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WO2025201610A1 - Production améliorée de gaz de synthèse à production améliorée d'hydrogène intégrée - Google Patents

Production améliorée de gaz de synthèse à production améliorée d'hydrogène intégrée

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Publication number
WO2025201610A1
WO2025201610A1 PCT/DK2025/000031 DK2025000031W WO2025201610A1 WO 2025201610 A1 WO2025201610 A1 WO 2025201610A1 DK 2025000031 W DK2025000031 W DK 2025000031W WO 2025201610 A1 WO2025201610 A1 WO 2025201610A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction zone
output stream
stream
gas
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/DK2025/000031
Other languages
English (en)
Inventor
Jan Kamyno RASMUSSEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sempercycle Aps
Original Assignee
Sempercycle Aps
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Filing date
Publication date
Application filed by Sempercycle Aps filed Critical Sempercycle Aps
Publication of WO2025201610A1 publication Critical patent/WO2025201610A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—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
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • 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
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • 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
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • 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
    • C10K3/001—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 thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/005—Reducing the tar content by partial oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1684—Integration of gasification processes with another plant or parts within the plant with electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam

Definitions

  • waste materials e.g. waste plastics
  • end of life materials is a substantial environmental challenge in society.
  • the end of life for such uses causes significant pollution and other environmental damage.
  • Even when collected properly the plastics still cause issues due to a plethora of different compositions of the plastics.
  • the easiest way of getting rid of the plastics and other waste materials is chosen as the solution, this solution being incineration.
  • the waste do have a certain heating value, however better end of life uses of the material are available.
  • Gasification of waste, e.g. plastics is a generally well-known process. In such process a gas may be produced that has several practical and beneficial uses, that goes beyond the beforementioned incineration and heating.
  • Waste and in particular plastics are however a more complex compositions as several different variants are known and used for various purposes.
  • this is achieved through a method for producing syngas from carbonaceous feedstock comprising two or more different compositions of carbonaceous material (e.g., plastics, textiles, biomass, organic matter, natural gas, biogas, carbon dioxide, waste gases), the method comprising: a. Gasification of the waste feedstock by feeding the feedstock into a primary reaction zone, hereby generating a first output stream; b. Feeding the first output stream from the first reactor into a secondary reaction zone hereby generating a second output stream; c. Feeding the second output stream into a cleaning and conditioning reaction zone, hereby generating a third output stream d.
  • carbonaceous material e.g., plastics, textiles, biomass, organic matter, natural gas, biogas, carbon dioxide, waste gases
  • SOEC solid oxide electrolysis system
  • Providing a heat exchanger system comprising one or more heat exchangers, to provide a steam input to the SOEC system, where the hot side of the heat exchanger system is receiving a hot output stream from the gasification process and/or from the methanol synthesis process and where the cold side of the heat exchanger system is receiving a water or steam input to generate the steam input to the SOEC system k.
  • Operating the SOEC system primarily on sustainable energy input to generate hydrogen and oxygen.
  • the steam to the SOEC system is delivered at a temperature in the range 500 to 900 degrees C, preferably in the range 600 to 800 degree C.
  • the SOEC system is receiving a power input from a renewable source.
  • an oxygen output stream from the SOEC system is at least partly utilized in the gasification process.
  • the carbon is kept longer in the system to arrive at the highest yield of desired products when operating with a varying feedstock composition, i.e., reducing the amount of carbon otherwise lost from the process due to inconsistent operating conditions.
  • the otherwise lost thermal energy is utilized to create a more efficient electrolysis process and hence contributes to an increased overall process efficiency.
  • the steam to the SOEC system is delivered at a temperature in the range 500 to 900 degrees C, preferably in the range 600 to 800 degree C.
  • the SOEC system is receiving a power input from a renewable source.
  • FIG. 1A a heat exchanger system is shown receiving heat from the gasification process through the hot syngas stream and water or steam from an external source, where steam is generated and/or superheated in the heat exchanger and led to the SOEC electrolysis unit.
  • the cooled syngas stream is led back to the second output stream.
  • the SOEC electrolysis unit generates hydrogen and oxygen with high efficiency and through the use of heat energy recovered from the gasification unit the overall efficiency of the system is further enhanced.
  • the hydrogen and oxygen produced from the electrolysis can be used in the process (the oxygen in the gasification process and the hydrogen in the conditioning process prior to the methanol synthesis) or may be exported.
  • FIG. 2 shows the gasification system having:
  • FIG. 3 shows the gas treatment system with:
  • FIG. 4 shows the methanol synthesis system comprising:
  • FIG. 5 shows the methanol distillation system comprising:
  • Reboiler 510 Reflux air cooler
  • the waste plastic is delivered by road to a reception hall and mechanical pretreatment.
  • the reception hall any material deemed unacceptable after a visual inspection is removed. Typically, this could include oversize material, car batteries or the like.
  • MPT mechanical pre-treatment
  • the feedstock is shredded and sorted to make it suitable for the gasifier and its feeding system. Sorting could for example include ferrous and non-ferrous metal rejection systems.
  • the pre-treated feedstock is then delivered to a buffer store ready for feeding to the gasifier.
  • the buffer store is designed to allow separate storage of different qualities of feedstock, so that a stable mixture can be fed to the gasifier.
  • Oxygen and hydrogen are supplied from an electrolysis plant, preferably supplied with electricity from renewable sources.
  • the oxygen and hydrogen requirements of the plant are nearly in balance. On the basis of the material balance attached to this report, there will be surplus of the total oxygen supplied.
  • Hydrogen need not be produced on site and could be provided through a pipeline from a remote electrolysis facility or transported in batches and stored locally.
  • the gasifier system is an oxygen-fired stationary fluid bed first stage gasifier followed by an entrained flow secondary gasifier to remove tars.
  • An essentially nitrogen-free syngas is required, so oxygen-firing has been selected.
  • a dual fluid bed system would achieve this also but has the disadvantage of emitting CO2 from the combustor bed.
  • the high temperature secondary gasifier has the advantage of reducing the methane content of the syngas and is able to make use of the oxygen infrastructure of the oxygen-fired primary gasifier.
  • the primary gasifier is a stationary fluid bed operating at a temperature of 750°C.
  • the plastics are gasified in the bed, but it must be assumed that some material will vaporize without full conversion to H2 and CO leaving some tars in the gas exiting the gasifier.
  • Solids are drawn off at the bottom of the reactor together with some of the bed material. Bed material and solids can be at least partially separated, and the recovered bed material recycled to the reactor. Fine solids, which may include a small amount of unconverted carbon, will be carried out of the reactor at the top of the freeboard. This will be captured in a cyclone and recycled to the bed.
  • the scrubber also removes any ammonia and HCN formed in the gasifier.
  • the gas at this point has a hydrogenxarbon monoxide ratio of slightly over 1 and a CO2 content of about 12%.
  • hydrogen must be added to achieve an optimum value of just over 2 for the stoichiometric ratio (H2-CO2)/(CO+CO2). Hydrogen from the electrolysis unit co-produced with the oxygen is taken to accomplish this.
  • Fresh syngas is compressed and fed to a desulphurization vessel and/or guard bed or other absorption unit to absorb the H2S, COS and other non-desired components in the gas.
  • the steam pressure of about 40 bar maintains the desired gas outlet temperature of 250 °C.
  • the unconverted gas together with the methanol leaves the reactor and is cooled successively in the Feed-Effluent-Exchanger, an air-cooler and a final water cooler, thus condensing the methanol.
  • the crude methanol is separated out in a separator and fed to the distillation section.
  • Inert gases mainly methane and nitrogen
  • the purge gas also contains some H2 and CO.
  • the Distillation Unit is shown in FIG. 5.
  • the crude methanol contains a small amount of low- boiling co-formed products such as DME as well as some physically dissolved gases.
  • the dissolved gases are flashed off in a Flash Vessel and low boiling impurities (light ends) removed in a Light Ends Column.
  • the stabilized methanol is then distilled in the Atmospheric Column to obtain a specification product.
  • the process water produced as the distillation bottoms stream contains various co-produced impurities such as ethanol.
  • Fuel gas is produced in the form of the methanol synthesis purge and the light ends removed in the distillation unit. Approximately 80 wt% of this is recycled to the gasifier, which allows for the contained carbon still to be converted to methanol. The remaining 20 wt% is combusted in a furnace used to superheat the saturated steam generated in the process. This also allows for the removal of inert gases such as nitrogen from the system. This 80:20 split between recycle and combustion is to some extent arbitrary. This ratio causes a 4-times increase in the nitrogen flowing around the system, but the small amount entering the system means that this is still acceptable. The amount of gas combusted provides suitable superheat ( ⁇ 320°C) to ensure that the turbine exhaust is still dry.
  • An intermediate raw methanol tank will also be required to maintain a stable flow to the distillation unit in the event of fluctuations in the upstream plant including the energy supply to the electrolysis unit.
  • Ash will be discharged from the gasifier. This is expected to contain up to about 5% carbon.
  • the allowable carbon-in ash for disposal or onward sale needs to be checked on a project basis.
  • the main contaminant is ethanol, but other hydrocarbons (e. g. ketones) are also present.
  • Controlling the process under stationary conditions and with essentially one feedstock type will correspond to the well-known state of the art technology. However in order to accommodate a higher degree of feedstock flexibility and at the same time a high yield and efficiency of the process, independent of the desired end product, and according to the invention, a recycling of certain gas streams and corresponding adaptation of the process conditions is applied. Reference is made to FIG. 6 indication the measurements and input streams forming part of the most important control loops as explained in the following.
  • a heat exchanger system is shown receiving heat from the gasification process and water from an external source, where steam is generated from the heat exchanger and led to the SOEC electrolysis unit.
  • the SOEC electrolysis unit generates hydrogen and oxygen with high efficiency and through the use of heat energy recovered from the gasification unit the overall efficiency of the system is further enhanced.
  • the hydrogen and oxygen produced from the electrolysis can be used in the process (the oxygen in the gasification process and the hydrogen in the conditioning process prior to the methanol synthesis) or may be exported.
  • the aim is to design a system which can provide a very high conversion of carbon-containing feedstock of fluctuating and unknown composition to desired product (e.g. methanol).
  • desired product e.g. methanol
  • the system is preferably run on renewable (fluctuating) electricity providing energy for water electrolysis.
  • a connection to a hydrogen-pipeline could be considered, this allowing for a remote location of an electrolysis facility.
  • the produced hydrogen and oxygen will be stored as a buffer to avoid too much ramping up and down (complete shut-downs due to lack of green electricity should be avoided) it might be beneficial to add a certain degree of modulation in the design.
  • the plastic waste feedstock enters the side of the reactor slightly above the top of the fluidized region. As the density of the feedstock is higher than of the gas in the reactor it will drift down and enter the fluidized bed. Light particles with a large surface will have a very short residence time in the fluidized bed before they are converted to gas and the opposite goes for heavy particles with small surface.
  • reactor 1 The intention of reactor 1 is to perform partial oxidation, steam reforming and cracking reactions with the purpose of bringing all feedstock to a gas phase which will leave the reactor and be converted further in reactor 2.
  • the aim is not to perform a full conversion to syngas in the first reactor.
  • the gas at the exit of reactor 1 is expected to contain primarily CO, H 2 , CO 2 and some amounts of CH 4 , C 2 + (incl tar), HCI, H 2 S and NH 3 as well as other species
  • the temperatures will be measured in the bed and above the bed.
  • the gas analyzers will measure CO, CO 2 and H 2 in the outlet.
  • a non-catalytic reactor has been chosen but in principle a catalytic reactor (catalytic tar reformer) could be used.
  • the catalytic reactor could be fully or partially heated by electromagnetic induction. This would have the advantage of a lower temperature, e.g. 900- 1000 °C, but the disadvantage would be higher CAPEX and the risk of catalyst deactivation and additional maintenance.
  • steam could be added as and oxidizing agent in combination with the oxygen, but as the reaction is endothermic this would require even more oxygen or electrical energy to keep the desired temperature. Steam would have the advantage of producing more H2 than oxygen and thus increasing the H2:CO ratio.
  • oxygen should be sufficient to raise the temperature to the desired level (e.g. 1200 °C) and provide enough oxygen for conversion of carbon containing species to CO.
  • a lack of oxygen could result in uncomplete tar conversion.
  • too much oxygen would convert some of the CO to CO2, which is a "waste" of energy and CO for the methanol synthesis. In reality some CO has to be "sacrificed" in the process.
  • the reactor will be controlled by monitoring temperatures and gas composition, the controlled input will be the oxygen flow and optionally recycle flow.
  • the temperatures will be measured in the inlet, outlet and possibly somewhere in-between.
  • the gas analyzers will measure CO, CO 2 and H 2 in the inlet, outlet and possibly somewhere inbetween.
  • the control system will be relatively complicated and might be constructed as a number of feedback/feedforward control loops (e.g. PID controllers) or ideally a model predictive control (MPC) system based on a mathematical model of the system.
  • PID controllers e.g. PID controllers
  • MPC model predictive control
  • Control loop 1 Maintain desired fluidization flow of reactor 1
  • Constraint The fluidization flow, u2 + u3 + u4, must be within a defined interval (minimum fluidization velocity to minimum blow-out velocity).
  • Control loop 2 Maintain desired temperature of reactor 1
  • the reactor temperature, Tl must be in an interval around 750 °C (e.g. 740-760 °C).
  • Control loop 3 Maintain desired gas composition from reactor 1
  • the CO/CO2 ratio indicates whether the level of oxidant should be adjusted, it should be in a certain interval.
  • Control loop 4 Maintain desired temperature of reactor 2 Constraint:

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Abstract

L'invention concerne un procédé de production de gaz de synthèse à partir d'une charge d'alimentation carbonée comprenant au moins deux compositions différentes de matière carbonée (par exemple, des matières plastiques, des textiles, de la biomasse, de la matière organique, du gaz naturel, du biogaz, du dioxyde de carbone, des gaz résiduaires), le procédé consistant à : gazéifier la charge d'alimentation de déchets par introduction de la charge d'alimentation dans une zone de réaction primaire, générant ainsi un premier flux de sortie ; introduire le premier flux de sortie du premier réacteur dans une zone de réaction secondaire, générant ainsi un deuxième flux de sortie ; introduire le deuxième flux de sortie dans une zone de réaction de nettoyage et de conditionnement, générant ainsi un troisième flux de sortie ; introduire le troisième flux de sortie provenant de la zone de réaction de nettoyage et de conditionnement dans une zone de réaction de synthèse de produit, générant ainsi un quatrième flux de sortie ; séparer le quatrième flux de sortie de la réaction de produit en un cinquième flux de produit brut liquide qui est envoyé pour un traitement ultérieur (par exemple, une distillation) et au moins un sixième et un septième flux de gaz ; au moins une partie du sixième flux de gaz est recyclée vers la zone de réaction de synthèse de produit ; au moins une partie du septième flux de gaz est renvoyée en boucle vers la zone de réaction primaire pour une conversion supplémentaire ; des paramètres de gazéification pour les première et seconde zones de réaction sont commandés pour prendre en compte la composition et la quantité des flux de gaz recyclés ; et la fourniture d'un système d'électrolyse à oxyde solide (SOEC) pour créer une entrée d'hydrogène et d'oxygène dans le processus ; la fourniture d'un système d'échangeur de chaleur pour fournir une entrée de vapeur au système SOEC, le côté chaud du système d'échangeur de chaleur recevant un flux de sortie chaud provenant de la seconde zone de réaction ou du processus de synthèse de méthanol et le côté froid du système d'échangeur de chaleur recevant une entrée d'eau pour générer l'entrée de vapeur dans le système SOEC.
PCT/DK2025/000031 2024-03-25 2025-02-26 Production améliorée de gaz de synthèse à production améliorée d'hydrogène intégrée Pending WO2025201610A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
EP3027715B1 (fr) * 2013-08-01 2017-09-06 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Procede de conversion thermochimique d'une charge carbonee en gaz de synthese contenant majoritairement h2 et co
EP3433341B1 (fr) * 2017-01-17 2021-03-17 NextChem S.p.A. Procédé et appareil pour la fabrication de bio-methanol pur à partir de syngas issu de la gaséification de déchet
US20220112429A1 (en) * 2020-10-14 2022-04-14 Velocys Technologies Ltd Gasification process
DK202270355A1 (en) * 2022-07-01 2024-02-16 Sempercycle Aps Syngas production from waste materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
EP3027715B1 (fr) * 2013-08-01 2017-09-06 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Procede de conversion thermochimique d'une charge carbonee en gaz de synthese contenant majoritairement h2 et co
EP3433341B1 (fr) * 2017-01-17 2021-03-17 NextChem S.p.A. Procédé et appareil pour la fabrication de bio-methanol pur à partir de syngas issu de la gaséification de déchet
US20220112429A1 (en) * 2020-10-14 2022-04-14 Velocys Technologies Ltd Gasification process
DK202270355A1 (en) * 2022-07-01 2024-02-16 Sempercycle Aps Syngas production from waste materials

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