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WO2024218391A1 - Nettoyage de gaz d'alimentation contenant du co2 - Google Patents

Nettoyage de gaz d'alimentation contenant du co2 Download PDF

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Publication number
WO2024218391A1
WO2024218391A1 PCT/EP2024/060944 EP2024060944W WO2024218391A1 WO 2024218391 A1 WO2024218391 A1 WO 2024218391A1 EP 2024060944 W EP2024060944 W EP 2024060944W WO 2024218391 A1 WO2024218391 A1 WO 2024218391A1
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Prior art keywords
feed
rich
rich gas
stream
process according
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English (en)
Inventor
Martin ØSTBERG
Birgitte Staal HAMMERSHØI
Mads Kristian KAARSHOLM
Christian PILEKÆR
Thomas Sandahl Christensen
Morten Thellefsen
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Topsoe AS
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Haldor Topsoe AS
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Priority to CN202480025598.1A priority Critical patent/CN120957802A/zh
Priority to AU2024259560A priority patent/AU2024259560A1/en
Publication of WO2024218391A1 publication Critical patent/WO2024218391A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • 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
    • 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
    • C10K3/02—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
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/202—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • 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
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • 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
    • 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
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • 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

Definitions

  • the present invention relates to a process for cleaning a CO 2 -rich gas feed, in particular for removing sulfur-containing impurities, and optionally oxygen (O 2 ).
  • the catalyst/absorbent systems developed to remove sulfur impurities from CO2 have been found to be sensitive to relatively high oxygen concentrations as well, and a solution has been developed to remove the 02 from the CO2 gas before the CO2 gas enters the sulfur removal process.
  • the present invention relates to a process for cleaning a CCh-rich gas feed, said CC -rich gas feed comprising at least 80 wt% CO2 and one or more sulfur- containing impurities; wherein said process comprises the step of: passing the CCh-rich gas feed together with a hydrogen-rich feed over a guard material, and adsorbing one or more sulfur-containing compounds on said guard material, to provide a cleaned CC -rich gas stream.
  • a process for production of a syngas stream comprising the process described above, and further comprising : providing at least a portion of said cleaned CCh-rich gas stream from the process described above; providing a second hydrogen-rich feed, optionally obtained from the process of electrolysis of water in one or more electrolysis unit(s); reacting said portion of the cleaned CCh-rich gas stream with the second hydrogenrich feed, to provide at least one syngas stream.
  • a process is also provided for production of a synthetic fuel stream, said process comprising the process described above, and further comprising the step of converting said at least one syngas stream to at least one synthetic fuel stream, preferably being a MeOH (methanol) stream, a DME (dimethyl ether) stream, or a synthetic fuel stream, where the synthetic fuel could be aviation fuel, gasoline, diesel or similar.
  • a synthetic fuel stream preferably being a MeOH (methanol) stream, a DME (dimethyl ether) stream, or a synthetic fuel stream, where the synthetic fuel could be aviation fuel, gasoline, diesel or similar.
  • Figure 1 shows a simple layout of one embodiment of the process of the invention.
  • Figure 2 shows a layout for production of a syngas stream.
  • FIG. 3 shows another layout of the CO2 gas purification process
  • any given percentages for gas content are %, ppm (parts per million) or ppb (parts per billion) by volume. All feeds are preheated as required. Unless specified, the concentrations will be given on dry basis, i.e. without taking any water present into account.
  • a cleaned CO2 stream is defined as the outlet stream from the CO2 cleaning process, in which minimum 95% of the combined sulfur containing impurities in the feed is removed or the sum of sulfur containing impurities in the clean CO2 stream is lower than 500 ppb (parts per billion by volume), preferably lower than 100 ppb and most preferably lower than 50 ppb.
  • the sum of sulfur containing in the cleaned CO2 stream should be understood as sulfur- equivalents, i.e. 100 ppb SO2 correspond to 100 ppb sulfur whereas 100 ppb CS2 correspond to 200 ppb sulfur.
  • cleaned CO2 stream is defined as the outlet stream from the CO2 cleaning process, in which minimum 95% of the oxygen in the feed is removed or the 02 concentration in the clean CO2 stream is lower than 200 ppm, preferably lower than 100 ppm and most preferably lower than 50 ppm.
  • Syngas is used as reference for a synthesis gas, a gas mixture comprising hydrogen, carbon monoxide, carbon dioxide and typically water as steam and methane. It is referred to as syngas I synthesis gas because it is the feed for a downstream catalytic synthesis leading to the desired product.
  • the feed downstream the referred purification can be mixed with hydrogen and be used as synthesis gas e.g. for methanol synthesis in other applications, the purified gas may after mixing with hydrogen and optionally steam need conversion in a reverse water gas shift reactor (RWGS) or combined RWGS and methanation reactor to form the final synthesis gas for the synthesis of the final product.
  • RWGS reverse water gas shift reactor
  • the proposed solution ensures that the feed gases for any downstream conversion to synthesis gas and synthesis for chemicals like MeOH, DME, FT (Fischer Tropsch) synthetic fuels, TIGAS based gasoline etc. will be unproblematic with regard to sulfur and oxygen poisoning of the downstream synthesis catalyst. This will ensure that operation can be made over time and allow catalyst lifetime as expected for industrial catalyst.
  • a process for cleaning a CC -rich gas feed is provided.
  • the CCh-rich gas feed provided to the process suitably comprises at least 90 wt% CO2, such as at least 95 wt% CO2, such as at least 99.0 wt% CO2, preferably at least 99.5 wt% CO2, more preferably as at least 99.9 wt% CO2.
  • the CC -rich gas feed is thus already of high purity prior to the process of the present invention.
  • the CC -rich gas feed is derived from a renewable source, such as: combustion or gasification of a lignocellulosic biomass such as wood products, algae, grass, forestry waste and/or agricultural residue; combustion or gasification of municipal waste, in particular the organic portion thereof, where the municipal waste is defined as a feedstock containing materials of items discarded by the public, such as mixed municipal waste given in EU Directive 2018/2001 (RED II), Annex IX, part A; microbial conversion of nitrogen-rich renewable feedstock such as manure or sewage sludge; fermentation of hydrocarbon(sugar) rich feed streams such as corn, sugar cane and beets.
  • a renewable source such as: combustion or gasification of a lignocellulosic biomass such as wood products, algae, grass, forestry waste and/or agricultural residue
  • combustion or gasification of municipal waste in particular the organic portion thereof, where the municipal waste is defined as a feedstock containing materials of items discarded by the public, such as mixed municipal waste given in EU Directive 2018/
  • the CCh-rich gas feed can also be obtained from direct air capture processes, metallurgical processes, cement production or fossil fuel combustion.
  • the CO2 concentration in most of the above-mentioned gas streams may typically be too low for further chemical processing and a concentration step is required to increase the CO2 concentration to the desired value as mentioned above.
  • the CCh-rich gas feed comprises one or more sulfur-containing impurities.
  • the one or more sulfur-containing impurities within the CCh-rich gas feed may be selected from organosulfur compounds such as thiols, sulfides, disulfides, sulfones, sulfoxides and thioketones, CS2, COS, SO3, SO2 and H2S, preferably H2S and SO2, most preferably SO2.
  • the total content of SO2 in the CO2-rich gas feed is 0.1-50 ppm SO2, such as 0.2-10 ppm SO2, such as 1-10 ppm SO2, such as 0.5-5 ppm SO2, such as 1-5 ppm SO2.
  • the CCh-rich gas feed may also comprise water.
  • the total content of H2O in the combined feed of the CC -rich gas feed and the hydrogen-rich feed, after mixing of said feeds is no more than 10 vol%, preferably no more than 5.0 vol%, preferably no more than 1.0 vol%, e.g. approximately 0.5 vol%.
  • the CC -rich gas feed may - in certain cases - comprise oxygen (O2).
  • Oxygen may also contaminate, poison or lead to degradation of downstream catalysts and guard material, so any oxygen in the CO2-rich gas feed should often be reduced or eliminated.
  • the total content of O2 in the CO2 -rich gas feed is 50-10,000 ppm O2, such as 50-5,000 ppm O2, such as 100- 3,000 ppmV O2.
  • the process comprises the step of: passing the CCh-rich gas feed together with a hydrogen-rich feed over a guard material, and adsorbing one or more sulfur-containing compounds on said guard material, to provide a cleaned CCh-rich gas stream.
  • the CCh-rich gas feed additionally comprises oxygen (O2)
  • the process comprises the additional step of: passing the CCh-rich gas feed together with said hydrogen-rich feed over a catalyst active in hydrogenation of oxygen and reducing the oxygen in the CO2/H2 gas mixture, to provide a first CCh-rich gas stream, prior to the step of passing the CCh-rich gas feed over the guard material for absorbing one or more sulfur-containing impurities, to provide a cleaned CO2 rich gas stream.
  • the CCh-rich gas feed to be purified may be first mixed with a hydrogen-rich feed, which acts as a reductant for one or more sulfur-containing impurities, and optionally for oxygen, in the CCh-rich gas feed.
  • the hydrogen-rich feed to the process comprises at least 90 wt% hydrogen such as at least 95 wt% hydrogen such as at least 98 wt% hydrogen.
  • hydrogen is suitably added such that, the total content of H2 in the combined feed of the CCh-rich gas feed and the hydrogen-rich feed, after mixing of said feeds, is 0.2-10 vol% H2 such as 0.5-3 vol% H2.
  • the advantage of this embodiment is that addition of H2 is controlled, so as to limit undesired side reactions, e.g. methanol formation.
  • the addition of hydrogen should always be sufficient to achieve excess H2 in the product gas exiting the guard material.
  • hydrogen is suitably added such that, the molar ratio HziOz is greater than 2 in the combined feed of the CCh-rich gas feed and the hydrogen-rich feed, after mixing of said feeds and the purified CO2 leaving the CO2 purification system contains 0.2-10 vol% H2 such as 0.5-3 vol% H2.
  • the advantage of this embodiment is that addition of H2 is controlled, so as to limit undesired side reactions, e.g. methanol formation while still having to sufficient H2 surplus to ensure high degree of hydrogenation of any oxygen and the sulfur impurities.
  • the total gas flow is kept at a minimum, thus providing the smallest possible reactor and equipment size.
  • hydrogen is added to the CC -rich gas feed in an amount corresponding to the feed composition to the downstream process for production of synthesis gas, methanol, synthetic fuels and other chemical products.
  • the feed composition to the methanol process will be around 12 %w/w H2 and 88 %w/w CO2. This corresponds to a ratio of 3 moles H2 per mole of CO2.
  • the advantage of this embodiment is that H2 and CO2 can be mixed and preferably compressed prior to the CO2 cleaning.
  • the CO2 cleaning process can be located downstream the final compression step or between intermediate compression steps, whichever is best suited with regard to cost, water concentration, risk of carbonate formation on the guard material and risk of formation of undesired side products such as water and methanol.
  • Another advantage of this embodiment is that any O2 present in the H2 rich feed will also become hydrogenated.
  • H2 from electrolysis of water can contain varying amounts of O2, depending on the operation of the electrolyser.
  • the one or more sulfur-containing compounds adsorbed onto the guard material are typically selected from COS, SO2 and H2S, preferably SO2.
  • the guard material is suitably active in absorption of SO2 and H2S, and is preferably a Cu-Zn-AI guard material.
  • the guard material is capable of catalytically reducing the SO2 in the CO2 feed rich to H2S, which is much more efficiently adsorbed on the guard than the SO2.
  • the guard is also capable of reacting oxygen content in the CO2 feed stream with hydrogen to form water.
  • the process provides a cleaned CO2-rich gas stream.
  • This cleaned CO2-rich stream typically comprises: less than 500 ppb, preferably less than 100 ppb, preferably less than 50 ppb sulfur and more preferably less than 25ppb sulfur, less than 200 ppmV O2, less than 100 ppmV O2, less than 50 ppmV C
  • the guard material used in the process of the invention is suitably located within a reactor vessel, said reactor vessel being arranged to receive the CCh-rich gas feed and the hydrogen-rich feed, optionally in admixture.
  • the guard material is preferably having a chemical composition of 25-60 %w/w Cu, 15-70 %w/w Zn, and optionally 2-10 %w/w Al. It may comprise minor amounts of K and C as well. The elements will either be found in a reduced or oxidised state.
  • the CO2 cleaning process is typically operated in the pressure range 1- 100 bar, preferably 1- 50 bar, depending on the pressure of the CO2 feed stream and the pressure of the downstream conversion process.
  • the CO2 cleaning process is typically operated in the 120-250 °C temperature range.
  • a pressure in the interval 1-90 bar is also typical.
  • more than 95% of the one or more sulfur containing impurities are retained on the guard material or the total concentration of sulfur containing impurities in the cleaned CC -rich gas stream is ⁇ 500 ppb, such as ⁇ 100 ppb, such as ⁇ 50 ppb.
  • the cleaned CC -rich gas stream is sufficiently pure that catalyst poisoning of downstream processes is significantly reduced.
  • the invention therefore provides a process for production of a syngas stream, said process comprising the process as described above, and further comprising : providing at least a portion of said cleaned CCh-rich gas stream from the process described herein; providing a second hydrogen-rich feed, optionally obtained from the process of electrolysis of water in one or more electrolysis unit(s); reacting said portion of the cleaned CCh-rich gas feed with the second hydrogen-rich feed, to provide at least one syngas stream.
  • the step of reacting the portion of the cleaned CC -rich stream feed with the second hydrogen-rich feed, to provide at least one syngas stream may be carried out in the presence of a catalyst active in reverse water gas shift.
  • a process for production of a synthetic fuel stream comprising providing at least one syngas stream, as described herein, and further comprising the step of converting said at least one syngas stream to at least one synthetic fuel stream, preferably being a MeOH stream, a DME stream, or a synthetic fuel stream, preferably wherein said synthetic fuels are aviation fuel, gasoline or diesel fuels.
  • the process of converting said at least one syngas stream to at least one synthetic fuel stream is a Fisher-Tropsch process, which provides a synthetic fuel stream.
  • the process of converting said at least one syngas stream to at least one synthetis fuel stream is a TIGAS process, which provides a synthetic fuel stream.
  • FIG. 1 shows a simple layout of one embodiment of the process of the invention.
  • a CCh-rich gas feed 1 is mixed with a hydrogen-rich feed 2 and passed over a guard material 10 in reactor vessel 100. Sulfur-containing compounds are adsorbed on the guard material 10 and a cleaned CC -rich gas stream 50 is outputted.
  • Figure 2 shows a layout for production of a syngas stream.
  • the reactor vessel 100, CCh-rich gas feed 1, hydrogen-rich feed 2 and cleaned CCh-rich gas stream 50 are according to Figure 1.
  • a second hydrogen-rich feed 202 is reacted with the cleaned CCh-rich stream feed 50, in a syngas section 300 to provide at least one syngas stream 301.
  • FIG 3 one embodiment for the layout of the CO2 gas purification process is shown.
  • the CO2 gas feed (1) comprising O2 and one or more sulfur-impurities is mixed with an amount of a H2 rich gas (2).
  • the mixed gas is sent to a compressor (5) in which the pressure is increased.
  • the high-pressure feed gas (6) is then preheated in a heat exchanger (7) and the heated feed gas (9) is sent to the oxygen hydrogenation reactor (11) in which an oxygen hydrogenation catalyst (12) is installed and hydrogenates O2 to H2O.
  • the substantially O2 free CO2 gas stream (17) is then cooled in heat exchanger (18) such that the feed gas (20) to the sulfur removal reactor (22) has the optimal temperature.
  • a guard material (10) is installed, removing sulfur impurities.
  • the off-gas from the sulfur removal reactor (26) is substantially free of oxygen and sulfur impurities and can be further processed to synthesis gas and other products.
  • Liquid water is supplied via a pump, passing through an evaporator and mixed with the feed gas upstream of the fixed bed reactor.
  • the guard material used is a coprecipitated Cu/ZnO/alumina-based guard material.
  • the guard material can be separated in several fractions (beds), the weight of the total guard material and the number of fractions I beds are given. Each fraction will typically be equally sized.
  • the guard material has been crushed and sieved before loading to a particle fraction between 600 pm to 1000 pm from the original material size to achieve an optimal size in the laboratory reactor. Before measuring SO2 removal from the CO2 feed gas, the guard material was reduced in 2% H2 in N2 at 220°C and 3 barg.
  • Table 1 lists the different tests carried out with SO2 in the CO2 feed gas and the exit analysis given are after 200 hours with continuous dosing of SO2.
  • the O2 hydrogenation activity was investigated for Topsoe's O2XtractTM hydrogenation catalyst, comprising Pd and Pt as the active components.
  • the hydrogenation activity was measured in a CO2 feed gas comprising 2.5 vol% H 2i 2,000 ppm O2 and either 0 or 10 ppm SO2.
  • the catalyst space velocity was 180,000 Nm 3 /h/m 3 and the temperature was varied in the range 50-350 °C.
  • O2 concentrations were measured at the inlet and outlet of the catalyst with a dedicated O2 in CO2 sensor and O2 hydrogenation conversion was based on these concentrations. The conversions as a function of catalyst temperature are seen in figure 4.
  • the hydrogenation catalyst is very active in O2 hydrogenation, but also that the catalyst activity is significantly hampered by the presence of SO2.
  • the temperature should be higher than 200 °C and preferably closer to 250-350 °C or above.
  • EXAMPLE III In a process layout as depicted in figure 3, the CO2 feed gas is mixed with H2 in amount corresponding to 3 mol H2 per mol CO2 after the CO2 gas purification, making the mixed gas suitable for the production of methanol in a downstream synthesis plant.
  • the CO2 feed gas contains 1 vol% O2 and 5 ppm SO2.
  • the CO2 feed gas is mixed with the entire H2 feed and compressed to 90 barg and preheated to 185 °C in a dedicated heat exchanger, i.e. heat exchanger 7 in figure 3 is split up in a feed gas preheater with its own heat source, such as steam or electricity, and a feed/effluent heat exchanger, connecting the cold side of heat exchanger 7 with the hot end of heat exchanger 18.
  • the 185 °C feed gas is then preheated to 300 °C in the feed/effluent exchanger by heat exchange with the hot gas from the outlet of O2 hydrogenation reactor 11.
  • the O2 hydrogenation catalyst is active and not poisoned by the SO2 in the mixed gas.
  • the O2 hydrogenation reaction is highly exothermic and increase the temperature by 35 °C to 335 °C, more than compensating for the temperature approach in the feed/effluent heat exchanger.
  • 15-20 % of the hot gas from the O2 hydrogenation reactor (17) bypasses the feed/effluent heat exchanger.
  • the hot gas from the reactor is cooled to 195 °C in the feed/effluent heat exchanger and mixed with the bypassed hot gas to end up with a mixed temperature of 220 °C to the downstream guard material (10), well within the optimal temperature range for this process.
  • the SO2 become hydrogenated to H2S and captured on the Cu and Zn sites of the guard material.
  • the cleaned process gas can then be directed to the methanol synthesis plant at a temperature well suited for the methanol converter.
  • feed/effluent heat exchangers are designed with a minimum temperature approach of 10-20 °C to provide an economical and still efficient heat exchanger.
  • the adiabatic temperature increase in the O2 hydrogenation reactor in this example with be 7 °C, which is in the lower than the normal design rules.
  • the heat exchange surface can be increased to decrease the design temperature approach, or a small support heater can be installed to increase the temperature by the necessary 3-13 °C.
  • an amount of O2 could also be added to the CO2 gas, providing more hydrogenation reaction and thus heat evolved but that may option be too expensive with regard to H2 consumption, and the extra water formed will reduce the capacity of the guard material and conversion efficiency in the downstream methanol plant.
  • the formed water vapor may beneficially be removed at a position upstream the guard material and synthesis plant.
  • Water removal can be achieved by cooling the gas mixture to a temperature below the water dew point to condense and withdraw a fraction of the water as liquid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

La présente invention concerne un procédé de nettoyage d'une alimentation en gaz riche en CO2, en particulier pour éliminer des impuretés contenant du soufre, et éventuellement de l'oxygène.
PCT/EP2024/060944 2023-04-21 2024-04-22 Nettoyage de gaz d'alimentation contenant du co2 Pending WO2024218391A1 (fr)

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CN202480025598.1A CN120957802A (zh) 2023-04-21 2024-04-22 含co2进料气体的净化
AU2024259560A AU2024259560A1 (en) 2023-04-21 2024-04-22 Cleaning of co2 containing feed gases

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521387A (en) * 1982-11-23 1985-06-04 Basf Aktiengesellschaft Purification of gases containing CO and/or CO2
US20070028764A1 (en) 2005-08-08 2007-02-08 Carsten Wittrup Method for enabling the provision of purified carbon dioxide
EP2457636A1 (fr) 2010-11-30 2012-05-30 General Electric Company Systèmes de capture de carbone et procédés pour l'élimination sélective du soufre
US20130209338A1 (en) * 2010-07-15 2013-08-15 Quadrogen Power Systems, Inc. Integrated biogas cleaning system to remove water, siloxanes, sulfur, oxygen, chlorides and volatile organic compounds
CN112957872A (zh) 2021-03-17 2021-06-15 西北大学 一种提纯co2脱除so2的装置与方法
CN112999843A (zh) 2021-01-05 2021-06-22 西南化工研究设计院有限公司 一种含硫化氢和有机硫排放气的净化工艺
US20210402368A1 (en) * 2019-06-27 2021-12-30 Korea Institute Of Energy Research Hydrogen sulfide adsorbent in biogas and biogas purification system using the same
US20220333015A1 (en) 2021-04-13 2022-10-20 Infinium Technology, Llc Process for purification and conversion of carbon dioxide using renewable energy

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521387A (en) * 1982-11-23 1985-06-04 Basf Aktiengesellschaft Purification of gases containing CO and/or CO2
US20070028764A1 (en) 2005-08-08 2007-02-08 Carsten Wittrup Method for enabling the provision of purified carbon dioxide
US20130209338A1 (en) * 2010-07-15 2013-08-15 Quadrogen Power Systems, Inc. Integrated biogas cleaning system to remove water, siloxanes, sulfur, oxygen, chlorides and volatile organic compounds
EP2457636A1 (fr) 2010-11-30 2012-05-30 General Electric Company Systèmes de capture de carbone et procédés pour l'élimination sélective du soufre
US20210402368A1 (en) * 2019-06-27 2021-12-30 Korea Institute Of Energy Research Hydrogen sulfide adsorbent in biogas and biogas purification system using the same
CN112999843A (zh) 2021-01-05 2021-06-22 西南化工研究设计院有限公司 一种含硫化氢和有机硫排放气的净化工艺
CN112957872A (zh) 2021-03-17 2021-06-15 西北大学 一种提纯co2脱除so2的装置与方法
US20220333015A1 (en) 2021-04-13 2022-10-20 Infinium Technology, Llc Process for purification and conversion of carbon dioxide using renewable energy

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