the water may be removed from the process .
In one embodiment , the energy production unit and power production device are combined to form a single power production unit for producing electricity and/or heat from the pyrolysis gas .
In one embodiment, the sulphur used as a binding agent in the recycled material , e . g . in a vulcanization, is collected from the pyrolysis gas or from flue gas produced in the energy production process.
In one embodiment, flue gas of the power production unit, e.g. flue gas of the energy production unit, is treated by a gas cleaning and/or sulphur capture. In one embodiment, the apparatus comprises at least one gas cleaning device for gas cleaning and sulphur capture. In one embodiment, the apparatus comprises at least one scrubber for cleaning flue gas of the power production unit, e.g. flue gas of the energy production unit, and/or for sulphur capturing from the flue gas. In the gas cleaning device, e.g. the scrubber, sulphur can be removed from the flue gas. In one embodiment, at least one chemical is added to the gas cleaning device, e.g. the scrubber, for facilitating sulphur capture from the flue gas. The sulphur can be removed without added chemicals or with added chemicals, depending on the process and process conditions.
In one embodiment, the method and apparatus are based on a continuous process.
In one embodiment, the apparatus is a mobile apparatus, which can be transported to a desired place for treating the recycled material. In one embodiment, the apparatus is arranged into a container, and then a transport of the apparatus can be facilitated.
The product comprising carbon black is formed. Also a gas product comprising the pyrolysis gas is formed. In one embodiment, the present method and apparatus is based on a co-production of carbon black and energy. In one embodiment, the product comprising carbon black is porous and have high specific surface area.
In one embodiment, the method and the apparatus are used and/or utilized in a production of carbon black, in a treatment of waste rubber, tire waste and/or tire-derived rubber waste, in a treatment of asphalt felt waste, in a production of tires, in a production of fillers, plastic fillers, colorants, pigments, inks, printing inks, additives, paints, coatings, rubber goods, films or other substances, or their combinations. In one embodiment, the product comprising carbon black obtained by the method is used in tires, fillers, inks, printing inks, colorants, additive agents, pigments, rubber goods, paints, coatings, plastics, films, other substances, or their combinations.
Thanks to the method and apparatus the high- quality carbon black and the pyrolysis gas with high heating value can be produced. Further, significant amount of energy in form of electricity and heat can be generated by burning the burnable pyrolysis gas. Further, sulphur as a side product can be produced. Further, by means of the method and process, the apparatus has a simple construction, and there are no moving parts in the reactor. Further, the integrated grinding and separation of the carbon black particles can be achieved, desired particle size of the carbon black and classification of the carbon black into desired particle size distribution can be achieved, and several particle sizes can be produced in one process. Further, the particle size can be reduced by attrition in the fluidized bed. Further, thanks to the process high separation efficiency of the carbon black product and the pyrolysis gas can be achieved. Further, energy such as power and heat can be produced by combusting the pyrolysis gas which has high heating value. An efficiency of the process is excellent, and all fractions can be recovered and recycled, and energy can be utilized.
In the apparatus, a long residence time for the raw material can be achieved in a small reactor volume. Further, good heat transfer and mass transfer for the raw material can be achieved in a small reactor volume. Further, small footprint can be achieved when at least the fluidized bed reactor and the separation device are installed in vertical position.
The method and apparatus offer a possibility to form products with good properties easily, and energy- and cost-effectively. The present invention provides an industrially applicable, simple and affordable way to treat the recycled materials, and further simultaneously to produce desired products and energy. For example, different tire waste materials, tire-derived rubber waste, waste rubbers, asphalt felts and other hazardous wastes and their fractions can be treated easily and effectively in the process to form new products. Further, the process allows parallel production of different products. The method and apparatus are easy and simple to realize in connection with production processes. Further, the present apparatus can be used as a transportable process arrangement.
EXAMPLES
Fig. 1 presents the process and the apparatus for producing carbon black from recycled waste material, e.g. tire waste powder.
The apparatus of Fig. 1 comprises a fluidized bed reactor (1) , a cyclone (7) and a filter (12) , and optionally an energy production unit (15) , a power production device (18) and a gas cleaning device (22) .
The fluidized bed reactor (1) is a vertical circulating fluidized bed reactor in which the waste material (2) is treated. The waste material comprising at least rubber material and/or bituminous material is fed by a feeder via a waste material inlet to the fluidized bed reactor. The waste material forms a bed in the reactor. A heated gaseous fluidizing agent (5) is supplied via a fluidizing agent inlet to a lower part of the reactor (1) . The fluidizing agent may be formed by heating in a heating device (3) , e.g. in a heat source device, for example from LNG or flue gas (4) . In the reactor (1) , the fluidizing agent (5) is supplied into the bed of the waste material and through the bed such that the waste material is fluidized by the fluidizing agent and treated by a pyrolysis in the fluidized bed reactor. Then a pyrolysis gas (6) is formed. The pyrolysis gas (6) is discharged via a pyrolysis gas outlet from a top of the fluidized bed reactor. The pyrolysis gas is supplied to a cyclone (7) arranged after the fluidized bed reactor and integrated with the fluidized bed reactor in order to separate coarse particles and/or solid material (8) from the pyrolysis gas. The coarse particles and/or solid material are recirculated to the fluidized bed reactor (1) , preferably to a bottom part in a reactor chamber in which the pyrolysis is carried out. The coarse particles and/or solid material may be recirculated to a loop seal (9) and from the loop seal to the reactor (1) .
The pyrolysis gas (11) from the cyclone (7) is supplied to a filter (12) . The pyrolysis gas (11) may be cooled by means of a cooling device or heated by means of a heating device before the filter (12) . In the filter (12) , a product (14) comprising carbon black is formed by filtrating carbon black particles from the pyrolysis gas (11) . The carbon black product (14) comprising carbon black particles is recovered. After the filter a purified pyrolysis gas (13) , which is a combustible gas, is recovered.
In one embodiment, the pyrolysis gas (13) is supplied to a power production unit comprising at least the energy production unit (15) and optionally also the power production device (18) . The energy production unit (15) comprises a burner and/or a steam boiler for forming flue gas (16) and steam (17) . The steam may be supplied to the power production device (18) . The power production device comprises a steam turbine, or a steam turbine and a generator, or a gas engine, or a gas turbine, or a gas turbine and a generator in order to produce electricity (21) and/or heat (20) . The power production device may comprise also a condenser (19) for condensing the steam or a part of the steam into water (26) . The water may be recirculated to the energy production unit (15) . Alternatively, the energy production unit and power production device are combined to form a power production unit in which electricity and/or heat can be produced. The flue gas (16) from the energy production unit (15) may be supplied to a gas cleaning device (22) , e.g. a scubber, for gas cleaning and sulphur capture. In the gas cleaning device, sulphur (23) can be removed from the flue gas, and a purified flue gas (24) can be achieved. The sulphur can be removed without added chemicals or with added chemicals (25) , depending on the process and process conditions.
The apparatus of Fig. 1 may be a mobile apparatus. The apparatus may be arranged into a container, and then the apparatus is easy to transport.
Fig. 2 presents the process arrangement according to example 1.
Example 1
In this example, the process arrangement (Fig. 2) , i.e. the apparatus, is for pyrolysis of rubber tire waste aiming for co-production of carbon black and energy. The tire waste contains significant amounts (up to 50 %) carbon black, which can be recycled as a material component. The polymers, e.g. rubber, binding the carbon black can be pyrolyzed into burnable gas, which is a good source of energy. The sulphur used as a binding agent (vulcanization) may be collected from the gas or from the flue gas produced in the energy production process. The process arrangement comprises a heat source (3) , a fluidized bed reactor (1) , a cyclone separator (7) , a filter (12) , an energy production unit (15) , a power production device (18) and a gas cleaning device (22) .
The heat source (3) produces a hot fluidizing gas (5) , for example 350 °C with pressure up to 0.5 bar (g) , for the pyrolysis and fluidization of the tire waste powder (2) . The fluidizing gas can be formed from a suitable starting material (4) , e.g. from methane, LNG or flue gas. The hot fluidizing gas (5) is supplied to the fluidized bed reactor (1) . The fluidizing gas enters a wind box, from which it is distributed through a special grate into a reaction chamber of the fluidized bed reactor ( 1 ) .
The fluidized bed reactor (1) , which is a vertical reactor, uses the hot gas (5) for fluidization, pyrolysis and attrition (grinding of the material) . The tire waste (2) is fed above the fluidizing gas inlet in the reactor, and a bed of tire waste powder is formed in the reactor. The tire waste powder is fluidized by the fluidizing gas to flow through the bed of reactor. This fluidization helps to gain maximal heat transfer from the hot gas into the particles of the tire waste. The polymers binding the carbon particles are broken down by the heat in the reactor, and pyrolysis gas comprising carbon black is formed. The hot pyrolysis gas (6) leaves the vertical reactor together with solid particles through an opening at the top side wall of the reactor. The pyrolysis gas is supplied to a gas cyclone separator ( 7 ) .
The cyclone separator (7) which is integrated with the fluidized bed reactor (1) is adjustable. In the cyclone separator solid material (8) with desired particle sizes are separated from the pyrolysis gas. Further, the solid material may be fractionated of smaller particles. Then desired particle size and reduction of size in large particles can be achieved. Over-size particles (8) are returned to a bottom part of the reactor (1) . Alternatively, material can be taken also from a loop seal (9) after the cyclone. A "water lock" called loop seal prevents the gases from leaving the reactor into the cyclone. The pyrolysis gas (11) together with the finest particles leave the cyclone (7) via a central tube called vortex finder, and the pyrolysis gas (11) is supplied to the filter (12) . The pyrolysis gas may be cooled before the filter.
The filter (12) which is a fabric filter, alternatively an electrostatic filter, separates carbon black particles from the pyrolysis gas. A carbon black product (14) comprising carbon black particles is recovered, and the purified pyrolysis gas (13) , i.e. burnable gas, is supplied to an energy production unit (15) . The carbon black product (14) consisting of mainly carbon black particles can be pelletized or treated in other way for facilitating transport, storage and use.
The energy production unit (15) comprises a burner and a steam boiler for forming flue gas (16) and steam (17) . The steam is supplied to a power production device (18) . The power production device comprises a steam turbine, or a steam turbine and a generator, or a gas engine, or a gas turbine, or a gas turbine and a generator in order to produce electricity (21) and/or heat (20) . The power production device can comprise also a condenser (19) in which the steam or a part of the steam is condensed into water (26) . Alternatively, the energy production unit and power production device are combined to form a power production unit in which electricity and/or heat can be produced.
The flue gas (16) from the energy production unit is supplied to a scubber (22) for gas cleaning and sulphur capture. In the scubber (22) , sulphur (23) can be removed from the flue gas (24) . The sulphur can be removed without added chemicals or with added chemicals ( 25 ) , depending on the process and process conditions .
The benefits of the present process arrangement , for example over a drum pyrolyzer arrangement , are a simple construction , no moving parts in the reactor, integrated grinding and separation of the carbon black particles , possibility to produce several particle si zes in one process because the particle material can be taken also from a loop seal after the cyclone , desired particle si ze distribution due to the adj ustable cyclone separator, high efficiency separation of the carbon black product , the pyrolysis gas with a high heating value , in-built odor control where all pyrolysis gas components operate in low vacuum, and small footprint as at least the fluidi zed bed reactor and the filter are installed in vertical position .
Example 2
In this example the tire waste material is treated according to example 1 .
Table 1 shows an example chemical composition of pyrolysis gas formed from tire waste .
Table 1
Figure imgf000024_0001
The process arrangement is capable of handling 16 000 ton/a tire waste and then it may be able to produce more than 5000 ton/a carbon black, more than 20 GWh electricity and 40 GWh heat. The estimated HHV (Higher Heating Value) of such a pyrolysis gas is over 30 MJ/kg.
Example 3
In this example the tire waste material was treated in laboratory scale tests.
In order to test the hypothesis that the tire rubber can be pyrolyzed without getting a liquid phase, tests with two different types of ovens were made. A small laboratory oven was used for accurate temperature and exposure time tests, while a simpler kitchen-oven type allowed a larger batch but less accurate control. Several test runs with both ovens were conducted.
The first test was run with the laboratory oven so that the pulverized sample was set on a mesh inside a crucible at 275 °C for two (2) hours. In the first tests, it was observed that there is no liquid at the bottom of the crucible. Testing results are shown in Fig. 3.
Tests were continued with the bigger oven with 300 °C temperature and same pyrolysis time (2 hours) in larger scale tests. It was observed that the tire rubber can be treated easily by means of heat at temperature of 300 °C.
Further, tests with 50 mm particles (crushed aggregate) were carried out. l m3 bag of larger, 50 mm rubber tire particles were collected from Hyvinkaa and pyrolyzed with the laboratory oven. The behavior was very different from the powder, as the particles stayed in the original dimensions, but the structure became very hard, almost like a ceramic. A longer residence time was needed to achieve this, and still some of the larger particles maintained rubbery structure . However, this is one possibility to reduce the need of energy for particle si ze reduction, for example according to following processes :
- an initial chopping to 50 mm, pyrolysis with a long residence time and collection of pyrolysis gas , optionally mechanical breaking with for instance with a hammer mill , and separation of metals and carbon black, or
- slow pyrolysis of entire tire and collection of pyrolysis gas , optionally mechanical breaking, and separation of metals and carbon black, or
- pyrolysis of tire material and collection of pyrolysis gas , separation in solids separator, treatment in a heated ball mill , and recovery of carbon black .
Testing results with larger tire particles are shown in Fig . 4 in which left side comprises large particle and right side comprises hard ceramic-like structure which is mostly carbon black .
In the tests , it was observed that the pyrolysis without a liquid phase works .
Further, it was observed that the tire rubber can be pyrolyzed easily into pyrolysis gas .
The fluidi zed bed reactors , heat source devices , solids separators and separation devices , and energy and power production devices and gas cleaning devices , and other devices used in these examples are known per se , and therefore they are not described in any more detail in this context .
The method and apparatus are suitable in different embodiments for producing products , e . g . carbon black products and combustible gases , from different kinds of recycled materials . Further, the method and apparatus are suitable in different embodiments for treating different recycled materials comprising rubber material and/or bituminous material, e.g. different haz- ardous materials.
The invention is not limited merely to the ex- amples referred to above; instead many variations are possible within the scope of the inventive idea defined by the claims.

Claims

1. A method for producing at least one product from recycled material, c h a r a c t e r i z e d in that the method comprises steps
- feeding the recycled material (2) comprising at least rubber material and/or bituminous material to a fluidized bed reactor (1) which is a vertical reactor, and forming and heating a gaseous fluidizing agent, and supplying the heated gaseous fluidizing agent (5) to a lower part of the reactor,
- fluidizing the recycled material by the fluidizing agent and treating the recycled material by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas (6) , which is a gaseous pyrolysis product,
- discharging the pyrolysis gas (6) from a top of the fluidized bed reactor,
- separating coarse particles and/or solid material (8) from the pyrolysis gas (6) in a solids separator (7) arranged after the fluidized bed reactor, and
- supplying the pyrolysis gas to a separation device (12) and forming a product (14) comprising carbon black by separating carbon black particles from the pyrolysis gas in the separation device.
2. The method according to claim 1, c h a r a c t e r i z e d in that the pyrolysis gas is supplied to a power production unit (15,18) , and the power production unit comprises at least one energy production unit (15) , and the pyrolysis gas (13) is supplied to the energy production unit where the pyrolysis gas is burned, and energy of the energy production unit is recovered.
3. The method according to claim 2, c h a r a c t e r i z e d in that the power production unit comprises at least one energy production unit (15) and at least one power production device (18) , and energy (17) is supplied from the energy production unit comprising a burner and/or steam boiler to the power production device comprising a steam turbine, gas engine, gas turbine, generator, condenser or their combinations for producing electricity (21) and/or heat (20) .
4. The method according to any one of claims 1 to 3, c h a r a c t e r i z e d in that pyrolysis temperature is 270 - 320 °C.
5. The method according to any one of claims 1 to 4, c h a r a c t e r i z e d in that the gaseous fluidizing agent (5) is heated to temperature of 250 - 400 °C.
6. The method according to any one of claims 1 to 5, c h a r a c t e r i z e d in that the gaseous fluidizing agent is formed from methane, LNG, flue gas, process gas or their combinations (4) in a heat source device (3) in which the methane, LNG, flue gas and/or process gas is burned to form the gaseous fluidizing agent (5) .
7. The method according to any one of claims 1 to 6, c h a r a c t e r i z e d in that the recycled material (2) is selected from the group consisting of waste rubber, tire waste, tire-derived rubber waste, polymer waste, plastic waste, asphalt felt and their combinations .
8. The method according to any one of claims 1 to 7, c h a r a c t e r i z e d in that the recycled material (2) is in the form of crushed aggregate, chips, granules, powder or their combinations.
9. The method according to any one of claims 1 to 8, c h a r a c t e r i z e d in that the coarse particles and/or solid material (8) is recirculated from the solids separator (7) to the fluidized bed reactor (1) .
10. The method according to any one of claims 1 to 9, c h a r a c t e r i z e d in that the pyrolysis gas is supplied to a power production unit (15,18) , and flue gas (16) of the power production unit (15,18) is treated by a gas cleaning and/or sulphur capture.
11. An apparatus for producing at least one product from recycled material, c h a r a c t e r i z e d in that the apparatus comprises
- at least one fluidized bed reactor (1) which is a vertical reactor and in which the recycled material (2) is treated,
- at least one recycled material inlet for feeding the recycled material (2) comprising at least rubber material and/or bituminous material to the fluidized bed reactor (1) and at least one fluidizing agent inlet for supplying a heated gaseous fluidizing agent (5) to a lower part of the fluidized bed reactor (1) such that the recycled material is fluidized by the fluidizing agent and treated by a pyrolysis in the fluidized bed reactor to form a pyrolysis gas (6) , which is a gaseous pyrolysis product,
- at least one pyrolysis gas outlet for discharging the pyrolysis gas (6) from a top of the fluidized bed reactor ( 1 ) ,
- at least one solids separator (7) arranged after the fluidized bed reactor for separating coarse particles and/or solid material (8) from the pyrolysis gas (6) , and
- at least one separation device (12) for forming a product (14) comprising carbon black by separating carbon black particles from the pyrolysis gas.
12. The apparatus according to claim 11, c h a r a c t e r i z e d in that the apparatus comprises a power production unit (15,18) to which the pyrolysis gas is supplied, and the power production unit comprises at least one energy production unit (15) , which comprises at least one burner and/or steam boiler.
13. The apparatus according to claim 12, c h a r a c t e r i z e d in that the power production unit comprises at least one energy production unit (15) and at least one power production device (18) for producing electricity and/or heat, and the power production device is selected from the group consisting of a steam turbine, gas engine, gas turbine, generator, condenser or their combinations .
14. The apparatus according to any one of claims 11 to 13, c h a r a c t e r i z e d in that the apparatus comprises a heat source device (3) which comprises at least a burner and in which the gaseous fluidizing agent (5) is formed by burning.
15. The apparatus according to any one of claims 11 to 14, c h a r a c t e r i z e d in that the apparatus comprises at least one circulating device for recirculating the coarse particles and/or solid material (8) from the solids separator (7) to the fluidized bed reactor ( 1 ) .
16. The apparatus according to any one of claims 11 to 15, c h a r a c t e r i z e d in that the apparatus comprises a power production unit (15,18) to which the pyrolysis gas is supplied and at least one scrubber (22) for cleaning flue gas (16) of the power production unit and/or for sulphur capturing from the flue gas (16) .
17. The apparatus according to any one of claims 11 to 16, c h a r a c t e r i z e d in that the apparatus is a mobile apparatus.
18. A use of the method according to any one of claims 1 to 10, c h a r a c t e r i z e d in that the method is used in a production of carbon black, in a treatment of waste rubber, tire waste or tire-derived rubber waste, in a treatment of asphalt felt waste, in a production of tires, in a production of fillers, plastic fillers, colorants, pigments, inks, printing inks, additives, paints, coatings, rubber goods, films or other substances, or their combinations.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0768345A2 (en) * 1995-10-09 1997-04-16 Mitsubishi Jukogyo Kabushiki Kaisha Method for producing carbon black from a waste tire and apparatus therefor
CN1228367C (en) * 2002-12-04 2005-11-23 安顺企业股份有限公司 Spouted bed low-temp. pyrolysis method of waste rubber and its equipment
EP2147963A2 (en) * 2007-04-12 2010-01-27 Energy & Environment Consulting, S. L. Method for treating tyres and pyrolysis reactor for carrying out said method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0768345A2 (en) * 1995-10-09 1997-04-16 Mitsubishi Jukogyo Kabushiki Kaisha Method for producing carbon black from a waste tire and apparatus therefor
CN1228367C (en) * 2002-12-04 2005-11-23 安顺企业股份有限公司 Spouted bed low-temp. pyrolysis method of waste rubber and its equipment
EP2147963A2 (en) * 2007-04-12 2010-01-27 Energy & Environment Consulting, S. L. Method for treating tyres and pyrolysis reactor for carrying out said method

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