WO2025242536A1 - Élimination de soufre et d'oxygène à partir de flux riches en co2 - Google Patents

Élimination de soufre et d'oxygène à partir de flux riches en co2

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Publication number
WO2025242536A1
WO2025242536A1 PCT/EP2025/063403 EP2025063403W WO2025242536A1 WO 2025242536 A1 WO2025242536 A1 WO 2025242536A1 EP 2025063403 W EP2025063403 W EP 2025063403W WO 2025242536 A1 WO2025242536 A1 WO 2025242536A1
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Prior art keywords
gas
reaction zone
scavenger
ppm
zone
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Inventor
Morten Thellefsen
Birgitte Staal Hammershøi
Mads Kristian KAARSHOLM
Martin ØSTBERG
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Topsoe AS
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Haldor Topsoe AS
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Publication of WO2025242536A1 publication Critical patent/WO2025242536A1/fr
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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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • 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
    • 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
    • B01D53/75—Multi-step processes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/102—Oxygen
    • 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
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • 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
    • B01D2253/102—Carbon
    • 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
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • 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
    • B01D2257/30—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
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • 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
    • B01D2257/308—Carbonoxysulfide COS

Definitions

  • the invention pertains to the field of green or low-carbon chemical technologies, specifically focusing on the purification of carbon dioxide-rich streams comprising oxygen and a sulfur-containing impurity, by removing therefrom the oxygen and the sulfur-containing impurities such as SO2, thereby producing a purified CC>2-rich gas.
  • the invention relates also to the conditioning of carbon dioxide-rich streams comprising oxygen and a sulfur-containing impurity, by removing therefrom the oxygen and the sulfur-containing impurities such as SO2, thereby producing a synthesis gas.
  • the synthesis gas is suitably used for downstream production of methanol and/or hydrocarbon fuels.
  • Carbon dioxide (CO2) is commercially available in different grades. Typically, “food grade” or “beverage grade” CO2 has a purity of 99.9%. However, for processes involving catalytic conversion of CO2 to other chemical products, such as methanol via methanol synthesis and hydrocarbon products i.e. hydrocarbon fuels via Fischer-Tropsch (FT) synthesis, impurities such as sulfur-containing compounds and oxygen in the CO2 stream may poison the synthesis catalyst, even when present in concentrations of for instance 0.00001% (100 ppb) or even lower.
  • FT Fischer-Tropsch
  • Green or low-carbon chemical technologies are gaining increasing attention due to the associated reduction of carbon emissions. These technologies often involve the reaction of a CC>2-feed with a H2-feed to convert them into desired chemicals such as methanol and FT-based hydrocarbon fuels.
  • the catalysts involved in these processes are vulnerable to impurities in the feeds.
  • a CC>2-rich feed gas can be challenging to handle as the impurities depend on the origin of the CO2 and can vary significantly.
  • One such CO2-rich feed gas can contain both O2 and a sulfur-containing impurity, both compounds being undesired in downstream catalyst systems such as in methanol synthesis reactor or a FT-synthesis reactor. The presence of these compounds, in particular O2, e.g.
  • PA 2023 00340 discloses SO2 removal from a CO2 stream by catalytically converting the SO2 to H2S by H2 on a Ni-Mo or Co-Mo based catalyst and absorbing the H2S on a Zn-based absorbent.
  • US20190126199 discloses a process for the purification of a raw gas by selective catalytic oxidation, in which organic and inorganic sulfur compounds, halogenated and non-halogenated volatile organic compounds are selectively oxidized without substantially oxidizing the lower hydrocarbons and the sulfur containing compounds present in the gas to sulfur trioxide and excess of oxygen is removed by oxidation of lower alcohols, ethers or hydrogen added to the raw gas stream upstream the catalytic oxidation.
  • US 11083995 discloses a process to treat/clean a gas, containing SO2, CO2 and O2 comprising the steps of: bringing the gas in contact with an activated carbon catalyst, converting SO2 to SO3/H2SO4 on the activated carbon catalyst, washing the SO3/H2SO4 from the activated carbon catalyst to obtain a sulfuric acid solution and a SO2 depleted gas; bringing the SO2 depleted gas in contact with an aqueous ammonia solution wherein CO2 is converted to obtain a SO2 and CO2 depleted gas containing ammonia; and bringing the SO2 and CO2 depleted gas containing ammonia in contact with the sulfuric acid solution obtained in step a. to form a solution containing ammonium sulfate and a treated, clean gas.
  • a process for producing a purified CCh-rich gas or a synthesis gas from a feed gas comprising carbon dioxide (CO2), oxygen (O2) and one or more sulfur (S)-containing impurities comprising: i) supplying the feed gas comprising CO2, one or more sulfur (S)-containing impurities and O2, to a S-scavenger zone, said S-scavenger zone being a S-scavenger reaction zone, a S-absorption zone, or a combination thereof, and withdrawing therefrom a S- depleted gas; ii) supplying a first hydrogen feed and at least a portion of the S-depleted gas, or a combination thereof, to an Ch-hydrogenation reaction zone and withdrawing therefrom a S-and-Ch-depleted gas as said purified CCh-rich gas or said synthesis gas; wherein the feed gas, i.e. CCh-rich feed gas, comprises:
  • first aspect of the invention means the process of the invention.
  • second aspect of the invention means a plant (process plant) of the invention.
  • process/plant means process and/or plant.
  • invention or “present invention” may be used interchangeably with the term “application” or “present application”, respectively.
  • feed gas comprising carbon dioxide (CO2), oxygen (O2) and one or more sulfur (S)-containing impurities
  • CO2 carbon dioxide
  • O2 oxygen
  • S sulfur-containing impurities
  • a given process stream means a conduit, which may be referred interchangeably as a process line, such as a pipe or duct, carrying a given process stream.
  • S-scavenger zone means a physically delimited space, where: a catalytic reaction takes place and thus comprises a catalyst, for instance in a fixed bed such as an adiabatic fixed bed, or a reactor comprising a fixed bed such as an adiabatic fixed bed, hence the term “S-scavenger reaction zone”; or an absorption takes place, for instance in a fixed bed of absorbent, hence the term “S-absorption zone”.
  • the S-scavenger reaction zone is a SCh-scavenger reactor.
  • Ch-hydrogenation reaction zone means a physically delimited space where the catalytic Ch-hydrogenation reaction 2 H2 + O2 -> 2 H2O takes place and thus comprises a hydrogenation catalyst.
  • a fixed bed such as an adiabatic fixed bed, or a reactor comprising a fixed bed such as an adiabatic fixed bed.
  • the Ch-hydrogenation reaction zone is an Ch-hydrogenation reactor.
  • any given percentages for gas content are % by volume (vol. %) or correspondingly in ppm or ppb units. 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 purified CCh-rich gas is defined as the outlet stream from the Ch-hydrogenation reaction zone, in which minimum 95% of the combined sulfur containing impurities in the feed gas is removed and at least 95% of the O2 is hydrogenated to H2O.
  • the sum of sulfur containing impurities in the purified CCh-rich gas is preferably lower than 100 ppb, more preferably lower than 50 ppb and most preferably lower than 20 ppb.
  • the lower limit is the measurement detection limit. For instance, for SO2 the detection limit of a PFPD detector is in the range 0.02-0.05 ppm (20-50 ppb).
  • the sum of sulfur containing impurities in the purified CCh-rich gas 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.
  • the O2 concentration in the purified CCh-rich gas is preferably lower than 500 ppm, such as less than 100 ppm, for instance lower than 100 ppm, preferably lower than 10 ppm.
  • a S-scavenger reaction zone such as a SCh-scavenger reactor
  • a dual SCh-scavenger reactor for instance a dual SCh-scavenger reactor arranged in series.
  • the term “at least a portion” of a given item means a portion or the entire portion.
  • at least a portion of a stream means a portion of the stream or the entire stream.
  • the product gas at the outlet of the Ch-hydrogenation reaction zone is, an embodiment, purified CCh-rich gas.
  • the CCh-concentration in the purified CCh-rich gas is thus higher than the CCh-concentration in the feed gas, i.e. the feed gas comprising carbon dioxide (CO2), oxygen (O2) and one or more sulfur (S)-containing impurities.
  • the CCh-concentration in the purified CCh-rich gas is at least: 99 or 99.5 vol.%.
  • the product gas at the outlet of the Ch-hydrogenation reaction zone is, in an embodiment, a synthesis gas.
  • the CCh-concentration at the outlet of the Ch-hydrogenation reaction zone hence in the synthesis gas, is thus lower than the CCh-concentration in the feed gas, i.e. the feed gas comprising carbon dioxide (CO2), oxygen (O2) and one or more sulfur (S)-containing impurities.
  • the CCh-concentration in the feed gas is at least 80 vol.% CO2, such as at least: 85, 90, 95 vol.
  • % CO2 for instance, at least: 99 or 99.5 vol%, while the CCh-concentration in the synthesis gas is for instance 20 vol.% or higher, such as 25 vol.%, or such as 20-40 vol.%, or such as or 20-30 vol.%.
  • synthesis gas and “syngas” may be used interchangeably.
  • the term means a gas mixture comprising hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2) and optionally water (H2O) as steam and optionally methane (CH4).
  • H2O hydrogen
  • synthesis gas or “syngas” as it is the feeding gas to a downstream catalytic synthesis leading to a desired product, such as a chemical product like methanol, or a hydrocarbon product such as a hydrocarbon fuel in the transportation fuel range, particularly any of jet fuel, diesel and gasoline.
  • the invention enables operation of the Ch-hydrogenation reaction zone over a wide range of temperatures, for instance at low temperatures, these being in the range 50-100°C; and/or at high temperatures, these being 100-400°C, such as 300-400°C.
  • the invention describes a process and plant to first remove the sulfur containing impurities, particularly SO2, from a CCh-rich feed gas comprising O2, such that a catalyst for O2 hydrogenation can be used without risk of sulfur poisoning of the catalyst.
  • the SO2 removal process utilizes in turn the O2 present in the feed gas to increase the S-re- moval efficiency, in particular the SO2 removal efficiency, hence the SCh-removal capacity, as well as to decrease the equilibrium SCh-slip at the outlet of the S-scavenger zone.
  • a simpler and more flexible solution is thereby also achieved. There is for instance no need for extra heating being supplied to the corresponding gas.
  • the solution according to the invention ensures, that the purified CCh-rich gas, or synthesis gas serving as a feeding gas for any downstream conditioning into synthesis gas and synthesis for chemicals like methanol (MeOH), dimethyl ether (DME), FT (Fischer Tropsch) synthetic fuels etc., is unproblematic regarding sulfur and oxygen poisoning of the downstream synthesis catalyst. This ensures that stable operation can be made over time and allow catalyst lifetime as expected for an industrial catalyst.
  • the feed gas i.e. CCh-rich feed gas, comprises:
  • the one or more S-containing impurities is any of: organosulfur compounds such as thiols, sulfides, disulfides, sulfones, sulfoxides and thioketones, COS, SO3, SO2, H2S and combinations thereof; preferably at least one of: H2S and SO2, most preferably at least SO2.
  • organosulfur compounds such as thiols, sulfides, disulfides, sulfones, sulfoxides and thioketones, COS, SO3, SO2, H2S and combinations thereof; preferably at least one of: H2S and SO2, most preferably at least SO2.
  • the term “one or more S-containing impurities” means a sulfur compound, as any one of the above recited compounds.
  • the one or more S-containing impurities is SO2 and the content of SO2 in the feed gas is 0.1-50 ppm SO2, such as: 0.5-20 ppm SO2, or 1-10 ppm SO2, or 0.5-5 ppm SO2.
  • the S-scavenger reaction zone and the Ch-hydrogenation reaction zone are in direct fluid communication prior to the addition of the first hydrogen feed.
  • direct fluid communication means that there is no intermediate unit or step changing the composition of a process stream. Hence, in connection with the present embodiment, there is no intermediate step changing the composition of the S-depleted gas prior to the addition of the first hydrogen feed.
  • the S-depleted gas may pass through process equipment such as a heater, cooler or compressor, before entering the Ch-hydrogenation reaction zone and/or before combining with the first hydrogen feed, as for instance shown in the appended figures 1 and 2.
  • the S-scavenger zone comprises any of: an activated carbon, an alkaline absorbent, and combinations thereof; preferably arranged as a one or more fixed beds; more preferably, activated carbon arranged as one or more fixed beds, and downstream an alkaline absorbent arranged as one or more fixed beds.
  • the S-scavenger zone is a S-scavenger reaction zone, preferably a SCh-scavenger reaction zone, comprising said activated carbon; wherein the process further comprises: supplying a water stream to the SCh-scavenger reaction zone and forming a sulfuric acid product; and wherein: - said sulfuric acid product is continuously withdrawn from the S-scavenger reaction zone; or
  • S-scavenger reaction zone such as “SC>2-scavenger reaction zone” is utilized where a reaction of water with SO2 to produce sulfuric acid takes place in a fixed bed, in particular in activated carbon.
  • S-absorption zone is utilized where an absorbent, in particular an alkaline absorbent, is provided.
  • the S-scavenger zone is a SCh-scavenger reaction zone, which is arranged to receive a liquid or gaseous water stream e.g. water vapor and provide a sulfuric acid stream.
  • a SCh-scavenger reaction zone may thus for instance be a SC>2-removal unit.
  • the activated carbon is most effective when some water, e.g. water vapor, is present.
  • continuously means “continuous operation”, which as is well known in the art means that the incoming stream during a given production cycle is constant, as also is the stream being withdrawn as the outcoming product, here the sulfuric acid product.
  • the catalytic activity of the activated carbon enables reaction of the SO2 with the O2 in the CO2 of the feed gas and thus strongly bind the formed SO3 to the activated carbon.
  • the activated carbon is suitably washed with water to remove the SO3 and sulfuric acid, H2SO4, thus making e.g. a continuous system and thus significantly reducing the use for absorbents which must be replaced over time.
  • an amount of water is present and preferably there is a relative humidity in the 20-70% range.
  • a continuous system to remove SO2 from the CCh-rich feed gas is thus suitably achieved, utilizing the existing O2 in the CCh-rich gas feed to form SO3 over an activated carbon bed, thus providing a substantially SCh-free CCh-rich stream as said S- depleted gas for the downstream Ch-hydrogenation.
  • Water may also be present in the feed gas, which normally is undesirable, as high concentrations of water can limit or inhibit the uptake of S-compounds in typical guard (absorbent) materials.
  • limiting the water concentration provides for a more efficient operation of the guard material and thereby the SCh-scavenger absorption zone.
  • the total content of H2O entering the SCh-scavenger absorption zone is no more than 2 vol%, such as no more than 1.0 vol%, or no more than 0.5 vol%, e.g. approximately 0.2 vol%.
  • the present invention takes advantage of any water present, for producing sulfuric acid.
  • Gas/solid contactors can be made with the same alkaline species as above, now just found as a solid on a porous carrier system. Such systems will have a higher removal efficiency, but typically with the cost of a lower removal capacity as the amount of active reagent gets depleted as the reaction proceeds.
  • the recited two systems of the above embodiment are suitable for removal of low concentrations of SO2, each with its own advantages and which combine synergistically for enabling the withdrawal of a S-depleted gas in step i).
  • the two systems can be used individually or be combined to take advantage of both systems.
  • Activated carbon is known to be able to remove SO2 from off-gases from e.g. sulfuric acid plants and flue gases from combustion processes.
  • the process was developed in the 1960’s and is known as the Sulfacid process.
  • the SO2 is absorbed into the pores of the activated carbon and in the presence of O2 it is oxidized to SO3 which then can react with water to form sulfuric acid, H2SO4.
  • the sulfuric acid can then be washed out of the pores by liquid water and the SO2 removal capability is regained.
  • the Sulfacid process typically operates at 30-60°C in process gases with up to 10 vol% O2, up to 1 ,000 ppm SO2 around 5-15 vol% H2O and up to 15 vol% CO2. No references about purification of CC>2-rich feed gases with much lower concentrations of SO2, O2 and H2O has been reported.
  • Alkaline based absorbents are well known for their ability to capture acidic compounds and for SO2 purification in CO2, yet there is a competition between the more acidic SO2 against the less acidic CO2, and with a molar CO2 to SO2 ratio in the typical range of 100,000 to 1 ,000,000.
  • Potassium based absorbents have been shown to be effective in SO2 removal.
  • the potassium will typically be applied on a porous carrier in the form of KOH, KHCO3 or K2CO3.
  • the origin of the K precursor is insignificant as the potassium compound will equilibrate with the CO2 and form a mixture of KHCO3 and K2CO3, the ratio depending on the CO2 and H2O partial pressures and the temperature.
  • the more acidic SO2 replaces the CO2 in the potassium carbonate and form a SOs 2 ' or HSOs' compound. If they can react with the O2 also present in the CO2 gas, SO4 2 ' or HSO4' is formed and these ions are much more stable than the sulfites and will have less tendency to be desorbed from the absorbent.
  • an oxygen stream is added to the feed gas.
  • an oxygen stream is added for increasing the oxygen content in the feed gas, i.e. the CCh-rich feed gas, which is beneficial for situations where there are significant fluctuations in the composition of the feed gas.
  • it may even be beneficial to add an amount of O2 to the CCh-rich feed gas should the O2 concentration in the CO2 from the source be constantly low or too low or experience periods where the O2 concentration for some reason decreases or drops to zero.
  • This O2 addition increases the stability and removal efficiency of alkaline and activated carbon solutions, by e.g. making stable sulfates, yet it is also limited as the O2 must be hydrogenated in a downstream step (step ii) and thus increases the H2 consumption therein and thereby operating costs.
  • a S-removal unit such as a SO2 removal unit, could either be designed as a single vessel of either an activated carbon bed or an alkaline absorbent bed or a combination of an activated carbon bed followed by an alkaline absorbent bed.
  • two separate vessels i.e. two separate units
  • auxiliary equipment can be placed, such as a compressor, heat exchanger, liquid separator or other equipment.
  • the two beds can be placed in the same vessel, the beds preferably separated with e.g. different bed support structures.
  • the 02-hydrogenation reaction zone comprises a hydrogenation catalyst which comprises an alumina and/or silica carrier impregnated with a metal, such as: Cu, Mn, Pt, Pd, or combinations thereof; preferably, the 02-hydrogenation reaction zone is arranged as a fixed bed or as a monolithic type catalyst, and the hydrogenation catalyst comprises an alumina and/or silica carrier impregnated with Pt and/or Pd.
  • this hydrogenation catalyst in particular alumina and/or silica carrier impregnated with Pt and/or Pd, provides the best removal of O2 from the S-depleted gas.
  • the hydrogenation catalyst is provided as a monolithic type catalyst, for instance a monolith catalyst structure coated with the hydrogenation catalyst, as this enables, among other things, operation with lower pressure drop compared to a fixed bed, the latter typically being provided as a fixed bed of particles such as pellets.
  • a monolithic type catalyst offers also advantages in terms of surface area, mass transfer, heat transfer, scalability, and durability, making them well-suited for the Ch-hydrogenation reaction zone.
  • monolithic type catalyst means a catalyst structure that is characterized by a single, solid piece or block-like structure. It is typically made of a porous material, such as ceramics or metals, with a high surface area to facilitate the catalytic reaction.
  • the S-scavenger zone and the Ch-hydrogenation reaction zone are arranged as fixed beds within the same unit;
  • said first hydrogen feed is provided between said two zones; preferably by providing a gas distribution device or a gas mixing device for combining the first hydrogen feed with the at the least a portion of the S-depleted gas.
  • the S-scavenger zone is a S-scavenger reaction zone and the S-scavenger reaction zone is a S-scavenger reactor;
  • the Ch-hydrogenation reaction zone is a Ch-hydrogenation reactor; the S-scavenger reactor and the Ch-hydrogenation reactor being provided in separate units.
  • the concentration of O2 in said purified CCh-rich gas i.e. the S-and-Ch-depleted gas, or said synthesis gas, is less than 500 ppm, such as less than 100 ppm, such as less than 50 ppm and preferably less than 20 ppm.
  • the concentration of the one or more S-containing impurities in said S-depleted gas is less than 100 ppb, such as less than 50 ppb, preferably less than 20 ppb.
  • the content of any of the S-containing impurities in the purified CCh-rich gas or in the synthesis gas is less than 100 ppb, such as less than 50 ppb, preferably less than 20 ppb.
  • the first hydrogen feed to the Ch-hydrogenation reaction zone is provided such that:
  • the H2/O2 molar ratio at the inlet to said Ch-hydrogenation reaction zone is at least 2;
  • the first hydrogen feed is suitably added to carry out the hydrogenation of O2.
  • the first hydrogen feed flow can be adjusted to practically any H2 concentration at the outlet of the Ch-hydrogenation reaction zone, i.e. in the purified CCh-rich gas being withdrawn from the Ch-hydrogenation reaction zone, but to ensure complete O2 hydrogenation it is preferred to have a H2/O2 molar ratio, i.e. volume ratio, of at least 2 at the inlet of the Ch-hydrogenation reaction zone.
  • the H2 is thus added as said first hydrogen feed to the S-depleted gas to obtain a H2 surplus, such that the H2 concentration after the Ch-hydrogenation is in the range 0.5-5 vol.%, e.g.1-5 vol%.
  • This is to ensure that the dilution of the purified CCh-rich gas is minimized, while still ensuring that there is a H2 surplus and thereby sufficient H2 for the Ch-hydrogenation.
  • This embodiment decreases the size of the Ch-hydrogenation reaction zone or and any equipment positioned downstream the hydrogenation reactor. Such equipment could e.g. be a compressor, heat exchanger, cooler, another absorbent reactor or liquid separator.
  • the invention relates also to the conditioning of carbon dioxide-rich streams comprising oxygen and a sulfur-containing impurity, by removing therefrom the oxygen and the sulfur-containing impurity such as SO2, thereby producing a synthesis gas.
  • the synthesis gas is suitably used for downstream production of methanol and/or hydrocarbon fuels.
  • the first hydrogen feed to the Ch-hydrogenation reaction zone is provided such that: the H2/CO2 molar ratio at the outlet of the Ch-hydrogenation reaction zone, thereby in said synthesis gas, is in the range 1-5, such as 2-4 or such as 2.5-3.5, preferably 3.
  • the full amount of H2 required for Ch-hydrogenation and downstream synthesis into e.g. methanol is mostly or in its entirety added as said first hydrogen feed, such that the composition at outlet of the Ch-hydrogenation reaction zone resembles that required for a synthesis gas being fed to a downstream synthesis plant.
  • the optimal H2/CO2 molar ratio is about 3, giving a composition of around 70-75 vol% H2 and 20-25 vol% CO2, preferably 75 vol.% H2 and 25 vol.% CO2 corresponding to a H2/CO2 molar ratio of 3.
  • This mixture can then be compressed to downstream synthesis pressure, such as 50-110 barg for a methanol synthesis plant.
  • the process further comprises:
  • Ch-hydrogenation reaction zone inlet mixture is a combination of the first hydrogen feed and the at least a portion of the S-depleted gas, recited in one or more of above or below embodiments.
  • This Ch-hydrogenation reaction zone inlet mixture corresponds to 111 , 211 in appended figures 1 and 2, respectively.
  • the compressor comprises a plurality of compressor stages and the Ch-hydrogenation reaction zone is provided downstream the compressor or in between the compressor stages.
  • the Ch-hydrogenation reactor is then suitably positioned at a position downstream of the compressor, i.e. a feed gas compressor, as for instance shown in appended figure 2, or at an intermediate pressure between the compressor stages.
  • the provision of the H2 mixing at inlet of the Ch-hydrogenation reaction is at first being seen as a disadvantage due to the increased risk of methane formation on the hydrogenation catalyst, which can take place on some catalyst formulations and reactor temperatures, with methane typically being an unwanted compound or the highly exothermic methanation reaction increasing the process gas temperature downstream the Ch- hydrogenation reaction zone to an undesired value.
  • the recited embodiments provide at least the advantage of having only a main or a single H2 addition point, thus as said first hydrogen feed, and that the heat of the Ch-hydrogenation be utilized for preheating of the produced syngas to a downstream synthesis gas unit.
  • the compression of the Ch-hydrogenation reaction zone inlet mixture (CO2/H2 gas mixture) is simpler, there is a main or only a single H2 addition line and furthermore it is easier to carry out the Ch-hydrogenation at high pressure.
  • said first hydrogen feed comprises O2, such as 5 vol.% O2, or less; preferably 1 vol.% or less.
  • the first hydrogen feed contains O2, which can be the case when the H2 comes from e.g. a water electrolysis unit and thereby the O2 from the H2 stream is hydrogenated in the same unit.
  • the process further comprises: - providing an electrolysis unit being fed with a water feedstock, i.e. water or steam, for producing a hydrogen-rich stream and an oxygen-rich stream;
  • a water feedstock i.e. water or steam
  • said first hydrogen feed may be provided as at least a portion of the hydrogenrich stream.
  • thermonuclear power is regarded as a renewable source. It will be understood that the term “hydro” means hydropower.
  • the S-scavenger zone operates at: 20-150°C, such as 30-80°C; and 1-90 barg, such as 20-40 barg; and/or
  • the 02-hydrogenation reaction zone operates at: 50-400°C, such as 50-350°C, preferably at 50-100°C; and 1-120 barg, such as 20-120 barg, preferably 50-110 barg.
  • the operating temperature of the S-scavenger zone is any of: 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150°C.
  • the operating pressure of the S-scavenger zone is any of 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120 barg.
  • Ch-hydrogenation reaction zone operates at 50- 100°C.
  • operation at this temperature range of 50-100°C may be conducted without the risk of sulfur poisoning when the S-scavenger zone works as intended.
  • the purified CCh-rich gas or synthesis gas may then be processed further downstream.
  • the purified CCh-rich gas is provided as feed gas to a solid oxide electrolysis (SOE) unit for thereby producing a product gas comprising CO and CO2.
  • SOE solid oxide electrolysis
  • This product gas stream may be combined with a hydrogen stream, such as hydrogen produced from an electrolysis unit being fed with a water feedstock, e.g. as recited above, thereby forming a synthesis gas suitable for downstream methanol synthesis or Fischer-Tropsch synthesis.
  • Applicant’s WO 2022136374 discloses such a process.
  • the process further comprises: iii) providing at least a portion of the synthesis gas; optionally after mixing with a second hydrogen feed, preferably the second hydrogen feed being a portion of said first hydrogen feed; supplying the synthesis gas to: a methanol synthesis unit and withdrawing therefrom a methanol product; or a Fischer-Tropsch (FT) synthesis unit and withdrawing therefrom a hydrocarbon fuel product.
  • a second hydrogen feed preferably the second hydrogen feed being a portion of said first hydrogen feed
  • supplying the synthesis gas to: a methanol synthesis unit and withdrawing therefrom a methanol product; or a Fischer-Tropsch (FT) synthesis unit and withdrawing therefrom a hydrocarbon fuel product.
  • FT Fischer-Tropsch
  • the methanol conversion may be conducted in a once-through methanol conversion process; or more traditionally by recycling unconverted synthesis gas separated from the reaction effluent and diluting the fresh synthesis gas with the recycle gas.
  • the latter is traditionally referred to as methanol synthesis loop comprising a methanol synthesis unit i.e. methanol conversion reactor.
  • FT technology is also well-known in the art and reference is particularly given to Steynberg A. and Dry M. “Fischer-Tropsch Technology”, Studies in Surface Sciences and Catalysts, vol. 152.
  • the synthesis gas has a preferred H2/CO molar ratio of about 2, such as 1.9-2.1.
  • the synthesis gas prior to supplying the synthesis gas to said methanol synthesis unit or said FT-synthesis unit, the synthesis gas is subjected to reverse water gas shift (RWGS) or combined RWGS and methanation in a RWGS reactor, optionally methana- tion in a methanation reactor.
  • RWGS reverse water gas shift
  • the synthesis gas is further conditioned to provide the module “M” of about 2, such as 1.9-2.1 for methanol synthesis, or the H2/CO molar ratio of about 2, such as 1.9-2.1 for FT-synthesis.
  • RWGS and methanation units and associated processes are also well-known in the art.
  • An integrated process and plant which comprises the recited CO2 purification, or the conditioning into syngas, and subsequent downstream synthesis, this being any of methanol synthesis and FT-synthesis.
  • the hydrocarbon fuel product is jet fuel, for instance as sustainable aviation fuel (SAF), diesel, and gasoline.
  • SAF sustainable aviation fuel
  • diesel diesel
  • gasoline gasoline
  • the methanol product may be further converted into jet fuel, for instance as sustainable aviation fuel (SAF), as well as diesel, and/or gasoline.
  • SAF sustainable aviation fuel
  • diesel diesel
  • gasoline diesel
  • the process and plant may include the source providing the feed gas comprising carbon dioxide (CO2), oxygen (O2) and a sulfur (S)-containing impurity.
  • the process further comprises, prior to step i):
  • renewable source feed being any of: a) a lignocellulosic biomass such as wood products, algae, grass, forestry waste and/or agricultural residue; b) 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 Ell Directive 2018/2001 (RED II), Annex IX, part A; c) combinations of a) and b); and withdrawing from the thermal decomposition unit said feed gas comprising carbon dioxide (CO2), oxygen (O2) and one or more sulfur (S)-containing impurities.
  • CO2 carbon dioxide
  • O2 oxygen
  • S sulfur
  • the carbon dioxide is typically captured in amine- and/or potassium carbonate-based solutions in absorber units and released as almost pure CO2 streams in stripper units, stripping off the captured CO2 from the liquid amine and/or potassium carbonate solutions.
  • SO2 and O2 are to a (limited) extent also captured in the solutions and can be released to the almost pure CO2 stream.
  • the thermal decomposition unit is any of a gasification unit, pyrolysis unit, and hydro- thermal liquefaction unit. These units are well-known in the art.
  • a plant for producing a purified CC>2-rich gas or a synthesis gas from a feed gas comprising carbon dioxide (CO2), along with oxygen (O2) and one or more sulfur (S)-containing impurities preferably in accordance with anyone of the preceding process embodiments, the plant comprising:
  • a S-scavenger zone arranged to receive said feed gas, in which the feed gas comprises at least 80 vol.% CO2 and 10 ppm-2 vol.% O2 (20,000 ppm O2), and provide a S- depleted gas;
  • said S-scavenger zone being a S-scavenger reaction zone, a S-absorp- tion zone, or a combination thereof;
  • plant item I) corresponds to step i) according to the first aspect (process) of the invention
  • plant item II) corresponds to step ii) according to the first aspect (process) of the invention.
  • any of the embodiments and associated benefits of the first aspect of the invention may be used in connection with the second aspect of the invention (plant) or vice versa.
  • Fig. 1 shows a process/plant layout according to an embodiment of the invention, in which the S-containing impurity is SO2, and the layout comprises a single SCh-scaven- ger reactor with an Ch-hydrogenation reactor arranged downstream.
  • Fig. 2 shows process/plant layout according to an embodiment of the invention, in which the S-containing impurity is SO2, and the layout comprises a dual SCh-scavenger reactor setup, along with an O2 hydrogenation reactor arranged downstream the dual SCh-scavenger reactor as well as downstream a feed gas compressor.
  • Fig. 3 is in accordance with Example 2 and shows the relationship between Ch-hydrogenation activity and temperature for conditions with and without SO2 in the S-depleted gas to the Ch-hydrogenation reactor.
  • Fig. 4 is in accordance with Example 3 and shows the evolution of SO2 capture as a function of time in a SCh-scavenger reactor loaded with an alkaline absorbent comprising K2CO3 and KHCO3 impregnated on a porous alumina carrier.
  • Fig. 5 is in accordance with Example 4 and shows the evolution of SO2 capture as a function of time in a SCh-scavenger reactor loaded with an activated carbon material.
  • the process/plant 100 comprises a SCh-scavenger reaction zone which is shown here as a SCh-scavenger reactor 102 and downstream an Ch-hydrogenation reaction zone which is shown here as Ch-hydrogenation reactor 106.
  • a feed gas 101 comprising CO2 along with the impurities SO2 and O2, i.e. a CCh-rich gas feed, is supplied to the SCh-scavenger reactor 102 comprising a fixed bed of solid material 102’, such as activated carbon, optionally under the addition of liquid or gaseous water (water vapor) via line 103, thereby providing a SCh-depleted gas 105, optionally also H2SO4 107 when the optional water 103 is added.
  • solid material 102 such as activated carbon
  • the Ch-hydrogenation reactor 106 comprises a hydrogenation catalyst 106’ and is arranged to receive: a first hydrogen feed 109 and at least a portion of the SCh-depleted gas, for instance as preheated stream 105’ which has passed through heat exchanger 104. These streams 105’ and 109 are mixed into a combined inlet 111 (Oz-iniet), herein also referred to as Ch-hydrogenation reaction zone inlet mixture, to the Ch-hydrogenation reactor 106. From the Ch- hydrogenation reactor 106 a SCh-and-Ch-depleted gas 113 is withdrawn (Oz-ouitet) as purified CCh-rich gas or synthesis gas 113. The purified CCh-rich gas or synthesis gas 113 is sent to a downstream process plant for chemical synthesis, such as methanol synthesis unit or a Fischer-Tropsch synthesis unit (not shown).
  • chemical synthesis such as methanol synthesis unit or a Fischer-Tropsch synthesis unit (not shown).
  • feed gas 201 comprising CO2 along with the impurities SO2 and O2 is optionally mixed with a stream of liquid or gaseous water 203 and supplied to a first SO2 scavenger reactor 202 being loaded with an activated carbon product 202’.
  • a large fraction of the SO2 is then converted to SO3 and optionally H2SO4, the latter being withdrawn via line 207 by washing the activated carbon bed with water.
  • a partially SCh-depleted gas 205 is withdrawn and supplied to a second SCh-scavenger reactor 202’” arranged in series and being loaded with an alkaline SO2 absorbent 202 iv .
  • the SCh-depleted gas 205’ i.e.
  • SCh-depleted gas being withdrawn from the second SO2 scavenger reactor 202’” is mixed with an amount of H2, added as a first hydrogen feed via line 209.
  • the resulting CO2/H2 gas mixture 211 herein also referred to as Ch-hydrogenation reaction zone inlet mixture, is led to a compressor 208, i.e. feed gas compressor 208, in which the gas pressure is increased and the high-pressure CO2/H2 gas mixture 21 T is then optionally heated or cooled in heat exchanger 204.
  • the temperature-controlled CO2/H2 gas mixture 211 i.e.
  • the temperature-controlled Ch-hydrogenation reaction zone inlet mixture 211 is then supplied to the Ch-hydrogenation reactor 206 in which O2 in said inlet gas mixture 211” is reacted to H2O via hydrogenation catalyst 206' and a SCh-and-Ch-depleted gas 213 is withdrawn (02-ouitet) as purified CCh-rich gas or synthesis gas 213.
  • the purified CCh-rich gas or synthesis gas 213 is sent to a downstream process plant for chemical synthesis, such as methanol synthesis unit or a Fischer-Tropsch synthesis unit (not shown).
  • a CCh-rich feed gas comprising 5,000 ppm O2 and 5 ppm SO2 is purified for subsequent synthesis to methanol.
  • the CCh-rich feed gas also contains 1 vol% H2O.
  • the SO2 is first removed by a combination of an activated carbon bed followed by a bed of alkaline absorbent material, comprising I ⁇ CCh and KHCO3 with an amount corresponding to 5% w/w K.
  • the absorbent has an SO2 capture capacity of 60 kg SCh/ton.
  • This SCh-scavenger zone here a SCh-removal unit, serves as a first CCh-purification operating at 30-80 °C.
  • the CCh-rich feed gas flow is 5,000 Nm 3 /h and the SCh-removal unit is designed to operate for about two years between shutdowns for absorbent renewal.
  • the activated carbon utilizes O2 and some H2O, both of which are present in the CCh-rich feed gas.
  • the activated carbon then oxidizes SO2 to SO3, which is then trapped in the pores of the activated carbon.
  • the SO3 is washed out as dilute sulfuric acid, H2SO4, and the activated carbon is reused and practically functions as a catalyst not being consumed in the SCh-removal.
  • the mass of KHCO3 absorbent can be greatly decreased by having a first bed of regenerable activated carbon to remove a fraction of the SO2.
  • the O2 is then hydrogenated in an Ch-hydrogenation reactor by means of H2 addition and a hydrogenation catalyst, operating in the temperature range 50-400°C.
  • the best temperature for operation depends on the downstream process equipment and whether the Ch-hydrogenation is better positioned downstream other equipment, such as a compressor, mixer, heater etc.
  • the Ch-hydrogenation activity was investigated with a hydrogenation catalyst comprises an alumina and/or silica carrier impregnated with Pt and Pd as the active components, such as the catalyst ChXtractTM by TOPSOE.
  • the hydrogenation activity was measured in a CCh-gas comprising 2.5 vol% H2, 2000 ppm O2 and either 0 or 10 ppm SO2.
  • the CCh-gas with 0 ppm SO2 is here regarded as a S-depleted gas.
  • the catalyst space velocity was 180000 Nm 3 /h/m 3 and the temperature was varied in the range 50- 350°C.
  • Inlet and outlet Ch-concentrations were measured with a dedicated O2 in CO2 sensor and Ch-hydrogenation conversion was based on the measured inlet and outlet concentrations.
  • the SCh-removal efficiency and capacity in a SCh-scavenger reactor was tested for an alkaline absorbent comprising K2CO3 and KHCO3 impregnated on a porous alumina carrier.
  • the potassium concentration was 5% w/w.
  • the absorbent was loaded in a tubular reactor and a CCh-rich feed gas comprising 5000 ppm O2 and 9 ppm SO2 was passed over the absorbent. No water was added to the feed gas.
  • the pressure was 30 barg and the reactor temperature was 80°C.
  • SO2 was measured at the inlet and outlet of the reactor by means of a gas chromatograph fitted with a PFPD detector for detecting sulfur species, such as H2S, COS and SO2.
  • the reactor was first pressurized and heated up in a N2 atmosphere, then CO2 and O2 was added and after some hours SO2 was added.
  • O2 was added as a 2 vol% O2 in N2 gas mixture and SO2 was added as a 100 ppm SO2 in CH4 for safety reasons, i.e. exposure to and detection of toxic compounds and risk of forming explosive mixtures.
  • the Ch-hydrogenation catalyst after addition of a surplus of H2 as a first hydrogen feed, efficiently hydrogenates the O2 without risking sulfur poisoning.
  • the SO2 slip starts to increase as a consequence of saturation of the absorbent and eventually the SO2 slip reaches a concentration equal to the inlet concentration.
  • the SO2 feed was stopped after 135 hours and a small trail of SO2 emissions was observed, probably due to release of loosely bound SO2 on the absorbent.
  • the fraction of SO2 reacted with the potassium and oxidized to K2SO4 by means of the O2 in the CCh-rich feed gas as well as the added O2, is stable and is not foreseen to release SO2. Based on these data, the amount of absorbent needed for the industrial plant is calculated with input from CO2- rich feed gas flow, SO2 concentration and time between replacement of the absorbent.
  • the SO2 removal efficiency in a SCh-scavenger reactor was tested for an activated carbon material in a laboratory unit.
  • the carbon material was loaded into a tubular reactor and the reactor was operated at 80°C and 30 barg pressure.
  • the CCh-rich feed gas contained 5,000 ppm O2 and 10 ppm SO2.
  • the O2 was added as a 2 vol% O2 in N2 and the SO2 was added as 100 ppm SO2 in CH4 for safety reasons, to avoid formation of an explosive atmosphere and to be able to detect leakages from the laboratory unit.
  • Experiments were carried out both without addition of water to the process gas and by intermittent addition of 0.3 vol% H2O.
  • SO2 was measured at the inlet and outlet of the reactor by means of a gas chromatograph fitted with a PFPD detector for detecting sulfur species, such as H2S, COS and SO2.
  • the reactor was first pressurized and heated up in a N2 atmosphere, then CO2 and O2 was added and after some hours SO2 was added.
  • the activated carbon After the reintroduction of water at 82 hours, the SO2 conversion is quite stable and even slightly increasing over time.
  • the results indicate that the activated carbon not only absorbs the SO2 into the pores, but also oxidizes the SO2 to SO3, which then reacts with the water to form H2SO4, which starts filling the pores of the activated carbon. If nothing else is done, the pores eventually reach a saturation point at which the SO2 concentration starts increasing. Where the formed H2SO4 is drained from the pores, either by direct flushing with water or by means of gravitational drainage, the saturation point is not reached, and the activated carbon works as a continuously working catalyst, i.e. in a continuous operation.
  • the SO2 slip from the reactor is undesirable high to act as the only SO2 removal step and the slip can be reduced by one or more of the following adjustments: a. Changing the temperature to optimize the absorption and conversion rates b. Adding more activated carbon c. Adjusting the water concentration in the process gas d. Changing the activated carbon material to another type with other properties, e.g. pore system e. Changing the activated carbon to a type, which has been impregnated with an alkaline material such as KOH, creating a dual purpose SO2 conversion and absorption material. The experiment with same conditions but without water addition, showed a much lower SO2 conversion efficiency, confirming that the activated carbon is most effective when some water vapor is present.

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Abstract

L'invention concerne un procédé et une installation de production d'un gaz riche en CO2 purifié ou d'un gaz de synthèse à partir d'un gaz d'alimentation comprenant du dioxyde de carbone (CO2), de l'oxygène (O2) et une ou plusieurs impuretés contenant du soufre (S), le procédé consistant à : i) fournir un gaz d'alimentation comprenant CO2, SO2 et O2 à une zone de piégeage de S, ladite zone de piégeage de S étant une zone de réaction de piégeage de S, une zone d'absorption de S, ou une combinaison de celles-ci, et retirer de celle-ci un gaz appauvri en S; ii) fournir une première charge d'hydrogène et au moins une partie du gaz appauvri en S, ou une combinaison de ceux-ci, à une zone de réaction d'hydrogénation de O2 et retirer de celle-ci un gaz appauvri en S et O2 en tant que gaz riche en O2 purifié ou ledit gaz de synthèse.
PCT/EP2025/063403 2024-05-22 2025-05-15 Élimination de soufre et d'oxygène à partir de flux riches en co2 Pending WO2025242536A1 (fr)

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EP24177358.9 2024-05-22

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20170152140A1 (en) * 2011-09-27 2017-06-01 Thermochem Recovery International, Inc. Method for syngas clean-up of semi-volatile organic compounds with carbonyl sulfide removal
US20190126199A1 (en) 2016-05-24 2019-05-02 Haldor Topsøe A/S A process for the purifying of a raw gas stream containing mainly c1-c5 hydrocarbons and carbon dioxide, and impurities of organic and inorganic sulfur compounds, halogenated and non-halogenated volatile organic compounds and oxygen
US11083995B2 (en) 2017-10-09 2021-08-10 Cppe Carbon Process & Plant Engineering S.A. Elimination of SO2 and CO2 from a gas
WO2022136374A1 (fr) 2020-12-22 2022-06-30 Topsoe A/S Conversion du dioxyde de carbone et de l'eau en gaz de synthèse pour la production de méthanol et de produits hydrocarbonés
US20220333015A1 (en) * 2021-04-13 2022-10-20 Infinium Technology, Llc Process for purification and conversion of carbon dioxide using renewable energy

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20170152140A1 (en) * 2011-09-27 2017-06-01 Thermochem Recovery International, Inc. Method for syngas clean-up of semi-volatile organic compounds with carbonyl sulfide removal
US20190126199A1 (en) 2016-05-24 2019-05-02 Haldor Topsøe A/S A process for the purifying of a raw gas stream containing mainly c1-c5 hydrocarbons and carbon dioxide, and impurities of organic and inorganic sulfur compounds, halogenated and non-halogenated volatile organic compounds and oxygen
US11083995B2 (en) 2017-10-09 2021-08-10 Cppe Carbon Process & Plant Engineering S.A. Elimination of SO2 and CO2 from a gas
WO2022136374A1 (fr) 2020-12-22 2022-06-30 Topsoe A/S Conversion du dioxyde de carbone et de l'eau en gaz de synthèse pour la production de méthanol et de produits hydrocarbonés
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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