WO2024023586A1 - Procédé de récupération de méthane à partir de gaz de traitement chaud lors de la réaction de matériaux post-consommation contenant du carbone - Google Patents

Procédé de récupération de méthane à partir de gaz de traitement chaud lors de la réaction de matériaux post-consommation contenant du carbone Download PDF

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WO2024023586A1
WO2024023586A1 PCT/IB2023/050664 IB2023050664W WO2024023586A1 WO 2024023586 A1 WO2024023586 A1 WO 2024023586A1 IB 2023050664 W IB2023050664 W IB 2023050664W WO 2024023586 A1 WO2024023586 A1 WO 2024023586A1
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Prior art keywords
gas
synthesis gas
filter
pipe
carbon
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PCT/IB2023/050664
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German (de)
English (en)
Inventor
Alfred Edlinger
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Radmat Ag
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Priority claimed from ATA217/2022A external-priority patent/AT525654B1/de
Application filed by Radmat Ag filed Critical Radmat Ag
Publication of WO2024023586A1 publication Critical patent/WO2024023586A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/50—Fuel charging devices
    • C10J3/506—Fuel charging devices for entrained flow gasifiers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0405—Apparatus
    • C07C1/041—Reactors
    • C07C1/0415—Reactors with moving catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive 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
    • C10B49/04—Destructive 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
    • C10B49/08—Destructive 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
    • C10B49/10—Destructive 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/026—Dust removal by centrifugal forces
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/90—Devices for taking out of action one or more units of multi-unit filters, e.g. for regeneration or maintenance
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/095—Exhaust gas from an external process for purification
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1253—Heating the gasifier by injecting hot gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/723—Controlling or regulating the gasification process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/04—Gasification
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/08—Drying or removing water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/547—Filtration for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the present invention relates to a method for obtaining methane from hot process gas by converting carbon-containing waste materials, in particular wood chips, biomass, waste fractions, waste plastics, waste solvents, shredder light fraction, waste wood, old tires and the like, as well a device for utilizing process gas by converting waste materials and forming synthesis gas, in particular for carrying out the method according to the invention.
  • a method of the type mentioned at the beginning comprises at least the following steps:
  • soot means in this context Invention that, compared to the waste materials, the process gas is only added in an amount at which no free oxygen and no CO2 are present in the resulting synthesis gas during the pyrolysis and partial gasification of the waste materials. In other words, the process gas is added substoichiometrically with respect to the conversion to synthesis gas.
  • the formation of soot preferably takes place to such an extent that the carbon f of the carbon-containing waste materials is produced as soot to an extent between at least 30% and 70%, preferably between 40% and 60% and particularly preferably between 45% and 55%.
  • the soot formation to be aimed at in the context of the present invention is adjusted in terms of control technology due to the composition of the carbon-containing waste materials used in the process according to the invention, which is not always exactly known, and due to the equally changing composition of the process gas used.
  • the target variable here is the desired ratio of CO to H2 in order to subsequently carry out methanation according to the formula
  • soot is formed.
  • carbon falls out of the gas phase as a solid and is thereby relatively depleted, so that the hydrogen content in the synthesis gas increases compared to the gaseous carbon content.
  • the exergy of process gases from various sources can be used to recycle and dispose of problematic waste materials.
  • the result is a process in which valuable heat from exhaust gases is used, waste materials are disposed of and valuable fuel gas is formed in the form of methane suitable for use in gas pipeline networks.
  • synthesis gas can be used for methanation, the additional electrolytic production of hydrogen can be dispensed with, which results in enormous savings in electrical energy compared to the conventional synthesis of methane.
  • hydrogen from the hydrolysis of water using renewable energy sources can still be added to the synthesis gas.
  • conventional methanation starts from synthesis gas of H2 and CO2 and/or CO, with CO2 and/or CO being present in excess.
  • the method according to the invention can also be used to produce a gas mixture of CH4 and H2.
  • homologues of CH4 such as ethane or propane as well as ethylene and acetylene can also be produced.
  • ethane or propane as well as ethylene and acetylene as well as other higher-chain hydrocarbons
  • O2 it is also conceivable to use O2 to adjust the process parameters. This leads to the formation of CO at the expense of the soot content, so that higher-chain hydrocarbons such as ethane, ethyne, ethane or precursors for methanol synthesis or precursors for Fischer-Tropsch synthesis also become accessible.
  • the formation of methane can preferably also take place under an increased pressure of preferably 2 bar to 5 bar.
  • the parameters of the pyrolysis are selected according to the invention so that the hot process gas is used for pyrolysis at temperatures of 1800 ° C to 2400 ° C, preferably 1900 ° C to 2300 ° C, more preferably 2000 ° C to 2200 ° C and particularly preferably 2100 ° C of the carbon-containing waste materials is used and the superstoichiometric addition of the carbon-containing waste materials is carried out to such an extent that the synthesis gas is obtained during pyrolysis and, if necessary, partial gasification at temperatures of 450 ° C to 800 ° C. In this way, at temperatures of the hot process gas of 1800°C to 2400°C, the old materials are reliably pyrolyzed and partially gasified, as well as those that are harmful to the environment
  • the carbon in the synthesis gas is present as CO.
  • the synthesis gas enriched with hydrogen due to the soot formation is optionally cooled.
  • the synthesis gas is preferably subjected to a drying step to remove water vapor in order to avoid the undesirable reverse reaction
  • CaO + H 2 O -> Ca (OH) 2 is removed from the synthesis gas, whereby the slaked lime formed (Ca (OH) 2 ) also chemically neutralizes and binds any sulfur species (H 2 S, COS, SO 2 ) present in the synthesis gas. This also applies to halogens and halides that may be contained in the synthesis gas.
  • the catalytic methanation of the synthesis gas takes place in a fluidized bed of nickel-containing steelworks dust, preferably at temperatures of 300 ° C to 500 ° C, more preferably at a temperature of 400 ° C.
  • the catalysis of the Sabatier reaction to form methane from CO and H 2 is carried out as standard with nickel catalysts; the use of nickel-containing steelworks dust, especially from stainless steel production, is considered particularly advantageous because these dusts have an enormous surface area, which ensures optimal catalysis is achieved.
  • the soot formed must be captured to meet various legal requirements.
  • the preferred procedure is such that the soot formed during pyrolysis is in a filter, e.g. B. Deep bed filter, with a filter column made of graphite, coke, and / or steel bodies, in particular balls, is separated.
  • the filter becomes increasingly loaded with soot, so that the filter must be regenerated at some point.
  • the soot in the filter is converted into water gas containing CO2 and H2 by preferably inductive heating of the filter column with the addition of water vapor. This frees the filter from the solid soot and thus makes it ready for further separation of soot (carbon black).
  • a particularly advantageous process results in a preferred embodiment of the present invention when, after a water-gas shift reaction, CO2 is separated from H2 by alkaline scrubbing and separated H2 is added to the synthesis gas for methanation.
  • CO2 is separated from H2 by alkaline scrubbing and separated H2 is added to the synthesis gas for methanation.
  • valuable hydrogen is formed, which in turn can be used to increase the relative hydrogen content of the synthesis gas for catalytic methanation.
  • the process according to the invention is preferred for the elimination of solid components from the stream of synthesis gas formed during pyrolysis and optionally partial gasification or from the methane formed further developed in such a way that solid components are separated off by means of a gas cyclone and/or bag filter connected to the fluidized bed and are preferably returned to the fluidized bed.
  • the carbon-containing waste materials are added to separate halogens, alkalis and/or alkaline earths.
  • Halogens such as bromides
  • Sulfur compounds such as H2S or COS are completely bound by the zinc content of the steelworks dust preferably used for catalysis.
  • the device according to the invention for utilizing process gas by converting waste materials and forming synthesis gas and for carrying out the method according to the invention comprises at least: a riser pipe formed along an axial direction and arranged vertically, a supply line for the process gas opening into the riser pipe and a feed pipe connected to the riser pipe subsequent exhaust gas treatment system for the synthesis gas and a feeding device for the waste materials with at least one projecting into the riser pipe over a defined length Delivery pipe, wherein the at least one delivery pipe has an open end opening into the riser pipe and the supply line opens into the riser pipe in the axial direction below the open end, so that process gas entering the riser pipe from the supply line can flow around the at least one delivery pipe, and is according to the invention, characterized in that the exhaust gas treatment system has at least one filter for separating soot from the synthesis gas, the at least one filter being connected to a supply line for water vapor and being heatable.
  • the device according to the invention allows waste materials to be converted or recycled, in particular wood chips, biomass, waste fractions, old tires, old solvents, food leftovers, used oils, used plastics, shredder light fraction, waste wood, old tires and the like, to be flowed around with hot process gas to heat, whereby pyrolysis and, depending on the intensity of the heating, partial decomposition of the used materials into synthesis gas takes place in the at least one delivery pipe.
  • the defined length of the at least one delivery pipe is between 40 cm and 200 cm, depending on the specific design described below.
  • waste materials in the delivery pipe gases are formed from the waste materials in the delivery pipe, which cause the waste materials introduced by the feeding device to be loosened and thrown explosively out of the delivery pipe and into the riser pipe.
  • the waste materials comminuted in this way end up in fine particles with a piece size of less than 1.5 mm effective diameter and with a relatively large surface area in the gas stream of the process gas in the riser pipe, which flows around the at least one delivery pipe from below at high speed and flows further up the riser pipe and the crushed waste materials.
  • the waste materials are pyrolyzed and, if necessary, partially gasified.
  • hydrogen and carbon monoxide water gas, also known as synthesis gas
  • waste gas process gas
  • waste materials which means that waste materials can be disposed of profitably and at the same time the waste heat from a wide range of combustion processes can be used.
  • the used substances are added in an amount that leads to the formation of soot, so that complete conversion to synthesis gas does not occur.
  • the process gas is therefore added substoichiometrically in relation to the conversion to synthesis gas.
  • soot is formed from the excess carbon added, which leads to a relative enrichment of hydrogen compared to carbon in the synthesis gas.
  • the exhaust gas treatment system has at least one filter for separating soot from the synthesis gas, wherein the at least one filter is connected to a supply line for water vapor and can be heated. This makes it possible to separate soot from the synthesis gas stream.
  • the filter can be regenerated by converting the soot into water gas containing CO2 and H2 using a water gas shift reaction.
  • the hydrogen f obtained in a simple manner can, as already mentioned in connection with the process according to the invention, in turn be used to positively influence the C:H ratio in the synthesis gas for the methanation of hydrogen f.
  • a suitable and advantageous configuration of the filter with regard to the regeneration of the filter results when the at least one filter is formed by a filter column made of graphite, coke, steel bodies, in particular spheres, and / or steel fleece and an induction device is arranged surrounding the filter column is, as corresponds to a preferred embodiment of the present invention.
  • the components of the filter column mentioned can be coupled to an induction field in a known effective manner and the filter column can thereby be heated relatively evenly right down to its interior in order to convert the soot, together with the added water vapor, into CO and H2.
  • CO2 and H2 are formed with an increased hydrogen content, since CO2 and H2 are formed from CO and H2O through rearrangement.
  • the invention is further developed according to a preferred embodiment in such a way that at least two filters are arranged parallel to one another and can be flowed through alternately with synthesis gas. This makes it possible to always leave one filter in filter mode and to remove soot from the other filter by preferably inductively heating the filter column and adding water vapor, thereby releasing CO2 and H2.
  • the CO2 can be washed out of the stream of CO2 and H2 by means of an alkaline wash in order to obtain hydrogen that is as pure as possible, with which the C/H ratio of the synthesis gas can be further shifted towards hydrogen fs moved can be used to promote the Sabatier reaction to form methane.
  • At least two exhaust pipes open out at the axially upper end of the riser pipe, each of which is connected to a filter and which can be individually shut off by at least one shut-off device, with preferably two exhaust pipes opening out which can be shut off alternately by a common shut-off device.
  • a separate exhaust pipe is provided from the riser pipe for each filter.
  • Such an exhaust pipe can be shut off with a shut-off device corresponding to the diameter of such an exhaust pipe, thereby avoiding small valves and thus blockages of the valves with soot.
  • the shut-off device can be designed as a flap, which only has to be moved back and forth between the outlets of the exhaust pipes in order to shut off one exhaust pipe at a time to divert the flow of synthesis gas to the other exhaust pipe.
  • the present invention is preferably further developed in such a way that a reactor is connected in a gas-tight manner to the at least one filter, in which the synthesis gas is mixed with nickel-containing steelworks dust Fluidized bed forms, preferably at temperatures of 300 ° C to 500 ° C, more preferably at a temperature of 400 ° C.
  • the catalysis of the Sabatier reaction to form methane from CO and H2 is carried out as standard with nickel catalysts.
  • the use of nickel-containing steelworks dust, especially from stainless steel production, is particularly advantageous because these dusts have an enormous surface area, which results in optimal catalysis becomes .
  • the present invention is further developed according to a preferred embodiment of the present invention in such a way that the reactor is at least partially penetrated axially by a rotor with a plurality of radially directed rods and the synthesis gas can be introduced through the rods.
  • the reactor has cooling fins between the rods of the rotor that project radially inwards through a wall of the reactor, through which a cooling medium can flow, preferably water, thermal oil, ionic liquids and/or tin melt, in order to remove excess heat from the exothermic Sabatier reaction to be able to derive from the reactor.
  • a cooling medium preferably water, thermal oil, ionic liquids and/or tin melt
  • the reactor has an exhaust for methane formed in the fluidized bed, with the exhaust preferably opening into a cyclone separator for separating off dust.
  • the invention can also be developed in such a way that the device has a plurality of reactors in series in order to maintain the reaction equilibrium To shift the direction of the methane yield and the undesirable reverse reaction
  • CaO + H 2 O -> Ca (OH) 2 is removed from the synthesis gas, whereby the slaked lime formed (Ca (OH) 2 ) also chemically neutralizes and binds any sulfur species (H 2 S, COS, SO 2 ) present in the synthesis gas. This also applies to halogens and halides that may be contained in the synthesis gas.
  • the feeding device is preferably formed by a plurality of delivery pipes projecting radially or tangentially into the riser pipe, the delivery pipes preferably being directed obliquely upwards with respect to the axial direction.
  • a plurality of conveying pipes are provided as the feeding device, so that for a certain throughput of waste materials, there are smaller amounts of waste materials in each individual conveying pipe of the feeding device.
  • the preferred orientation of the delivery pipes obliquely upwards results in an advantageous introduction of the pyrolyzed and partially gasified waste materials into the riser pipe in relation to the flow direction of the process gas in the riser pipe, by promoting the occurrence of turbulence in the riser pipe, which results in intense heat - and material exchange occurs in the riser pipe.
  • the defined length of the delivery pipes in this preferred embodiment is between 40 cm and 120 cm.
  • the feeding device is formed by a delivery pipe which projects into the riser pipe in the axial direction, in particular concentrically, at a lower end of the riser pipe.
  • This embodiment is to be regarded as advantageous in terms of the space-saving design without delivery pipes opening into the riser pipe from the side and in terms of the flow-efficient introduction of the pyrolysed waste materials into the riser pipe.
  • the defined length over which the delivery pipe projects into the riser pipe can be longer than with the above-described radial or tangential configuration of the delivery pipes, so that in turn a very effective heat transfer to the waste materials in the delivery pipe takes place.
  • the defined length of the delivery pipes in this preferred embodiment is between 40 cm and 200 cm.
  • the conveyor pipe points with its open end directly in the direction of the axis of the riser pipe, so that the pyrolyzed waste materials ejected from the conveyor pipe are thrown into the flow direction of the gas stream of the process gas for partial gasification.
  • the conveyance of the waste materials through the at least one conveyor pipe is accomplished in terms of apparatus in that the at least one conveyor pipe has a conveyor device at an end facing away from the open end, preferably in the form of one in the conveyor pipe arranged screw conveyor, a piston slide and/or a thick flow pump.
  • the type of conveyor device can be selected depending on the type of starting materials, and it can preferably also be provided that the conveyor device is removably fixed at the end facing away from the open end, whereby the conveyor device is removed when the waste materials to be recycled change and can be exchanged.
  • the at least one conveyor pipe has a conveyor device at an end facing away from the open end in the form of a screw conveyor arranged in the conveyor pipe, the screw conveyor having a central shaft which is hollow and hollow for introducing inert gas into the conveyor screw process gas, hydrogen and/or methane can flow through.
  • Methane which behaves inertly in the environment prevailing in the riser pipe, as well as other gases that are beneficial and/or inert in this environment and in relation to the Sabatier reaction to be promoted, such as H2, CO and N2, are well suited to promoting the old materials.
  • the introduction of hydrogen f in turn increases the proportion of hydrogen f in the synthesis gas formed, as is the object of the present invention.
  • the waste materials can be pyrolyzed by introducing hot process gas into the screw conveyor, which significantly reduces the conveying work required to operate the screw. Further This preferred embodiment enables the
  • the screw conveyor is burned out at certain intervals by blowing in hot process gas and without conveying old materials, which means that caking that has developed over time can be removed.
  • the method according to the invention is assessed below using the model substance polyethylene as an existing substance.
  • Bio-natural gas is burned as a process gas according to the following reaction equation:
  • FIG. 1 shows a sectional view of an axially lower region of a device according to the invention for carrying out the method according to the invention
  • FIG. 2 shows a sectional view of a device according to the invention with a shut-off element
  • FIG. 3 shows a filter arrangement in the sense of the present invention
  • the device according to the invention is designated by reference number 1.
  • the device 1 comprises a riser pipe 3 which is formed along an axial direction or flow direction 2 and is arranged vertically. The axial extension is also symbolized by the longitudinal axis designated by reference symbol 4.
  • the riser pipe 3 is lined on the inside with a refractory material, preferably made of graphite, Magcarbon (for example Magcarbon R 94A1 Horn & Co. Group) and/or SiC. 5 denotes a supply line for the process gas that opens into the riser pipe 3.
  • the waste materials are fed into the delivery pipe 9 via a feeding device 7.
  • a feeding device 7 In the embodiment shown in FIG.
  • the feeding device 7 is formed by a screw conveyor 6 accommodated in the conveying pipe, to which the waste materials intended for the production of the synthesis gas are fed laterally from the feeding device 7.
  • the screw conveyor 6 rotates around a hollow shaft 8, via which process gas, hydrogen, water vapor and/or methane can be introduced into the screw conveyor 6.
  • the process gas which is injected via the supply line 5, flows around the delivery pipe 9 along the route L.
  • the length L can be between 40 cm and 200 cm depending on the requirements for the pyrolysis of the waste materials.
  • E/R in Figure 1 stands for the supply of educt/reactant.
  • M/H2/PG stands for the supply of methane and hydrogen and/or process gas.
  • the designation "PG 1800/2400” stands for the supply of process gas at temperatures of 1800 ° C to 2400 ° C.
  • FIG. 3 now shows two mutually parallel filters 15a and 15b, which can be alternately supplied with synthesis gas containing soot via the exhaust line 16 and the three-way valve 17 or also via the exhaust lines 10 and 11 from FIG.
  • the filters 15a and 15b are filtered and regenerated in such a way that, in a first phase, synthesis gas containing soot flows through the filter 15b to separate soot is, for which the induction device 18b is switched off.
  • the soot accumulates in the filter 15b, which is preferably formed essentially from a filter column 19b made of graphite, coke, steel balls and/or steel fleece in a housing 20b.
  • a filter column 19b made of graphite, coke, steel balls and/or steel fleece
  • soot-cleaned synthesis gas containing carbon monoxide and enriched hydrogen is obtained, which is used for the Sabatier reaction to form methane.
  • the water vapor valve 22 is closed.
  • the filter 15a is separated from the synthesis gas stream by closing the exhaust gas valve 23.
  • the induction device 18a is activated to heat the filter column 19a, whereby carbon monoxide and hydrogen are obtained by the simultaneous addition of water vapor through the water vapor valve 24.
  • the filter 15b When the regeneration of the filter 15a is completed and the filter 15b is saturated with soot, the filter 15b is regenerated in the same way with water vapor through the water vapor valve 22 and the action of the induction device 18b and the filter 15a is used for filtering.
  • the reactor for carrying out the Sabatier reaction is provided with the reference number 26 in FIG.
  • the reactor 26 is connected in a gas-tight manner to the two filters 15a and 15b and contains a fluidized bed 27 made of synthesis gas with nickel-containing steelworks dust at temperatures of 300 ° C to 500 ° C.
  • methane is formed in an exothermic reaction according to one of the reaction equations listed above.
  • the synthesis gas is introduced via the perforated rods 28, optionally with adjustable gas nozzles, of the rotor 33. To cool the reactor
  • the reactor 26 also has cooling fins 29, which Wall 30 of the reactor 26 passes through and a cooling medium such as water, thermal oil, ionic liquids and / or tin melt flows through it.
  • a cooling medium such as water, thermal oil, ionic liquids and / or tin melt flows through it.
  • paddles knock down 31 nickel dust particles. Methane and water vapor are drawn off at the outlet 32 of the reactor 26.
  • Nickel-containing catalyst dust collects at an axially lower end 34 of the reactor 26 and can be recycled from there into the fluidized bed 27. If the catalyst dust is inactivated, for example by sulfur loading, it is removed and replaced or supplemented with fresh or regenerated dust.
  • the designation “SG” in Figure 4 stands for the supply of synthesis gas.

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Abstract

La présente invention concerne un procédé de récupération de méthane à partir de gaz de traitement chaud lors de la réaction de matériaux post-consommation contenant du carbone, en particulier des copeaux de bois, une biomasse, des fractions de déchets, des plastiques post-consommation, des solvants post-consommation, une fraction légère de déchiqueteuse, du bois post-consommation, des pneus post-consommation et similaire, le procédé comprenant au moins les étapes suivantes : pyrolyse et facultativement gazéification partielle des matériaux post-consommation contenant du carbone au moyen d'un gaz de traitement chaud pour former un gaz de synthèse contenant CO et H2, les matériaux post-consommation contenant du carbone étant ajoutés en une quantité qui conduit à la formation de noir de carbone ; méthanation catalytique du gaz de synthèse pour former du méthane.
PCT/IB2023/050664 2022-07-26 2023-01-26 Procédé de récupération de méthane à partir de gaz de traitement chaud lors de la réaction de matériaux post-consommation contenant du carbone WO2024023586A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ATA60112/2022 2022-07-26
AT601122022 2022-07-26
ATA217/2022A AT525654B1 (de) 2022-07-26 2022-11-17 Verfahren zur Gewinnung von Methan aus heißem Prozessgas unter Umsetzung von kohlenstoffhaltigen Altstoffen
ATA217/2022 2022-11-17

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WO2024023586A1 true WO2024023586A1 (fr) 2024-02-01

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100887137B1 (ko) * 2008-06-12 2009-03-04 김현영 탄화물 열분해 개질 방법 및 그 장치
CN108201762A (zh) * 2018-02-28 2018-06-26 中国华能集团清洁能源技术研究院有限公司 一种生物质燃气的焦油过滤器及反吹洗装置
AT524123B1 (de) * 2021-01-19 2022-03-15 Radmat Ag Vorrichtung zum Verwerten von Prozessgas unter Umsetzung von Altstoffen und Bildung von Synthesegas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100887137B1 (ko) * 2008-06-12 2009-03-04 김현영 탄화물 열분해 개질 방법 및 그 장치
CN108201762A (zh) * 2018-02-28 2018-06-26 中国华能集团清洁能源技术研究院有限公司 一种生物质燃气的焦油过滤器及反吹洗装置
AT524123B1 (de) * 2021-01-19 2022-03-15 Radmat Ag Vorrichtung zum Verwerten von Prozessgas unter Umsetzung von Altstoffen und Bildung von Synthesegas

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