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WO2009101669A1 - Procédé de récupération et de purification de méthane à partir de biogaz de fermentation à l'aide d'un adsorbant - Google Patents

Procédé de récupération et de purification de méthane à partir de biogaz de fermentation à l'aide d'un adsorbant Download PDF

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WO2009101669A1
WO2009101669A1 PCT/JP2008/052248 JP2008052248W WO2009101669A1 WO 2009101669 A1 WO2009101669 A1 WO 2009101669A1 JP 2008052248 W JP2008052248 W JP 2008052248W WO 2009101669 A1 WO2009101669 A1 WO 2009101669A1
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adsorbent
methane
tower
pressure
adsorption
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Japanese (ja)
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Jun Izumi
Hong Xiang Wang
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Adsorption Technology Industries Co Ltd
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Adsorption Technology Industries Co Ltd
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    • 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
    • B01D53/047—Pressure swing adsorption
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
    • C12M47/18—Gas cleaning, e.g. scrubbers; Separation of different gases
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
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    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40052—Recycled product or process gas
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
    • B01D2259/40066—Six
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    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/59—Biological synthesis; Biological purification

Definitions

  • the present invention relates to a method for recovering and purifying methane from biofermentation gas using an adsorbent.
  • biomass which is an organic resource derived from living organisms, instead of simply incineration.
  • biomass include food waste such as raw garbage, livestock manure, organic waste water, organic waste such as sewage sludge generated in a sewage treatment plant, resource crops or waste thereof.
  • Biogas (digestion gas) produced by anaerobic fermentation of sewage sludge generated in a sedimentation basin at a sewage treatment plant is mainly composed of methane and CO 2 , and sulfur such as hydrogen sulfide and methyl mercaptan as trace impurities. It is a gas containing. It is known that shampoo-derived siloxane compounds are contained in urban digestion gas.
  • the most frequently used method for recovering and purifying lysine is performed as follows. In this method, hydrogen sulfide and methyl mercaptan are absorbed and removed by a chemical absorption method, siloxane is adsorbed and removed by an activated carbon adsorbent, and CO 2 is absorbed and removed by another chemical absorption method.
  • an adsorbent is used to adsorb moisture, siloxane, hydrogen sulfide, and methyl mercaptan at a relatively high pressure, and then adsorb CO 2 to recover, purify, and adsorb methane.
  • a pressure swing method in which siloxane, hydrogen sulfide, methyl mercaptan, and CO 2 are removed at a relatively low pressure has been proposed.
  • activated carbon and X-type zeolite are used as the CO 2 adsorbent.
  • co-adsorption of methane accompanying CO 2 adsorption cannot be ignored, and siloxane and hydrogen sulfide used for pretreatment
  • the adsorption performance of high-silica zeolite for adsorbing methyl mercaptan is gradually deteriorated by long-term use due to precipitation of solid sulfur caused by hydrogen sulfide and methyl mercaptan, and precipitation of silica caused by siloxane.
  • An object of the present invention is to provide a method for recovering and purifying methane from biofermented gas using an adsorbent that overcomes the problems of the prior art described above.
  • the method includes the following steps: (1) Pressurize the biogas and supply it to the adsorption tower. (2) Silicalite or hydrogen sulfide, silica gel treated with acid as a moisture adsorbent, siloxane adsorbent, methane gas containing at least one of moisture, CO 2 and siloxane, hydrogen sulfide, methyl mercaptan or silicalite as a methyl mercaptan adsorbent Silicalite with acid treatment, Ca-A or Na-A type zeolite with silica coating on the crystal surface as CO 2 adsorbent, moisture, siloxane, hydrogen sulfide, methyl mercaptan, moisture under relative high pressure conditions By first adsorbing, then adsorbing CO 2 and separating it from methane, and then introducing the adsorbent adsorbing moisture, siloxane, hydrogen sulfide, methyl mercaptan, CO 2 to a relatively low pressure condition
  • step C The adsorbent adsorbing moisture, siloxane, hydrogen sulfide, methyl mercaptan, and CO 2 is guided to a relatively low pressure condition, and the respective components are desorbed from the adsorbent to regenerate the adsorbent.
  • a method for recovering and purifying methane by a pressure swing method that repeats the steps B and B is provided.
  • step A moisture, siloxane, hydrogen sulfide, methyl mercaptan, and CO 2 are adsorbed near atmospheric pressure, and desorbed under vacuum and reduced pressure conditions.
  • one column filled with the adsorbent at a relatively high pressure after completion of the adsorption step and another column filled with the adsorbent at a relatively low pressure after completion of the desorption step are connected at the rear of the column.
  • a method for recovering and purifying methane by a pressure swing method with a coexisting gas that improves methane recovery by transferring methane remaining from one tower after the adsorption process to the other tower after the desorption process is provided at the rear of the column.
  • a gas mainly composed of desorbed CO 2 is supplied to the adsorbent adsorption tower after completion of the adsorption process from the front of the tower, and methane remaining in the tower is purged from the rear of the tower to purge gas. To improve the methane recovery rate.
  • the waste is removed from the exhaust gas containing biofermented gas, and the environment is not polluted.
  • methane can be effectively recovered and used for fuel and the like, and resources can be recovered effectively.
  • biofermentation gas is generated as biogas by anaerobic fermentation of biomass, and includes moisture, CO 2 , siloxane, hydrogen sulfide, methyl mercaptan and methane and other impurities. Containing.
  • the acid-treated silica gel adsorbent used for adsorbing moisture and siloxane can be obtained by treating commercially available silica gel with an acid aqueous solution.
  • Silica gel reacts with hydroxyl groups and siloxanes, hydrolyzing siloxanes and precipitating silicic acid at the adsorption active sites, leading to a decrease in adsorption performance.
  • the silica gel is subjected to an acid treatment, the hydroxyl group is protonated and the hydrolysis of the siloxane is remarkably suppressed. For this reason, the adsorption of siloxane becomes reversible, and smooth adsorption-desorption proceeds.
  • the acid used to treat the silica gel is not particularly limited, and any acid may be used, but it is common to use sulfuric acid, nitric acid, etc., which are easily available. Further, the acid concentration of the acid aqueous solution is not particularly limited, and may be any concentration.
  • the temperature and time for treating the silica gel with the aqueous acid solution are not particularly limited, and any temperature may be used, but the higher the temperature, the shorter the treatment time.
  • the adsorbent used for adsorbing hydrogen sulfide and methyl mercaptan is silicalite or an adsorbed silicalite adsorbent.
  • a commercially available silicalite may be used.
  • Silicalite that has been subjected to acid treatment uses hydrochloric acid, phosphoric acid, boric acid, etc. as the acid, and the acid is added to pure or deionized water to prepare an aqueous solution with a pH of about 0.5-6. Suspends silicalite in an aqueous solution and stirs for about 10 minutes to 3 hours to allow the silicalite to carry an acid.
  • Hydrolysis proceeds by the reaction of the hydroxyl group with H 2 S and methyl mercaptan, and elemental sulfur is deposited at the adsorption active site, leading to a decrease in adsorption performance.
  • silicalite is used here, precipitation of elemental sulfur is suppressed because the hydroxyl group concentration on the adsorbent surface is low.
  • the silicalite is subjected to an acid treatment, the remaining hydroxyl group is protonated and the precipitation of elemental sulfur is remarkably suppressed. For this reason, the adsorption of H 2 S and methyl mercaptan becomes reversible, and smooth adsorption / desorption proceeds. You may mix and use the silicalite which performed the silicalite and the acid treatment.
  • a Ca-A or Na-A type zeolite having a silica coating on the crystal surface used for adsorbing CO 2 is obtained by suspending zeolite powder in a slurry form in a solvent, for example, methyl alcohol, to which a template, For example, when tetraethoxyorthosilicate (TEOS) is added to the crystal surface in an amount corresponding to the required thickness, and water is added thereto at a H 2 O / TEOS ratio of about 5 to 20, silica is precipitated.
  • a solvent for example, methyl alcohol
  • the surface moisture was removed at 0.5 ° C for about 0.5 to 3 hours, heated at about 30 to 80 ° C / h and maintained at about 250 to 450 ° C for about 0.5 to 3 hours to complete the dehydration of silicic acid.
  • the Si—O—Si network on the zeolite crystal surface is completed and the activation by dehydration is completed.
  • a silica thin film of 0.05 to 0.1 ⁇ m is purified on the crystal surface.
  • the amount of CO 2 adsorption is larger for Ca-A, and Na-A is larger for the CO 2 / CH 4 separation factor.
  • a silica thin film of 0.05 to 0.1 ⁇ m is purified on the crystal surface. Since Na-A has a window diameter of 4 mm, Ca-A has a window diameter of 5 mm, CO 2 molecular diameter of 3.2 mm, and CH 4 molecular diameter of 4.2 mm, both Na-A and Ca-A have CO 2 adsorption rates. CH 4 greater than the adsorption rate.
  • the silica-coated Ca-A and Na-A type zeolites may be mixed and used.
  • First step (equalization process between tower A, tower B and tower)
  • the valves 8a and 8b behind the tower are opened, and the methane remaining behind the tower A is transferred to the tower B for high efficiency. Since the pressure is recovered and the pressure in the towers A and B is equalized, smooth pressure increase for the adsorption process and smooth pressure decrease for the pressure reduction process proceed.
  • Second step (A tower-pressurization process, B tower-depressurization process)
  • the product methane is supplied from the rear of the tower A and the pressure is increased to a point close to an adsorption pressure of 80 to 150 kPA.
  • the B tower decompressed to equal pressure is connected to a vacuum pump through the valve 9b, the pressure inside the tower is reduced and adsorbed siloxane, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed.
  • siloxane is upstream of strongly adsorbed component, hydrogen sulfide, methyl mercaptan, to act as a purge gas at the time of moisture desorption significantly the partial pressure of these gases in the tower Desorption progresses with high efficiency because of lowering.
  • Biolite gas containing methane, CO 2 , moisture, hydrogen sulfide, methyl mercaptan, siloxane is treated with silicalite or acidite treated with hydrogen sulfide, methyl mercaptan as an adsorbent through flow blower 2 and valve 3a, It is supplied to a honeycomb of acid-treated silica gel as a moisture adsorbent, a siloxane adsorbent, and a Ca-A or Na-A type zeolite granular product having a silica coat on the crystal surface as a CO 2 adsorbent or a packed tower 4a of the honeycomb.
  • a honeycomb adsorbent filled with silicalite-based hydrogen sulfide, methyl mercaptan adsorbent, silica gel-based siloxane, moisture selective adsorbent, and CO 2 adsorbent of A-type zeolite silica coated product in this order from the upstream. 5 is filled.
  • the biofermentation gas supply is stopped immediately before CO 2 flows from the back of the packed tower 4a.
  • the packed tower 4b is in a state in which the CO 2 adsorption zone has moved to some extent by decompression to the rear of the tower, and is supplied from the flow path 7.
  • the product methane is supplied through the pressure reducing valve 18 and the valve 8b and brought into countercurrent contact with the adsorbent honeycomb 5, whereby siloxane, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed.
  • the same operation as the first to third steps is performed in the fourth to sixth steps by changing the A tower and the B tower.
  • the method of the present invention was carried out using the apparatus shown in FIGS. 1 and 2 under the following conditions.
  • First step (equalization process between tower A, tower B and tower)
  • the valves 8a and 8b at the rear of the tower are opened. Since the pressure in the towers A and B is equalized to about 60 kPa, smooth pressure increase for the adsorption process and smooth pressure reduction for the pressure reduction process proceed.
  • Second step (A tower-pressurization process, B tower-depressurization process)
  • the product methane is supplied from the rear of the A tower and the pressure is increased to a position close to the adsorption pressure of 120 kPa.
  • the column B reduced in pressure to about 60 kPa is connected to a vacuum pump through the valve 9b, the adsorbed siloxane, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed by reducing the pressure in the column to 10 kPa or less.
  • siloxane is upstream of strongly adsorbed component, hydrogen sulfide, methyl mercaptan, to act as a purge gas at the time of moisture desorption significantly the partial pressure of these gases in the tower Desorption progresses with high efficiency because of lowering.
  • Second step 100m 3 N / h of biofermented gas containing methane 60vol%, CO 2 35vol%, moisture 5vol%, hydrogen sulfide 100ppm, methyl mercaptan 10ppm, siloxane 100ppm is passed through the blower 2 and valve 3a through the blower 2 and valve 3a.
  • silicalite or acid-treated silicalite subjected as mercaptan adsorbent, moisture adsorbents, honeycomb silica gel acid treated as siloxane adsorbent, Ca-a was subjected to silica coated on the crystal surface as a CO 2 adsorbent or Na-a Is supplied to a granular zeolite product or honeycomb packed tower 4a.
  • the honeycomb 5 filled with the agent from the upstream in this order is filled.
  • the superficial velocity is 0.5 m / sec and the adsorption load is 650 m 3 N / h / ton.
  • the biofermentation gas supply is stopped immediately before CO 2 flows from the back of the packed tower 4a.
  • the packed tower 4b is in a state in which the CO 2 adsorption zone has moved to some extent by the decompression to the rear of the tower, and 4 m 3 N / h of product methane supplied from the flow path 17 is supplied through the pressure reducing valve 18 and the valve 8b.
  • siloxane siloxane
  • hydrogen sulfide hydrogen sulfide
  • methyl mercaptan moisture
  • CO 2 hydrochloride
  • the same operation as the first to third steps is performed in the fourth to sixth steps by changing the A tower and the B tower.
  • Example 1 Ca-A was subjected to silica-coated as CO 2 selective adsorbent, Preparation Examples and Evaluation CO 2 selective adsorbent honeycomb 5 of Na-A type zeolite, Na-A, Ca-A , Comparative evaluation of Na-A (10 nm), Ca-A (10 nm), Na-A (50 nm), Ca-A (50 nm), Na-A (100 nm), and Ca-A (100 nm) was performed.
  • the values in () of Na—A and Ca—A are the thickness of the silica coat thin film.
  • the zeolite powder is suspended in a slurry form in methyl alcohol, and tetraethoxyorthosilicate (TEOS) is added to the crystal surface at the required thickness.
  • TEOS tetraethoxyorthosilicate
  • Na-A, Ca-A and these silica-coated products showed high CO 2 adsorption performance showing a molecular sieve effect on methane.
  • Ca-A (50 nm) showed the highest CO 2 removal performance. This seems to be due to the relatively large CO 2 adsorption rate and the window diameter (crystal gas passage) that has a molecular sieving effect on methane.
  • Example 2 Preparation Example and Performance Evaluation of Silicalite Treated with Acid as Sulfur Compound-Selective Adsorbent Silicalite Silicalite (1), Silicalite (4), acid-treated as sulfur compound-selective adsorbent honeycomb 5 Siliconite (PO4-0.5), Siliconite (PO4-0.5), Siliconite (PO4-1), Siliconite (PO4-2), Siliconite (PO4-4), Siliconite (BO3-0.5), Siliconite ( BO3-0.5), Siliconite (BO3-1), Siliconite (BO3-2), Siliconite (BO3-4) and untreated silicalite were comparatively evaluated.
  • the values in () of Silicalite are the pH of the treatment solution when it is acid-treated with HCl, the carrying amount (mass%) when phosphoric acid treatment is carried, and the carrying amount (mass%) when boric acid is carried. .
  • HCl was added to pure water to prepare HCl solutions of pH 1 and pH 4, and silicalite was suspended in these aqueous solutions and stirred for 30 minutes.
  • HCl treatment, phosphoric acid dope, and boric acid dope all show durability against removal of hydrogen sulfide and methyl mercaptan during long-time operation compared to untreated silicalite. This is also confirmed from the fact that the amount of sulfur deposited on the adsorbent after operation for 720 hours is suppressed compared to untreated silicalite.
  • HCl treatment those with pH 1 showed more excellent durability, and it was evaluated that the addition of about 2 g was optimal for phosphoric acid dope and boric acid dope.
  • Example 3 Preparation Example and Performance Evaluation of Silica Gel Treated with Acid as Siloxane-Selective Adsorbent As Silica-Selective Adsorbent Honeycomb 5, acid-treated silicalite silica gel (1), silica gel (4), silica gel (PO4) -0.5), silica gel (PO4-0.5), silica gel (PO4-1), silica gel (PO4-2), silica gel (PO4-4), silica gel (BO3-0.5), silica gel (BO3-0) .5), silica gel (BO3-1), silica gel (BO3-2), silica gel (BO3-4) and untreated silica gel were comparatively evaluated.
  • silicalite silica gel (1), silica gel (4), silica gel (PO4) -0.5), silica gel (PO4-0.5), silica gel (PO4-1), silica gel (PO4-2), silica gel (PO4-4), silica gel (BO3-0.5), silica gel (
  • the values in () of silica gel are the pH of the treatment solution when it is acid-treated with HCl, the loading amount (mass%) when phosphoric acid treatment is performed, and the loading amount (mass%) when boric acid is supported. .
  • HCl was added to pure water to prepare HCl solutions of pH 1 and pH 4, and the silica gel was suspended in these aqueous solutions and stirred for 30 minutes.
  • HCl-treated silica gel shows durability against siloxane removal during long-time operation compared to untreated silica gel. This is also confirmed from the fact that the amount of silica deposited on the adsorbent after operation for 720 hours is suppressed compared to untreated silica gel.
  • those having a pH of 1 showed more excellent durability, and it was evaluated that the addition of about 2 g was the most optimal for the phosphoric acid dope and the boric acid dope.
  • the methane concentration at the outlet of the adsorption tower increases, but the methane recovery rate decreases. Therefore, when the flow rate is reduced to about 80 m 3 N / h, the methane concentration increases to 96 vol%, while when the raw material flow rate is increased to 150 m 3 N / h, the methane recovery rate increases to 95%.
  • the product methane concentration increases and reaches 98 vol% at 8 m 3 N / h.
  • the methane recovery rate is reduced to 86%.
  • the product methane purge amount is reduced to 2 m 3 N / h, the product methane concentration decreases to 84%. Since the recovery rate increases to 94%, this condition may be adopted when a high methane concentration is not required.
  • the product methane concentration increases to 94 vol%, but the product methane recovery rate remains at 72%.
  • the uniform pressure between the columns introduced so far is adopted, the product methane concentration is slightly reduced to 92 vol%, but the recovery rate is very high at 92%. It can be understood that the uniform pressure between the columns can be easily transferred from the pressure change of adsorption-desorption-adsorption, and is very effective from the viewpoint of improving the recovery rate and smooth PSA operation.
  • Example 4 In the first embodiment, the product adsorption of methane was performed in the “adsorption process” by means of pressure equalization / pressure increase / adsorption between the columns and in the “regeneration process” by pressure equalization / pressure reduction / counterflow purge between the columns. Since product methane is used as the purge gas in the countercurrent purge, the loss of product methane cannot be ignored.
  • the “regeneration process” when the adsorption tower after the adsorption process is purged with a desorption gas mainly composed of CO 2 from the front of the tower, the methane remaining in the adsorption tower is replaced with CO 2. Methane flows from the rear of the tower, and the loss of methane in the desorption process is significantly reduced.
  • Fig. 2 shows the flow sheet of the equipment at this time
  • Table 9 shows the equipment flow sheet.
  • the product methane recovery rate increases, reaching a co-current purge rate of 70% and a recovery rate of 98%.
  • the maximum value of the cocurrent purge rate should be limited to about 70%.

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Abstract

L'invention porte sur un procédé de récupération et de purification de méthane, qui est un procédé pour récupérer et purifier du méthane gazeux à partir de biogaz généré par la fermentation anaérobie de déchets organiques par un procédé modulé en pression comprenant les étapes consistant à : A : introduire du biogaz dans une tour d'adsorption par augmentation de la pression ; et B : dans la tour d'adsorption, (1) éliminer l'eau par passage du biogaz à travers un adsorbant d'eau dans des conditions de pression relativement élevée ; (2) éliminer le siloxane par adsorption de celui-ci à travers un adsorbant de gel de silice traité par un acide ; (3) éliminer le sulfure d'hydrogène et le méthylmercaptan par adsorption de ceux-ci à travers un adsorbant silicalite ou silicalite traité par un acide ; et (4) éliminer CO2 par adsorption de celui-ci à travers au moins un type d'adsorbant zéolite choisi dans le groupe constitué par les zéolites de type Ca-A et Na-A dont la surface cristalline a été recouverte par de la silice.
PCT/JP2008/052248 2008-02-12 2008-02-12 Procédé de récupération et de purification de méthane à partir de biogaz de fermentation à l'aide d'un adsorbant Ceased WO2009101669A1 (fr)

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Cited By (9)

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JP2008045060A (ja) * 2006-08-18 2008-02-28 Kyuchaku Gijutsu Kogyo Kk 吸着剤を利用したバイオ発酵ガスからのメタンの回収、精製方法
WO2011099616A1 (fr) * 2010-02-15 2011-08-18 ニッタ株式会社 Filtre chimique comprenant un agent d'imprégnation acide
WO2011110322A1 (fr) * 2010-03-12 2011-09-15 Dge Dr.-Ing. Günther Engineering Gmbh Procédé de séchage par adsorption d'un biogaz purifié et régénération d'un agent d'adsorption chargé
JP2015044175A (ja) * 2013-08-29 2015-03-12 東洋紡株式会社 シロキサン除去剤およびそれを用いたシロキサン除去フィルタ
CZ306061B6 (cs) * 2010-05-03 2016-07-20 Výzkumný ústav zemědělské techniky, v.v.i. Zařízení pro úpravu bioplynu na palivo typu zemního plynu
CN105861088A (zh) * 2016-05-24 2016-08-17 安徽瑞丝环保能源有限公司 一种沼气净化罐
WO2017059180A1 (fr) * 2015-10-01 2017-04-06 Regents Of The University Of Minnesota Matériaux et procédés d'élimination sélective de sulfure d'hydrogène présent dans un gaz corrosif
CN114854464A (zh) * 2022-04-07 2022-08-05 宁夏首朗吉元新能源科技有限公司 一种沼气净化回收装置及方法
CN117379995A (zh) * 2023-11-21 2024-01-12 中集安瑞科工程科技有限公司 一种选择性分离甲烷和乙烷气体的改性4a分子筛膜及其制备法与应用

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JP2006016439A (ja) * 2004-06-30 2006-01-19 Mitsubishi Heavy Ind Ltd ガス精製装置

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JP2001146416A (ja) * 1999-09-06 2001-05-29 Mitsubishi Chemicals Corp ゼオライト及びその製造方法ならびにゼオライトを利用した気体分離方法
JP2002058996A (ja) * 2000-08-23 2002-02-26 Nkk Corp 消化ガス精製剤および消化ガスの精製方法
JP2006016439A (ja) * 2004-06-30 2006-01-19 Mitsubishi Heavy Ind Ltd ガス精製装置

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008045060A (ja) * 2006-08-18 2008-02-28 Kyuchaku Gijutsu Kogyo Kk 吸着剤を利用したバイオ発酵ガスからのメタンの回収、精製方法
WO2011099616A1 (fr) * 2010-02-15 2011-08-18 ニッタ株式会社 Filtre chimique comprenant un agent d'imprégnation acide
JP5797564B2 (ja) * 2010-02-15 2015-10-21 ニッタ株式会社 酸性添着剤を用いたケミカルフィルタ
WO2011110322A1 (fr) * 2010-03-12 2011-09-15 Dge Dr.-Ing. Günther Engineering Gmbh Procédé de séchage par adsorption d'un biogaz purifié et régénération d'un agent d'adsorption chargé
CN102821833A (zh) * 2010-03-12 2012-12-12 Dge京特博士工程有限公司 对纯化沼气进行吸附式干燥和再生装满的吸附剂的方法
US8747522B2 (en) 2010-03-12 2014-06-10 Dge Dr.-Ing. Guenther Engineering Gmbh Method for the adsorptive drying of purified biogas and for regenerating laden adsorbents
CN102821833B (zh) * 2010-03-12 2014-07-02 Dge京特博士工程有限公司 对纯化沼气进行吸附式干燥和再生装满的吸附剂的方法
CZ306061B6 (cs) * 2010-05-03 2016-07-20 Výzkumný ústav zemědělské techniky, v.v.i. Zařízení pro úpravu bioplynu na palivo typu zemního plynu
JP2015044175A (ja) * 2013-08-29 2015-03-12 東洋紡株式会社 シロキサン除去剤およびそれを用いたシロキサン除去フィルタ
WO2017059180A1 (fr) * 2015-10-01 2017-04-06 Regents Of The University Of Minnesota Matériaux et procédés d'élimination sélective de sulfure d'hydrogène présent dans un gaz corrosif
CN105861088A (zh) * 2016-05-24 2016-08-17 安徽瑞丝环保能源有限公司 一种沼气净化罐
CN114854464A (zh) * 2022-04-07 2022-08-05 宁夏首朗吉元新能源科技有限公司 一种沼气净化回收装置及方法
CN117379995A (zh) * 2023-11-21 2024-01-12 中集安瑞科工程科技有限公司 一种选择性分离甲烷和乙烷气体的改性4a分子筛膜及其制备法与应用

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