WO2024203281A1 - Procédé de production de méthane liquéfié et appareil de production de méthane liquéfié - Google Patents

Procédé de production de méthane liquéfié et appareil de production de méthane liquéfié Download PDF

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Publication number
WO2024203281A1
WO2024203281A1 PCT/JP2024/009548 JP2024009548W WO2024203281A1 WO 2024203281 A1 WO2024203281 A1 WO 2024203281A1 JP 2024009548 W JP2024009548 W JP 2024009548W WO 2024203281 A1 WO2024203281 A1 WO 2024203281A1
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gas
methane
biogas
liquefied methane
moisture
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Japanese (ja)
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沙紀 藤井
真子 寺井
智大 西川
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Air Water Inc
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Air Water Inc
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0209—Natural gas or substitute natural gas
    • 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
    • B01D53/22—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 diffusion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0257—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/72—Refluxing the column with at least a part of the totally condensed overhead gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/50—Processes or apparatus using other separation and/or other processing means using absorption, i.e. with selective solvents or lean oil, heavier CnHm and including generally a regeneration step for the solvent or lean oil
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/80—Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/66—Landfill or fermentation off-gas, e.g. "Bio-gas"
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • 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

Definitions

  • This disclosure relates to a method for producing liquefied methane and an apparatus for producing liquefied methane.
  • Natural gas and liquefied natural gas have been attracting attention as clean energy sources that emit less carbon dioxide compared to fossil fuels such as coal and oil.
  • carbon dioxide is still emitted, and the amount of carbon dioxide emissions is steadily increasing. Therefore, there is a demand for alternative energy sources to replace natural gas and liquefied natural gas.
  • Biogas derived from livestock manure such as dairy and beef cows, food waste, and sewage sludge is attracting attention.
  • Biogas is composed of methane gas, carbon dioxide gas, nitrogen gas, etc., and is expected to be an alternative energy source to natural gas and liquefied natural gas.
  • Patent Document 1 JP 2018-188594 A discloses a method for increasing the concentration of methane gas by removing carbon dioxide from biogas using a high-pressure water absorption method
  • Patent Document 2 JP 2021-178269 A discloses a method for increasing the concentration of methane gas by removing carbon dioxide from biogas using a chemical absorption method
  • Patent Document 3 JP 2013-534863 A discloses a method for increasing the concentration of methane gas by removing carbon dioxide from biogas using a membrane separation method.
  • Patent Document 1 has problems such as the equipment becoming larger and being costly. Also, the methods described in Patent Documents 2 and 3 make it difficult to increase the purity of methane gas.
  • liquefied methane derived from biogas is used as ship and truck fuel, and a supply system has been established.
  • High-purity liquefied methane is also used as rocket fuel. As such, it is expected that demand will expand not only for methane gas, but also for liquefied methane.
  • the object of this disclosure is to provide a method and apparatus for producing liquefied methane from biogas.
  • a method for producing liquefied methane from a biogas containing methane gas, carbon dioxide gas, nitrogen gas, oxygen gas, argon gas and moisture, or from a concentrated gas obtained by concentrating methane gas in the biogas comprising: A first step of separating carbon dioxide gas and moisture from the biogas or the concentrated gas to obtain an intermediate gas; A second step of distilling and separating the intermediate gas in a distillation column to obtain liquefied methane.
  • An apparatus for producing liquefied methane from a biogas containing methane gas, carbon dioxide gas, nitrogen gas, oxygen gas, argon gas and moisture, or from a concentrated gas obtained by concentrating methane gas in the biogas comprising: A separation device for separating carbon dioxide gas and moisture from the biogas or the concentrated gas to obtain an intermediate gas; and a distillation apparatus for distilling and separating the intermediate gas to obtain liquefied methane.
  • the distillation apparatus includes a distillation column and a condenser connected to the top of the distillation column,
  • a main heat exchanger for cooling the intermediate gas The liquefied methane production apparatus according to claim 9, wherein nitrogen gas produced in the condenser is reused as a refrigerant in the main heat exchanger.
  • the present disclosure provides a method and apparatus for producing liquefied methane from biogas.
  • FIG. 1 is a schematic diagram showing an example of the configuration of a liquefied methane production apparatus according to the present embodiment.
  • FIG. 2 is a schematic diagram showing an example of a partial configuration of the liquefied methane production apparatus in this embodiment.
  • FIG. 3 is a schematic diagram showing the configuration of the liquefied methane production apparatus used in Example 1.
  • FIG. 4 is a schematic diagram showing the configuration of the liquefied methane production apparatus used in Example 2.
  • the method for producing liquefied methane in this embodiment includes a first step of obtaining an intermediate gas by separating CO2 and moisture from a biogas containing methane gas, carbon dioxide gas ( CO2 ), nitrogen gas, oxygen gas, argon gas, and moisture, or from a concentrated gas obtained by concentrating methane gas in the biogas, and a second step of obtaining liquefied methane by distilling and separating the intermediate gas in a distillation column.
  • biogas refers to a gas containing methane gas, CO 2 , nitrogen gas, oxygen gas, argon gas, and moisture.
  • the biogas may be, for example, a gas derived from at least one selected from the group consisting of livestock manure and food residue.
  • concentrations of each gas in the biogas are, for example, methane gas is 50% by volume to 60% by volume, CO 2 is 30% by volume to 40% by volume, nitrogen gas is 1% by volume to 15% by volume, oxygen gas is 0.1% by volume to 5% by volume, argon gas is 0.01% by volume to 1% by volume, and moisture is 0.01% by volume to 5% by volume. It is preferable that hydrogen sulfide is removed from the biogas in advance.
  • Concentrated gas refers to a gas obtained by concentrating methane gas in biogas.
  • concentration of methane gas in the concentrated gas is, for example, 75% by volume or more and 97% by volume or less.
  • This process is a process of obtaining intermediate gas by separating CO2 and moisture from biogas or concentrated gas.
  • the CO2 concentration in the intermediate gas is reduced to 0.0001% by volume or less.
  • the moisture in the intermediate gas is reduced to 0.0001% by volume or less.
  • separation methods in this process include temperature swing adsorption and pressure swing adsorption.
  • methods for mainly separating CO2 include separation membrane separation, high-pressure water absorption, and chemical absorption.
  • thermo Swing Adsorption Method In this method, biogas or concentrated gas is introduced into an adsorption tower filled with an adsorbent that adsorbs CO2 and moisture, and CO2 and water are separated.
  • an adsorption cycle of (1) an adsorption step, (2) a thermal regeneration step, (3) a purging step, and (4) a pressure recovery step is repeated in sequence.
  • the adsorption process is a process in which the biogas or concentrated gas is supplied to an adsorption tower and the CO2 and moisture are adsorbed by an adsorbent, thereby separating the CO2 and moisture from the biogas or concentrated gas.
  • the temperature of the supplied biogas or concentrated gas is adjusted to be, for example, 40°C or lower.
  • the adsorbent is a regenerative adsorbent that can adsorb CO2 and moisture and can recover its adsorption performance by being heated to release the adsorbed CO2 and moisture.
  • adsorbents include activated alumina, silica gel, and hydrophobic zeolite.
  • the thermal regeneration process is a process in which a gas inert to the adsorbent (hereinafter simply referred to as "inert gas”) is heated and supplied to the adsorption tower after the adsorption process, or the adsorbent is directly heated, thereby desorbing CO2 and moisture from the adsorbent.
  • the thermal regeneration process is a process in which the adsorbent filled in the adsorption tower is made reusable.
  • inert gases examples include gases from which CO2 and moisture have been removed by the adsorption process from biogas or concentrated gas, and nitrogen gas. Such gases are heated and brought into contact with the adsorbent filled in the adsorption tower, thereby increasing the temperature of the adsorbent surface and desorbing the CO2 and moisture adsorbed to the adsorbent. The adsorbent is regenerated by this process.
  • the heating temperature is, for example, 170°C or higher.
  • nitrogen gas is preferably used. In this case, it is preferable to reuse the nitrogen gas used in the second step described below. In this way, the nitrogen gas is used efficiently and the amount of nitrogen gas used throughout this manufacturing method is reduced.
  • the purge step is a step of removing the inert gas in the adsorption tower after the heating regeneration step.
  • the inert gas is removed by introducing a gas into the adsorption tower.
  • the gas introduced is, for example, a gas obtained by removing CO2 and moisture from the biogas or concentrated gas by the adsorption step.
  • This step is preferably performed multiple times until the inert gas is completely removed. Note that when the inert gas is a gas obtained by removing CO2 and moisture from the biogas or concentrated gas by the adsorption step, this step is not necessary.
  • a high-pressure gas is introduced into the adsorption tower after the desorption step to restore the pressure to the pressure required for the adsorption step.
  • the high-pressure gas used may be a gas from which CO2 and moisture have been removed by the adsorption step.
  • adsorption towers it is preferable to use a plurality of adsorption towers. For example, when two adsorption towers are used, while an adsorption step is being performed in one adsorption tower, a heating regeneration step, a purging step, and a pressure recovery step are being performed in the other adsorption tower, and by operating the two adsorption towers while switching in this manner, it is possible to continuously and efficiently separate CO2 and water from the biogas or concentrated gas.
  • the adsorption process is a process in which biogas or concentrated gas is supplied to an adsorption tower, and CO2 and moisture are adsorbed by an adsorbent, thereby separating CO2 and moisture from the biogas or concentrated gas. This process is carried out, for example, under a pressure of 0.7 MPaG or more.
  • the adsorbent is the same as the adsorbent that can be used in the above-mentioned temperature swing adsorption method, so a description thereof is omitted.
  • the desorption process is a process in which the adsorption tower after the adsorption process is depressurized to atmospheric pressure (0 MPaG) and the CO 2 and moisture adsorbed by the adsorbent are desorbed.
  • the pressure in the adsorption tower may be reduced to -0.1 MPaG by a vacuum pump.
  • Biogas or concentrated gas is introduced into a chemical absorption liquid and CO2 is separated by chemical reaction.
  • separation proceeds by reacting an alkaline compound in the chemical absorption liquid with CO2 in the biogas or concentrated gas.
  • An example of the alkaline compound is an amine compound.
  • the first step preferably includes at least one method selected from the group consisting of temperature swing adsorption and pressure swing adsorption. It is more preferable that the first step includes a plurality of separation methods. For example, when the first step includes two separation methods, it is preferable that the combination of one method selected from the group consisting of temperature swing adsorption and pressure swing adsorption and one method selected from the group consisting of membrane separation, high pressure water absorption, and chemical absorption is used. Of these, it is more preferable that separation by membrane separation and temperature swing adsorption is performed in this order. Note that when an intermediate gas is obtained from a concentrated gas, it is sufficient that the first step includes at least one method selected from the group consisting of temperature swing adsorption and pressure swing adsorption.
  • ⁇ Second step>> This process involves distilling the intermediate gas in a distillation column to obtain liquefied methane. This process includes (1) a cooling process, (2) a distillation process, and (3) a condensation process.
  • the cooling step is a step of cooling the intermediate gas obtained in the first step.
  • the temperature of the intermediate gas supplied to the cooling step is preferably 40° C. or lower.
  • the pressure of the intermediate gas during the cooling step is, for example, 0.1 to 0.8 MPaG.
  • a part of the methane gas contained in the intermediate gas may be liquefied by the cooling step.
  • the cooling step may be performed only once or may be performed multiple times.
  • the nitrogen gas in the condensation step described below may be reused as a cooling means in this step.
  • the pressure of the intermediate gas after this process may be adjusted before it is introduced into the distillation process described below.
  • the pressure during this process is usually higher than the pressure during the distillation process, so it is preferable to reduce the pressure.
  • the distillation step is a step in which the intermediate gas is introduced into a distillation column and distilled.
  • the pressure in the distillation column during the distillation step is, for example, 0.1 to 0.9 MPaG.
  • the nitrogen gas (boiling point at atmospheric pressure: -195.8°C), oxygen gas (boiling point at atmospheric pressure: -183°C), and argon gas (boiling point at atmospheric pressure: -185.8°C) contained in the intermediate gas are separated from methane gas (boiling point at atmospheric pressure: -161.6°C) due to their difference in boiling points.
  • the separated methane gas is converted into liquefied methane by heat exchange with a reboiler that is usually installed at the bottom of the distillation tower.
  • the condensation step is a step in which the methane gas that was not liquefied in the distillation step is condensed in a condenser to obtain liquefied methane.
  • the condenser is connected to the top of the distillation tower, and methane gas is introduced into the condenser from the top of the tower.
  • the methane gas introduced into the condenser is condensed, and at least a portion of it becomes liquefied methane.
  • the liquefied methane is returned to the distillation tower and recovered.
  • the methane gas introduced into the condenser is condensed, for example, by heat exchange with a refrigerant.
  • a refrigerant for example, liquid nitrogen is used as the refrigerant, and this process is carried out by supplying liquid nitrogen to the condenser.
  • the liquid nitrogen is introduced into the condenser under pressure, for example, of about 0.5 MPaG.
  • the nitrogen gas obtained in this process is preferably reused, for example, as a refrigerant for cooling the intermediate gas in the cooling process.
  • the reused nitrogen gas is also preferably reused in the purging process of the temperature swing adsorption method described above. In this way, the nitrogen gas is used effectively, and the amount of nitrogen gas used throughout this production method is reduced.
  • the liquefied methane production apparatus in this embodiment includes a separation device for obtaining an intermediate gas by separating CO2 and moisture from a biogas containing methane gas, CO2 , nitrogen gas, oxygen gas, argon gas, and moisture, or from a concentrated gas obtained by concentrating methane gas in the biogas, and a distillation device for distilling and separating the intermediate gas to obtain liquefied methane.
  • FIG. 1 is a schematic diagram showing an example of the configuration of a liquefied methane production apparatus in this embodiment.
  • the liquefied methane production apparatus 30 will be described below. Note that any explanation that overlaps with the contents explained in the above ⁇ Liquefied methane production method> will be omitted.
  • This device is a device for separating CO2 and moisture from biogas or concentrated gas to obtain an intermediate gas.
  • separation devices include temperature swing adsorption separation devices and pressure swing adsorption separation devices.
  • Devices that mainly separate CO2 include membrane separation devices, high-pressure water absorption devices, and chemical absorption devices. Note that FIG. 1 shows a membrane separation device 1 and a temperature swing adsorption device 10 as separation devices.
  • This apparatus is equipped with an adsorption tower 11 that adsorbs CO2 and moisture contained in the biogas or concentrated gas.
  • the adsorption tower 11 is filled with an adsorbent for adsorbing CO2 and moisture.
  • each step of the temperature swing adsorption method described above is performed, thereby separating CO2 and moisture from the biogas or concentrated gas.
  • the present apparatus is preferably equipped with a heating means 12.
  • the heating means 12 heats the inert gas used in the above-mentioned thermal regeneration process to such an extent that the adsorbent filled in the adsorption tower can be reused.
  • the heating means 12 There are no particular limitations on the heating means 12, but examples include a heater.
  • Temperature swing adsorption separation apparatus 10 preferably includes a plurality of adsorption towers 11.
  • temperature swing adsorption separation apparatus 10 is configured with two adsorption towers (adsorption tower 11a, adsorption tower 11b), and biogas or concentrated gas is alternately discharged to adsorption tower 11a and adsorption tower 11b, thereby enabling continuous and efficient separation of CO2 and moisture from the biogas or concentrated gas.
  • This apparatus (Pressure Swing Adsorption Separation Device) This apparatus (not shown) is equipped with an adsorption tower that adsorbs CO2 and moisture contained in the biogas or concentrated gas.
  • the adsorption tower is filled with an adsorbent for adsorbing CO2 and moisture.
  • each step of the pressure swing adsorption method described above is performed, thereby separating CO2 and moisture from the biogas or concentrated gas.
  • Membrane separation device This device is equipped with a separation membrane module (not shown) for selectively allowing CO2 contained in the biogas or concentrated gas to permeate.
  • the biogas or concentrated gas is discharged to the separation membrane module by a compressor (not shown), and the CO2 contained in the biogas or concentrated gas is separated by the separation membrane. Since the CO2 separated by the membrane separation device may contain methane gas, the separated CO2 may be separated again by the membrane separation device into CO2 and methane gas, and the methane gas may be recovered and recycled.
  • This apparatus (not shown) is equipped with a high-pressure absorption tower that absorbs the CO2 contained in the biogas or concentrated gas.
  • the high-pressure absorption tower contains water for absorbing the CO2 .
  • the biogas or concentrated gas is delivered to the high-pressure absorption tower by a compressor, and the CO2 contained in the biogas or concentrated gas is separated.
  • This apparatus (not shown) is equipped with an absorption tower that absorbs the CO2 contained in the biogas or concentrated gas.
  • the absorption tower contains a treatment liquid for absorbing the CO2 .
  • the biogas or concentrated gas is led to the absorption tower, and the CO2 contained in the biogas or concentrated gas is separated.
  • the separation device includes at least one device selected from the group consisting of a temperature swing adsorption separation device and a pressure swing adsorption separation device. It is more preferable that the separation device includes multiple separation devices. For example, when the separation device includes two separation devices, it is preferable that the separation device is a combination of one device selected from the group consisting of a temperature swing adsorption separation device and a pressure swing adsorption separation device and one device selected from the group consisting of a membrane separation device, a high-pressure water absorption device, and a chemical absorption device. Of these, it is more preferable that separation using the membrane separation device and the temperature swing adsorption separation device is performed in this order. Note that when an intermediate gas is obtained from a concentrated gas, it is sufficient that the separation device includes at least one separation device selected from the group consisting of a temperature swing adsorption separation device and a pressure swing adsorption separation device.
  • Fig. 2 is a schematic diagram showing an example of the configuration of the distillation apparatus. The following description will be given with reference to Fig. 2.
  • the intermediate gas obtained by the separation device is cooled, for example, by the main heat exchanger 21.
  • the main heat exchanger 21 it is preferable to reuse nitrogen gas, which will be described later, as a refrigerant.
  • nitrogen gas, oxygen gas, and argon gas that are separated in the distillation column 23 and not condensed in the condenser 24 may also be reused as refrigerants.
  • the pressure of the intermediate gas cooled by the main heat exchanger 21 may be adjusted, for example, by a pressure reducing valve (not shown) before being introduced into the distillation column 23.
  • the intermediate gas cooled by the main heat exchanger 21 is introduced into the distillation tower 23 and distilled. From the viewpoint of increasing the efficiency of distillation, it is preferable that the intermediate gas is introduced into the distillation tower 23 from the center of the tower by providing an inlet at the center of the tower.
  • the liquefied methane distilled and separated in the distillation tower 23 is taken out from the bottom of the distillation tower 23 and sent to the storage tank 25.
  • the intermediate gas cooled by the main heat exchanger 21 is usually introduced into the distillation tower 23 through a reboiler 22 installed at the bottom of the distillation tower 23.
  • a reboiler 22 installed at the bottom of the distillation tower 23.
  • some of the methane gas in the intermediate gas is liquefied, and the intermediate gas and liquefied methane are introduced into the distillation tower 23 in a mixed state.
  • the methane gas that is not liquefied in the distillation tower 23 is condensed by the condenser 24 connected to the top of the distillation tower 23, and at least a portion of it becomes liquefied methane.
  • the liquefied methane is returned to the distillation tower 23 and sent to the storage tank 25.
  • the methane gas introduced into the condenser 24 is condensed, for example, by heat exchange with a refrigerant.
  • a refrigerant for example, liquid nitrogen is used as the refrigerant.
  • the nitrogen gas is preferably reused, for example, as a refrigerant for cooling the intermediate gas in the main heat exchanger 21.
  • the nitrogen gas reused in the main heat exchanger 21 is preferably reused in the temperature swing adsorption separation device 10 described above.
  • the nitrogen gas, oxygen gas, and argon gas in the intermediate gas separated by the distillation column 23 are also introduced into the condenser 24.
  • These non-liquefied gases such as nitrogen gas, oxygen gas, and argon gas may be exhausted or reused as a refrigerant to cool the intermediate gas in the main heat exchanger 21.
  • the distillation apparatus may include a tank 26 for holding liquid nitrogen.
  • the melting point of liquefied methane is -182.5°C
  • the liquid nitrogen used in this embodiment is introduced into the condenser 24 under a pressure of about 0.5 MPaG.
  • the liquid nitrogen in this case is hotter than normal liquid nitrogen (e.g., -180 to -175°C) and is close to the melting point of liquefied methane. If the pressure of the liquid nitrogen drops, there is a risk that the liquefied methane will solidify in the condenser 24. Therefore, by installing a tank 26 for storing liquid nitrogen to suppress a drop in the temperature of the liquid nitrogen in the condenser 24, it is possible to prevent the condenser 24 from overcooling.
  • Example 1 A liquefied methane production apparatus having the configuration shown in FIG. 3 was prepared. Biogas derived from livestock manure was prepared. The concentrations of each gas in the biogas are as shown in point 1 of Table 1.
  • the first step was performed in the order of membrane separation method and temperature swing adsorption method, and then the second step was performed.
  • the membrane separation device a hollow fiber membrane was used as the separation membrane, and in the temperature swing adsorption separation device, zeolite was used as the adsorbent.
  • nitrogen gas obtained by vaporizing a part of the liquid nitrogen that was heat exchanged with methane gas in the condenser and nitrogen gas, oxygen gas, and argon gas separated by distillation were used. Note that the biogas at point 1 is compressed by a compressor.
  • the flow rate, pressure, temperature, and composition at points 1 to 6 in Figure 3 are shown in Table 1.
  • the composition at each point was analyzed by gas chromatography (GAS5000F HPID, manufactured by J Science Labs, Inc.).
  • Example 2 A liquefied methane production apparatus having the configuration shown in Fig. 4 was prepared.
  • a concentrated gas was prepared by concentrating the methane gas in the biogas used in Example 1. The concentrations of each gas in the concentrated gas are as shown in point 1 of Table 2.
  • the first step was performed in the order of the temperature swing adsorption method, and then the second step was performed.
  • the same temperature swing adsorption separation apparatus in the first step and the distillation apparatus in the second step were used as in Example 1.
  • the concentrated gas at point 1 was compressed by a compressor.
  • Example 1 liquefied methane with a purity of 99.99% or more was obtained from biogas containing 50% by volume of methane gas. In addition, the recovery rate of the liquefied methane was 95% by volume.
  • Example 2 liquefied methane with a purity of 99.99% or more was obtained from the concentrated gas obtained by concentrating the methane gas in the same biogas as in Example 1.
  • the recovery rate of the liquefied methane was 95% by volume.

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  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

L'invention concerne un procédé de production de méthane liquéfié à partir d'un biogaz contenant un gaz méthane, un gaz dioxyde de carbone, un gaz azote, un gaz oxygène, un gaz argon et de l'eau ou un gaz enrichi obtenu par enrichissement du gaz méthane dans le biogaz, le procédé comprenant une première étape comprenant la séparation du dioxyde de carbone gazeux et l'eau du biogaz ou du gaz enrichi pour produire un gaz intermédiaire et une seconde étape comprenant la soumission du gaz intermédiaire à une séparation par distillation au moyen d'une colonne de distillation pour produire du méthane liquéfié.
PCT/JP2024/009548 2023-03-24 2024-03-12 Procédé de production de méthane liquéfié et appareil de production de méthane liquéfié Ceased WO2024203281A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5472203A (en) * 1977-11-21 1979-06-09 Air Prod & Chem Production of liquefied methane
JPS5981483A (ja) * 1982-08-30 1984-05-11 エア・プロダクツ・アンド・ケミカルズ・インコ−ポレイテツド メタンの液化方法
JP2001162101A (ja) * 1999-12-13 2001-06-19 Tokyo Gas Co Ltd 蒸留用コンデンサ及び蒸留塔
JP2007297605A (ja) * 2006-04-04 2007-11-15 Taiyo Nippon Sanso Corp メタン分離方法、メタン分離装置及びメタン利用システム
JP2009242773A (ja) * 2008-03-14 2009-10-22 Air Water Inc メタンガス濃縮装置および方法ならびに燃料ガスの製造装置および方法
WO2022162059A1 (fr) * 2021-01-29 2022-08-04 Hitachi Zosen Inova Ag Procédé d'élimination de co2 provenant d'un gaz contenant du méthane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5472203A (en) * 1977-11-21 1979-06-09 Air Prod & Chem Production of liquefied methane
JPS5981483A (ja) * 1982-08-30 1984-05-11 エア・プロダクツ・アンド・ケミカルズ・インコ−ポレイテツド メタンの液化方法
JP2001162101A (ja) * 1999-12-13 2001-06-19 Tokyo Gas Co Ltd 蒸留用コンデンサ及び蒸留塔
JP2007297605A (ja) * 2006-04-04 2007-11-15 Taiyo Nippon Sanso Corp メタン分離方法、メタン分離装置及びメタン利用システム
JP2009242773A (ja) * 2008-03-14 2009-10-22 Air Water Inc メタンガス濃縮装置および方法ならびに燃料ガスの製造装置および方法
WO2022162059A1 (fr) * 2021-01-29 2022-08-04 Hitachi Zosen Inova Ag Procédé d'élimination de co2 provenant d'un gaz contenant du méthane

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