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WO2024002442A1 - Production de gaz de synthèse à partir de déchets - Google Patents

Production de gaz de synthèse à partir de déchets Download PDF

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Publication number
WO2024002442A1
WO2024002442A1 PCT/DK2023/000177 DK2023000177W WO2024002442A1 WO 2024002442 A1 WO2024002442 A1 WO 2024002442A1 DK 2023000177 W DK2023000177 W DK 2023000177W WO 2024002442 A1 WO2024002442 A1 WO 2024002442A1
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Prior art keywords
reaction zone
flow
gas
reactor
decrease
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English (en)
Inventor
Jan Kamyno RASMUSSEN
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Sempercycle Aps
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Sempercycle Aps
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Priority to EP23742196.1A priority Critical patent/EP4547795A1/fr
Publication of WO2024002442A1 publication Critical patent/WO2024002442A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • 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
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • 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
    • C01B2203/0455—Purification by non-catalytic desulfurisation
    • 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
    • C01B2203/06—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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0855—Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—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
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • C10J2300/1823—Recycle loops, e.g. gas, solids, heating medium, water for synthesis gas

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 does have a certain beating 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 a number of practical and beneficial uses, that goes beyond the beforementioned incineration and heating.
  • Waste and in particular plastics is however a more complex composition as a number of different variants are known and used for various purposes.
  • the carbon is kept longer in the system in order 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.
  • Advantageously adjusting the gasification parameters for the primary reaction zone (a) includes increasing/decreasing the flow velocity of the second stream in order to provide secondary fuel for the exothermic reaction (to maintain the desired temperature) and/or to maintain the desired total flow velocity in the reaction zone.
  • adjusting the gasification parameters of the secondary reaction zone includes increasing/decreasing the flow velocity of the third stream in order to provide secondary fuel for the exothermic reaction (to maintain the desired temperature) and/or to maintain the desired total flow velocity in the reaction zone.
  • the method includes that the produced syngas is subject to two or more cleaning and conditioning steps, one of them being an addition of externally supplied hydrogen to ensure a COrHa ratio of around 1:2, another one being a compression to e.g. 50-100 bar;
  • a method for producing chemicals e.g., methanol, Fischer-Tropsch derived compounds, ethylene, propylene
  • the produced syngas is subject to two or more cleaning and conditioning steps,
  • the conditioned syngas is subject to a conversion in a subsequent reaction zone/reactor to the desired product (e.g., methanol, Fischer-Tropsch derived compounds, ethylene, propylene).
  • the cleaning and conditioning steps may be incorporated independently of the additional steps mentioned above, preferably between the secondary reaction zone and the product synthesis reaction zone, i.e., second stream providing input to the cleaning and conditioning and the third stream being the output stream providing the input to the product reaction synthesis zone.
  • the method includes that one or more of the following parameters are monitored forming a basis for the adjustment of the gasification parameters: Tl, Temperature of reaction zone 1, T2, Temperature of reaction zone 2, yl, CO content at outlet of reaction zone 1 (molar/volume flow), y2, COz content at outlet of reaction zone 1 (molar/volume flow), y3, CO content at outlet of reaction zone 2 (molar/volume flow), y4, COz content at outlet of reaction zone 2 (molar/volume flow), y5, Hz content at outlet of reaction zone 2 (molar/volume flow), y6, Nz+Ar content in recycle gas (molar/volume flow).
  • the method further includes that one or more of the following input streams are monitored and controlled in order to optimize the gasification parameters: ul, Plastic waste feedstock flow, u2, Oxygen flow to reaction zone 1, u3, Steam flow to reaction zone 1, u4, Recycle gas flow to reaction zone 1, uS, Oxygen flow to reaction zone 2, u6, Recycle gas flow to reaction zone 2, u7, Hydrogen gas flow to product reaction zone/reactor, u8, Recycle gas flow to flare/exhaust.
  • one or more of the following input streams are monitored and controlled in order to optimize the gasification parameters: ul, Plastic waste feedstock flow, u2, Oxygen flow to reaction zone 1, u3, Steam flow to reaction zone 1, u4, Recycle gas flow to reaction zone 1, uS, Oxygen flow to reaction zone 2, u6, Recycle gas flow to reaction zone 2, u7, Hydrogen gas flow to product reaction zone/reactor, u8, Recycle gas flow to flare/exhaust.
  • the fluidization flow in reaction zone 1, u2 + u3 + u4 is kept within a predefined interval (minimum fluidization velocity to minimum blow-out velocity), and where, If the fluidization flow drops below the minimum threshold: increase u4, or if the fluidization flow goes above the maximum threshold: decrease u4.
  • reaction temperature in reaction zohe 1, Tl is kept within a range of 500 to 1000 °C, preferably 600 to 900 °C, most preferred between 700 and 800 °C and where If T1 drops below a lower predetermined value: decrease ul, increase u2, decrease u3, increase u4, or if T1 goes above an upper predetermined value: increase ul, decrease u2, increase u3, decrease u4.
  • the CO/CO2 ratio (yl/y2) is maintained in a predetermined interval and If yl/y2 drops below the threshold (too much oxidant): increase ul, decrease u2, decrease u3, increase u4, or if 'tlhl goes above the threshold (too less oxidant): decrease ul, increase u2, increase u3, decrease u4.
  • reaction temperature of reaction zone 2 is maintained in a predetermined range of 800 to 1600 °C , preferably in the range 900 to 1500 °C and most preferred in the range 1000 to 1400 °C and where if T2 drops below a predetermined lower value : increase u5, increase u6, or if T2 goes above a predetermined upper value : decrease u5, decrease u6.
  • the CO/CO2 ratio (y3/y4) from reaction zone 2 indicates whether the level of oxidant should be adjusted, it should be within a certain predetermined interval and if y3/y4 drops below the threshold (too much oxidant): decrease u5, increase u6, or if y3/y4 drops below the threshold (too less oxidant): increase u5, decrease u6.
  • the level of inert gases, y6 (e.g., nitrogen and argon), is maintained at a low level by controlling the purge gas to flare/exhaust, u8, and if y6 drops below the threshold: decrease u8, or if y6 goes above the threshold: increase u8.
  • y6 e.g., nitrogen and argon
  • FIG. 1 shows a system for production of methanol according to the invention
  • FIG. 2 shows in more detail a part of a system for production of methanol according to foe invention
  • FIG. 3 shows in more detail a part of a system for production of methanol according to the invention
  • FIG. 4 shows in more detail a part of a system for production of methanol according to the invention
  • FIG. 5 shows in more detail a part of a system for production of methanol according to foe invention
  • FIG. 6 shows a system for production of methanol according to the invention
  • Feedstock may as mentioned be of a variety of different types. Despite this fact the following description focus on plastics as the main feedstock.
  • the desired end product may be methanol as described in the following, the syngas produced may be used for a number of purposes. The following description therefore is only to be regarded an example of implementation of the invention.
  • the feedstock composition in terms of the contained components is based on data from a major waste supply company in Denmark.
  • the analysis of each component has been considered to develop an overall analysis of the mixed feed as shown in Table 0-1. This analysis may be used to develop the design case mass and energy balance.
  • Alternative compositions, in particular of significantly larger amounts of PVC, PET, Organics, Inorganics and Moisture may be a reality that will need to be accommodated In a specific design.
  • the heating value has been calculated from published values as shown in Table 0-2.
  • Table 0-2 Heating value of Feedstock Ash quality data are provided in Table 0-3. This is an indicative analysis of likely ash. It is not used in the simulation. Its importance is only in the expectation of an ash fusion temperature of the order of magnitude of 1100-1200X.
  • the deflection temperature is a measure of a polymer's ability to bear a given load at elevated temperatures. While this temperature is in principle arbitrarily defined, it gives an indication of the potential for a plastic to soften and under the force of a feeding system risk blockages at higher temperatures.
  • FIG. 1 a schematic diagram shows the main elements of a system for performing the method according to the invention.
  • the system comprises a waste plastics reception system and a waste plastics storage, a gasification system, a gas treatment system, a methanol synthesis system, a methanol distillation system and a electrolysis system.
  • Raw gas separator 304 Syngas compressor, first stage
  • FIG. 5 shows the methanol distillation system comprising:
  • 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, there will be surplus of the total oxygen supplied.
  • Hydrogen need not be produced oh site and could be provided through a pipeline from a remote electrolysis facility or transported in batches and stored locally.
  • Hie 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. In principle a dual fluid bed system would achieve this also but has the disadvantage of emitting COi 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 whole syngas train upstream the compressor must be under positive pressure to prevent accidental air ingress.
  • the feeding system must allow for this and lock hoppers with a screw feeder are proposed for this duty. Note that the screw feeder may well need cooling, particularly at the front end (closer to the gasifier) to avoid softening of the plastic and potential blocking of the feeder.
  • the secondary gasifier is an entrained flow reactor operating in a similar manner to a partial oxidation (POX) reactor at a temperature of around 1200'C, which is assumed high enough to ensure conversion of all the higher hydrocarbons still contained in the primary gasifier effluent.
  • POX partial oxidation
  • Hie gas leaving the Boiler Feedwater Preheater still contains any chlorine originating from PVC in the feedstock. In the formal mass balance this is calculated to present as 0.21 mol% HCI. Below the water dewpoint of about 70*C HC1 corrosion can be expected. But apart from this, there is also the potential for ammonium chloride formation from the ammonia formed during gasification. This must be removed at a higher temperature, typically in the range 170-190’C by washing with water, which also removes the hydrochloric add from the gas. The gas is therefore scrubbed with cold water to remove chlorine compounds and it leaves the scrubber at about 70 e C. This ensures that the gas is either dry (before entering the scrubber) or the chlorine compounds are sufficiently diluted in the scrubber Water that corrosion risks are avoided. The gas leaving the scrubber is water saturated but chlorine-free.
  • the scrubber also removes any ammonia and HCN formed in the gasifier.
  • the gas at this point has a hydrogen:carbon monoxide ratio of slightly over 1 and a COi content of about 12%.
  • hydrogen must be added to achieve an optimum value of just over 2 for the stoichiometric ratio (Hz-COjj/fCO+COa). 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 HaS, COS and other rion-desired components in the gas.
  • the cleaned and conditioned gas is fed to the suction side of the loop gas circulator, which recycles unconverted syngas from the methanol reactor on the same shaft as the syngas compressor.
  • the gas is preheated in the Feed-Effluent-Exchanger and fed to a tubular reactor in which the carbon oxides and hydrogen are converted to methanol.
  • the tubes are filled with catalyst, which is cooled by the boiling water on the outside of the tubes.
  • the steam pressure of about 40 bar maintains the desired gas outlet temperature of 250 e 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 Hz 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.
  • the distillation can take place in a three-column system to reduce the reboiler steam demand.
  • the quality of the methanol is not influenced by such change.
  • 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 (* v 320 e 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.
  • 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.
  • 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.
  • Atypical industrial methanol plant would have a stable flow of well-defined feedstock and the need for recycle loops would not be needed.
  • syngas is defined as a gas consisting primarily of CO, H 2 , CO 2 in various amounts.
  • the gas flow entering the reactor should be in a certain interval to *llft* the bed material and ensure fluidization (minimum fluidization velocity) and avoid "blow-out* of the bed material.
  • the fluidized bed has good mass and energy transfer properties and can be compared to a well-mixed liquid.
  • the bed material is typically quartz sand or olivine and might have limited catalytic effects on syngas formation.
  • the plastic waste feedstock enters the side of the reactor slightly above the top of the fluidized region. As toe density of the feedstock is higher than of toe 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.
  • the gas entering the reactor is composed of 3 separate gas flows;
  • the recycle gas will contain unconverted CO, CO 2 and H 2 from the methanol reactor as well as species entering the methanol reactor which it cannot convert, e,g., CH 4 and byproducts from the methanol reaction (e.g., ethanol and DME).
  • the recycle gas can have varying compositions but will have a high energy content and can act as a secondary feedstock for the primary reactor.
  • 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 toe 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 (incl tar), HCi, H 2 S and NH 3 as well as other species.
  • the key reactions performed in reactor 1 are as follows:
  • a fraction of the bed material is continuously taken out in the bottom of the reactor and filtered or replaced by new bed material.
  • Inorganic matter such as metal parts, fillers, sand and gravel
  • the reactor can be considered autothermic as it balances exothermic reactions (e.g. partial oxidation) with endothermic reactions (e.g. steam reforming) to keep a desired temperature (e.g. 750 °C) in the fluidized bed.
  • exothermic reactions e.g. partial oxidation
  • endothermic reactions e.g. steam reforming
  • a desired temperature e.g. 750 °C
  • the reactor is highly insulated and mainly exchanges energy with the material flows (gas in, gas out, feed In).
  • the temperature of 750 °C has been chosen as a compromise between conversion rate and material specifications.
  • the reactor is not lined which means that the metal must be suited to withstand the temperature. A higher temperature will give a better conversion to syngas but will restrain the selection of possible metal alloys. A lower temperature will give lower conversion to syngas, higher formation of tars (e g. RAM's) and carbon formation (coking) due to the Bouduard reaction which shifts CO to C and COz at lower temperatures.
  • the reactor will be controlled by monitoring temperatures and gas composition, the controlled input will be waste plastic feed flow, oxygen flow, steam flow and recycle gas flow.
  • 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-cataiytic 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.
  • 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 COz, 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 z in the inlet, outlet and possibly somewhere in* between.
  • One or more unit operations are used to clean and condition the syngas. Most likely a scrubber (possibly alkaline) will be used to remove HCI, NHj, other N-containing compounds, and most other impurities. A subsequent de-sulphurization unit and possibly guard-bed might be added to remove sulphur and other potential catalyst poisons, it is very important that catalyst poisons like Cl, Br, F and S are brought down to very low levels, e.g. ppb according to the catalyst manufacturers specifications. Otherwise the methanol catalyst will quickly deactivate.
  • a scrubber possibly alkaline
  • a subsequent de-sulphurization unit and possibly guard-bed might be added to remove sulphur and other potential catalyst poisons, it is very important that catalyst poisons like Cl, Br, F and S are brought down to very low levels, e.g. ppb according to the catalyst manufacturers specifications. Otherwise the methanol catalyst will quickly deactivate.
  • the compressed syngas enters the methanol reactor, which contains methanol catalyst and is controlled to a temperature of around 225 °C by cooling water.
  • the unconverted syngas is looped back the reactor for another pass. This happens a number of times and the recycle flow in the methanol loop is much larger than syngas inflow.
  • a methanol separator separates gas and liquid (oxide methanol).
  • a Fischer-Tropsch reaction could be used or in the future a direct syngas- to-olefins reaction might become commercialized.
  • the loop is essentially the same.
  • the methanol separator mentioned above separates die unconverted syngas, incl. species which have entered the reactor which cannot be converted (e.g. CH4 and Ci+) and byproducts from the methanol reaction (e.g. ethanol and DME).
  • the methanol separator is in principle just a drum where equilibrium between the gas and liquid phase is established.
  • the crude methanol contains a significant amount of water (e.g. 30%) and is distilled in subsequent distillation process.
  • the recycle to reactor 1 has the purpose of:
  • the recycle to reactor 2 has the purpose of:
  • the energy should be recovered and used for steam generation or steam superheating.
  • the total recycle gas flow from the methanol separation unit will be equal to: u4 + u6 + u8 + recycle flow to the methanol reactor
  • 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. Monitored outputs:
  • PID controllers e.g. PID controllers
  • MPC model predictive control
  • Control loop 1 Maintain desired fluidization flow of reactor 1
  • 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, T1 must be In an interval around 750 °C (e.g. 740-760 °C).
  • Control loop 4 Maintain desired temperature of reactor 2
  • the reactor temperature, T2 must be In an interval around 1200 °C (e.g. 1150-1250).
  • Control loop 5 Maintain desired gas composition from reactor 2
  • the CO/COz ratio (y3/y4) indicates whether the level of oxidant should be adjusted, it should be in a certain interval.
  • Control loop 6 Maintain desired gas composition for methanol reactor
  • the (H2-COj)/(CO+COz) ratio (module) should be kept around 2.1, e.g. 2.O-2.2.
  • the measurements made at the outlet of reactor 2 can be used to calculate the required addition of Hz as the gas composition should not change during the deaning process.
  • the added hydrogen, u7 can be calculated from:
  • Control loop 7 Maintain level of Inert gases
  • the level of inert gases, y6 (e.g. nitrogen and argon), should be maintained at a low level by controlling the purge gas to flare/exhaust, u8

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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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 formée de déchets dans un ou plusieurs gazéifieurs par introduction de la charge d'alimentation dans une première zone de réaction d'un gazéifieur à une température de 500 à 1000 °C, ce qui permet de générer : un premier flux de sortie; introduire le premier flux de sortie en provenance de la première zone de réaction dans une seconde zone de réaction d'un gazéifieur 8O046OQ AC, générant ainsi un deuxième flux de sortie comprenant le gaz de synthèse; introduire le deuxième flux de sortie en provenance de la seconde zone de réaction dans une zone de réaction de synthèse de produit, ce qui permet de générer un quatrième flux de sortie; séparer le quatrième flux de sortie issu de la réaction du produit en un cinquième flux de produit brut liquide, qui est envoyé vers un traitement ultérieur (par ex., distillation) et en 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 pour une conversion ultérieure du CO et du Hz en produit souhaité; au moins une partie du septième flux de gaz est réintroduite dans la boucle dans la première zone de réaction; les paramètres de gazéification pour les première et seconde zones de réaction sont régulés pour prendre en compte la composition et la quantité des flux de gaz recyclés.
PCT/DK2023/000177 2022-07-01 2023-06-30 Production de gaz de synthèse à partir de déchets Ceased WO2024002442A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
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WO2025218944A1 (fr) * 2024-04-15 2025-10-23 Siemens Energy Global GmbH & Co. KG Procédé de production d'hydrocarbures régénératifs par la voie méthanol et installation de synthèse correspondante

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WO2025201610A1 (fr) * 2024-03-25 2025-10-02 Sempercycle Aps Production améliorée de gaz de synthèse à production améliorée d'hydrogène intégrée

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US20130109765A1 (en) * 2011-10-26 2013-05-02 Rentech, Inc. Gasifier fluidization
AU2015402524A1 (en) * 2015-07-14 2018-02-08 Fulcrum Bioenergy, Inc. Processes for producing high biogenic concentration Fischer-Tropsch liquids derived from municipal solid wastes (MSW) feedstocks

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025201609A1 (fr) * 2024-03-25 2025-10-02 Sempercycle Aps Production améliorée de gaz de synthèse avec une rwgs
WO2025218944A1 (fr) * 2024-04-15 2025-10-23 Siemens Energy Global GmbH & Co. KG Procédé de production d'hydrocarbures régénératifs par la voie méthanol et installation de synthèse correspondante

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