WO2017159663A1 - 二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素処理システム - Google Patents

二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素処理システム Download PDF

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Publication number
WO2017159663A1
WO2017159663A1 PCT/JP2017/010143 JP2017010143W WO2017159663A1 WO 2017159663 A1 WO2017159663 A1 WO 2017159663A1 JP 2017010143 W JP2017010143 W JP 2017010143W WO 2017159663 A1 WO2017159663 A1 WO 2017159663A1
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Prior art keywords
carbon dioxide
silica gel
adsorbent
amine compound
dioxide adsorbent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2017/010143
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English (en)
French (fr)
Inventor
雄志 奥村
将大 根上
克浩 吉澤
明人 川野
嘉道 野村
英和 岩▲崎▼
祥平 西部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kawasaki Heavy Industries Ltd
Kawasaki Motors Ltd
Original Assignee
Kawasaki Heavy Industries Ltd
Kawasaki Jukogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kawasaki Heavy Industries Ltd, Kawasaki Jukogyo KK filed Critical Kawasaki Heavy Industries Ltd
Priority to CN201780016986.3A priority Critical patent/CN108778489B/zh
Priority to US16/085,044 priority patent/US11185842B2/en
Priority to AU2017232470A priority patent/AU2017232470B2/en
Publication of WO2017159663A1 publication Critical patent/WO2017159663A1/ja
Anticipated expiration legal-status Critical
Priority to US17/510,506 priority patent/US11529608B2/en
Ceased legal-status Critical Current

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    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a carbon dioxide adsorbent that reversibly adsorbs carbon dioxide contained in a gas to be treated, a method for producing the same, and a system using the carbon dioxide adsorbent.
  • Patent Documents 1 and 2 disclose this type of carbon dioxide separation system.
  • the carbon dioxide separation system (carbon dioxide removal system) described in Patent Document 1 includes a container containing a carbon dioxide adsorbent, and reversibly removes carbon dioxide from a gas to be treated in which the carbon dioxide adsorbent is introduced into the container.
  • Adsorb The carbon dioxide adsorbent comprises an amine, a carbon dioxide activated catalyst, and a porous material that supports the amine and the catalyst.
  • one cycle including an “adsorption process” in which the carbon dioxide adsorbent adsorbs and removes carbon dioxide from the gas to be treated and a “desorption process” in which the carbon dioxide adsorbed from the carbon dioxide adsorbent is desorbed.
  • Processing is performed by a “batch processing method” in which processing steps are repeated.
  • processing is performed by a “continuous processing method” in which an adsorption step and a desorption step are continuously performed in parallel.
  • the carbon dioxide separation system described in Patent Document 2 includes a hopper that is sequentially arranged downward in the vertical direction, an adsorption tower in which an adsorption process is performed, a desorption tower (regeneration tower) in which a desorption process is performed, and a drying tower that dries the adsorbent. And a cooling tower for cooling the adsorbent, and a conveyor for transferring the adsorbent from the cooling tower to the hopper.
  • the carbon dioxide adsorbent accommodated in the hopper moves by its own weight in the order of the adsorption tower, the desorption tower, the drying tower, and the cooling tower, and is conveyed from the cooling tower to the hopper by the conveyor.
  • the carbon dioxide adsorbent In the adsorption tower and desorption tower, a moving bed is formed by the carbon dioxide adsorbent that descends in the tower and the gas that rises in each tower.
  • the carbon dioxide adsorbent is a porous material carrying an amine compound, and examples of the porous material include activated carbon and activated alumina.
  • the carbon dioxide adsorbent In the system of Patent Document 1, the carbon dioxide adsorbent is stationary with respect to the container. On the other hand, in the system of Patent Document 2, the carbon dioxide adsorbent moves relative to the container, and friction and collision occur between the carbon dioxide adsorbent and the container and between the carbon dioxide adsorbents. Therefore, particularly in the continuous processing method, higher strength (particularly, abrasion resistance) is required than the carbon dioxide adsorbent used in the batch processing method.
  • the present invention has been made in view of the above circumstances, and its purpose is to provide a carbon dioxide adsorbent having excellent adsorptivity and strength sufficient to withstand use in a continuous processing method, and a method for producing the same, Another object is to provide a system using a carbon dioxide adsorbent.
  • the method for producing a carbon dioxide adsorbent according to the present invention comprises: Preparing an aqueous amine solution having an amine compound concentration of 5% to 70% and a temperature of 10 ° C to 100 ° C; Impregnating the aqueous amine solution with silica gel; And air-drying the silica gel carrying the amine compound,
  • the silica gel has a particle size of 1 mm to 5 mm, an average pore size of 10 nm to 100 nm, and a pore volume of 0.1 cm 3 / g to 1.3 cm 3 / g. It is said. However, the particle diameter, the pore volume, and the average pore diameter are all values in silica gel in a state where no amine compound is supported.
  • the carbon dioxide adsorbent according to the present invention has a particle size of 1 mm to 5 mm, an average pore size of 10 nm to 100 nm, and a pore volume of 0.1 cm 3 / g to 1.3 cm 3. It is characterized by comprising an amine compound supported on silica gel of / g or less.
  • a carbon dioxide treatment system includes an adsorption tank in which a moving bed is formed by the carbon dioxide adsorbent, and a gas to be treated containing carbon dioxide is supplied to a lower part of the adsorption tank.
  • a processing gas supply port is provided, and an off-gas discharge port for discharging off-gas from which the carbon dioxide is adsorbed and removed by the carbon dioxide adsorbent is provided at the upper portion of the adsorption tank.
  • a carbon dioxide adsorbent having excellent carbon dioxide adsorption performance and wear resistance that can withstand use in a continuous treatment type carbon dioxide treatment system is provided. be able to.
  • a carbon dioxide adsorbent having excellent adsorptivity and strength sufficient to withstand use in a continuous processing system, a manufacturing method thereof, and a system using the carbon dioxide adsorbent are provided. be able to.
  • FIG. 1 is a diagram showing a schematic configuration of a carbon dioxide treatment system in which a carbon dioxide adsorbent according to the present invention can be used.
  • FIG. 2A is a diagram schematically showing the particle diameter of silica gel.
  • FIG. 2B is a diagram schematically showing the pore volume and pore diameter of silica gel.
  • FIG. 3 is a chart showing the relationship between the carbon dioxide-air diffusion resistance in the porous material and the pore diameter.
  • FIG. 4 is a chart showing the relationship between the pore volume of silica gel and the carbon dioxide adsorption amount of an adsorbent obtained by supporting diethanolamine on silica gel.
  • FIG. 5 is a chart showing the results of the rotational wear test of silica gel.
  • the carbon dioxide adsorbent according to the present invention (hereinafter sometimes simply referred to as “adsorbent”) is used for reversibly adsorbing and removing carbon dioxide from a gas to be treated containing carbon dioxide.
  • This adsorbent has excellent carbon dioxide adsorption ability and wear resistance, and is suitable for use in a system that adsorbs and removes carbon dioxide from a gas to be treated by a continuous treatment method.
  • FIG. 1 shows a schematic configuration of a carbon dioxide treatment system 1 in which a carbon dioxide adsorbent can be used.
  • a carbon dioxide treatment system 1 shown in FIG. 1 has a carbon dioxide separation system 1A that selectively separates carbon dioxide contained in a gas to be treated using an adsorbent, and desorbs (desorbs) carbon dioxide from the adsorbent. This is a continuous processing system combined with a carbon dioxide recovery system 1B for recovery.
  • the carbon dioxide treatment system 1 includes an adsorption tank 11, a desorption tank 12, a drying tank 13, and a conveyor 15 that conveys the adsorbent from the outlet of the drying tank 13 to the inlet of the adsorption tank 11.
  • the adsorbent 11, the desorption tank 12, and the drying tank 13 are arranged in the vertical direction from the top so that the adsorbent moves by gravity from the adsorption tank 11 to the drying tank 13.
  • the adsorbent transported by the conveyor 15 is supplied to the adsorption tank 11 at a predetermined supply speed from an inlet provided in the upper part. Further, the adsorbent is discharged at a predetermined discharge speed from an outlet provided in the lower portion of the adsorption tank 11.
  • the gas to be processed generated by the gas source to be processed 35 is introduced through the gas supply pipe 36 to be processed.
  • the gas to be treated is, for example, a gas near atmospheric pressure containing 10 to 30% carbon dioxide, such as combustion exhaust gas.
  • the gas supply pipe 36 to be processed may be provided with at least one pretreatment tank 37.
  • the gas to be treated is cooled to a temperature suitable for the carbon dioxide adsorption reaction.
  • the gas to be treated introduced into the adsorption tank 11 may be subjected to pretreatment such as desulfurization, dust removal, temperature reduction, and dehumidification in addition to cooling.
  • a moving layer is formed in which the gas to be processed that flows upward and the adsorbent that moves downward are in contact with each other.
  • the adsorbent in contact with the gas to be processed selectively adsorbs carbon dioxide contained in the gas to be processed.
  • the temperature of the adsorbent at that time is 40 ° C., for example.
  • the treated gas (off-gas) from which carbon dioxide has been separated and removed is discharged from the upper part of the adsorption tank 11.
  • the adsorbent that has adsorbed carbon dioxide is discharged from the lower part of the adsorption tank 11 and moves to the inlet of the desorption tank 12 by its own weight.
  • the adsorbent that adsorbs carbon dioxide is supplied from the inlet provided in the upper part, and the adsorbent is discharged from the outlet provided in the lower part at a predetermined discharge speed. It moves at a predetermined speed from the top to the bottom. Further, desorption water vapor supplied from the steam generator 38 is supplied to the lower part of the desorption tank 12.
  • a moving layer is formed in which the desorption water vapor flowing upward and the adsorbent moving downward are in contact with each other.
  • the desorption water vapor and the adsorbent come into contact with each other, the desorption water vapor condenses on the surface of the adsorbent and releases heat of condensation at that time. Carbon dioxide is desorbed from the adsorbent using the heat of condensation as desorption energy.
  • a carbon dioxide holder 17 is connected to the top of the desorption tank 12 through a carbon dioxide recovery pipe 31.
  • the carbon dioxide recovery pipe 31 is provided with a pump 16 that sends the gas in the desorption tank 12 to the carbon dioxide holder 17.
  • the gas (that is, carbon dioxide) in the desorption tank 12 is forcibly exhausted to the carbon dioxide recovery pipe 31, compressed by the pump 16, and stored in the carbon dioxide holder 17.
  • the adsorbent containing the condensed water after desorption of carbon dioxide is discharged from the lower part of the desorption tank 12 and moves to the inlet of the drying tank 13 by its own weight.
  • the adsorbent containing condensed water is supplied from the inlet provided in the upper part, and the adsorbent is discharged from the outlet provided in the lower part at a predetermined discharge speed, so that the adsorbent is stored in the tank. It moves at a predetermined speed from the top to the bottom.
  • the adsorbent is dried while moving in the drying tank 13.
  • the drying of the adsorbent is performed by contact between the drying gas supplied from the drying gas source 39 to the lower portion of the drying tank 13 and flowing upward in the tank, and the adsorbent moving downward in the tank. Done.
  • the drying gas (dry exhaust gas) used for drying the adsorbent is discharged from the upper part of the drying tank 13.
  • the dried adsorbent is discharged from the lower part of the drying tank 13, falls onto the conveyor 15, is transferred to the adsorption tank 11 while being cooled by the conveyor 15, and is reused as an adsorbent for carbon dioxide.
  • the adsorbent (carbon dioxide adsorbent) used in the carbon dioxide treatment system 1 is formed by supporting an amine compound on silica gel.
  • the above-described amine compound is at least one selected from the group consisting of amines having at least one hydroxyl group and polyamines. That is, the amine compound may contain a mixture of amines and polyamines. Such amines and polyamines are known to reversibly desorb carbon dioxide, that is, adsorb and desorb carbon dioxide. Examples of the amine compound containing amines having at least one hydroxyl group include monoethanolamine, diethanolamine, and triethanolamine. Examples of the amine compound containing polyamines include polyethyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • the particle diameter of the silica gel is 1 mm or more and 5 mm or less.
  • the pore volume of silica gel is 0.1 cm 3 / g or more and 1.3 cm 3 / g or less.
  • the average pore diameter of silica gel is 10 nm or more and 100 nm or less.
  • the particle diameter, pore volume, and average pore diameter are all values in silica gel in which no amine compound is supported.
  • FIG. 2A is a diagram schematically showing the particle diameter of silica gel
  • FIG. 2A is a diagram schematically showing the pore volume and pore diameter of silica gel
  • FIG. 2B shows an enlarged cross section near the surface of the silica gel.
  • silica gel is a spherical particle.
  • “spherical” particles do not necessarily mean true spherical particles, and are particles having a shape in which 90% by mass or more falls when placed on a smooth plate inclined by about 30 ° from the horizontal. .
  • the carbon dioxide adsorbent based on silica gel having a particle diameter of 1 mm to 5 mm also has a particle diameter of 1 mm to 5 mm.
  • Silica gel carries an amine compound, but the amine compound enters the pores formed inside the silica gel, so that the diameter of the silica gel is not greatly expanded by carrying the amine compound.
  • the adsorbent fluidizes with a small amount of gas, and the moving bed cannot be established.
  • the particle diameter of the carbon dioxide adsorbent exceeds 5 mm, the weight increases with the increase in the particle diameter of the adsorbent, so that the wear due to the impact received at the time of dropping becomes severe and the life of the adsorbent is remarkably shortened. Therefore, by using a carbon dioxide adsorbent having a particle diameter in the range of 1 mm or more and 5 mm or less, it becomes easy to form a moving bed in which the adsorbent and the gas to be treated are preferably in countercurrent contact, and the adsorbent. Can give a proper lifespan.
  • the “particle diameter” of carbon dioxide and silica gel is the particle diameter.
  • the particle diameters of carbon dioxide and silica gel can be measured, for example, by the following steps (1) to (4).
  • (1) Arrange 100 or more silica gel samples on a black felt so that the particles do not contact each other as much as possible.
  • (2) Photograph the particles of the silica gel sample with a field of view of 100 mm ⁇ 140 mm.
  • (3) The imaged software ImageJ (National Institutes of Health NIH) is used to binarize the photographed image and determine the area of each particle.
  • the average pore diameter of the silica gel is an average value of the diameters of the pores opened on the surface of the silica gel.
  • the pore volume of silica gel is the volume of the pores.
  • the pore volume of silica gel is determined by the mercury intrusion method.
  • the average pore diameter of silica gel is obtained by obtaining the pore diameter distribution by the mercury intrusion method, and the average pore diameter (median diameter) is the pore diameter when 50% of the total pore volume of mercury is injected. is there.
  • the mercury intrusion method is a method that uses the high surface tension of mercury to apply pressure to inject mercury into the pores of the powder, and obtains the specific surface area and pore distribution from the pressure and the amount of mercury intruded. Yes, for example, it can be obtained by using a mercury porosimeter (PASCL240) manufactured by Thermo Qurest Italy.
  • the average pore diameter of silica gel has a significant effect on the adsorption rate of the adsorbent.
  • the adsorption rate of the adsorbent depends on the carbon dioxide diffusion rate in the pores and the adsorption reaction rate of the adsorbent. Of these, the adsorption reaction rate is sufficiently faster than the carbon dioxide diffusion rate in the pores, so the adsorption rate of the adsorbent is actually limited by the carbon dioxide diffusion rate in the pores.
  • FIG. 3 is a chart showing the relationship between the carbon dioxide-air diffusion resistance in the porous material and the pore diameter. From FIG. 3, it can be seen that when the pore diameter is smaller than about 10 nm, the carbon dioxide-air diffusion resistance increases rapidly and remarkably. This is considered because the ratio of Knudsen diffusion to the total diffusion resistance in the pores is 90% or more. Therefore, when the average pore diameter of silica gel is smaller than about 10 nm, it is considered difficult to cause carbon dioxide to be saturated and adsorbed on the adsorbent within a realistic processing time.
  • the average pore diameter of the silica gel exceeds 100 nm, the strength of the silica primary particle skeleton constituting the silica gel is lowered, so that the particle strength required for the adsorbent is not satisfied.
  • the carbon dioxide adsorption rate of the adsorbent can be maintained in a suitable range, and the particle strength required for the adsorbent can be provided.
  • the average pore diameter of silica gel can be controlled by subjecting the silica gel to a steaming treatment. More specifically, the average pore diameter can be controlled between 10 nm and 100 nm by adjusting the pressure during steaming and the pH of the xerogel.
  • the steaming treatment is usually carried out by circulating steam under pressure in an autoclave, and the treatment time is usually 10 minutes to 24 hours. The pressure at this time is 0.5 to 20 kg / cm 2 .
  • the pH of the xerogel during the steaming process is preferably controlled to 5-9.
  • FIG. 4 is a chart showing the relationship between the pore volume of silica gel and the amount of carbon dioxide adsorption of an adsorbent comprising diethanolamine (amine solution concentration 40%) supported on silica gel. It can be seen from FIG. 4 that carbon dioxide can be adsorbed with an adsorbent having a pore volume of silica gel of approximately 0.1 cm 3 / g or more.
  • silica gel having a pore volume of 0.1 cm 3 / g or more and 1.3 cm 3 / g or less carbon dioxide can be adsorbed and the particle strength required for the adsorbent can be given. it can.
  • a condition that the specific surface area is 10 m 2 / g or more and 300 m 2 / g or less may be added to silica gel having a particle diameter of 1 mm or more and 5 mm.
  • the specific surface area of silica gel can be determined by mercury porosimetry as with the average pore diameter and pore volume.
  • an aqueous amine solution having an amine compound concentration of 5% to 70% and a temperature of 10 ° C to 100 ° C is prepared.
  • the temperature of the aqueous amine solution is 10 ° C. or higher.
  • the temperature of the aqueous amine solution is preferably 10 ° C. or higher and 100 ° C. or lower.
  • the concentration of the amine compound in the aqueous amine solution is desirably an appropriate value corresponding to the amine compound in the range of 5% to 70%.
  • the concentration of the amine compound in the aqueous amine solution is appropriately 5% to 55%.
  • the amine compound is polyethyleneimine, since the viscosity is high, a concentration of about 10% is preferable.
  • the concentration of the amine compound in the aqueous amine solution is less than the lower limit, the amount of the amine compound supported on the silica gel is not sufficient, and the amount of drainage after the supporting treatment becomes enormous.
  • the concentration of the amine compound in the aqueous amine solution exceeds the upper limit, the amine compound may block the pores of the silica gel and reduce the adsorption performance of the adsorbent.
  • the concentration of the amine compound is within the range of 5 to 70%, the amount of the amine supported on the silica gel increases as the concentration of the amine compound in the aqueous amine solution increases, and the specific gravity of the adsorbent and the carbon dioxide adsorption amount of the adsorbent.
  • the impregnation time of silica gel can be set to 24 hours, for example.
  • the silica gel carrying the amine compound is dried by ventilation at a temperature close to room temperature.
  • the adsorbent can be manufactured through the above steps.
  • silica gel having water resistance is defined as silica gel having a water resistance N defined by the following formula (1) of 45% or more.
  • N (W / W 0 ) ⁇ 100 (1)
  • N Water resistance of silica gel [%]
  • W 0 Total number of silica gel particles immersed in water [pieces]
  • W Number of W 0 that did not crack [number]
  • water-resistant spherical silica As the silica gel having water resistance as described above, commercially available water-resistant spherical silica may be used.
  • This water-resistant spherical silica is obtained by, for example, calcining a spherical silica xerogel obtained by neutralizing an aqueous alkali silicate solution at a temperature of 100 to 1000 ° C. by superheat steam at 500 to 1000 ° C. Can be manufactured.
  • the inventors confirmed that the silica gel is hardly cracked or cracked in the step of impregnating the silica gel into the aqueous amine solution in the adsorbent production method. Has been. *
  • Samples of carbon dioxide adsorbent were prepared by the following procedures (1) to (5).
  • the weight ratio of the base material to the drug was set to 1: 3.
  • the base material is taken out from (3) and centrifuged (1100 rpm).
  • the container is filled, and a dry gas (nitrogen gas at 40 ° C., 15 L / min) is supplied to dry the substrate carrying the drug by ventilation. It should be noted that after 2 hours from the time when the gas temperature at the outlet of the drying tank for drying the substrate carrying the drug was stabilized, the drying completion condition of the substrate carrying the drug (that is, the carbon dioxide adsorbent) was set.
  • a dry gas nitrogen gas at 40 ° C., 15 L / min
  • the carbon dioxide adsorption test (column test) of the carbon dioxide adsorbent sample was performed according to the following procedures (1) to (4).
  • the sample is tightly filled in an adsorption tank having an inner diameter of 25 mm to a height of 300 mm. Here, the sample filled was 147 mL.
  • (2) Flow the adsorbed gas through the bypass line and confirm that the concentration is 10.0%.
  • the adsorption gas is 10% by volume of carbon dioxide, humidity of 5% RH or less, and air at 25 ° C.
  • the superficial velocity of the adsorbed gas is 0.05 m / s.
  • the amine compound of sample 1 and sample 2 is diethanolamine (DEA)
  • the amine compound of sample 2 and sample 3 is pentaethylenehexamine (PEHA)
  • the amine compound of sample 5 is tetraethylenepentamine (TEPA).
  • concentration of the drug-carrying solution in sample 1, sample 4 and sample 5 is 40%
  • concentration of the drug-carrying solution in sample 2 is 60%
  • concentration of the drug-carrying solution in sample 3 is 20%.
  • Sample 1 has a carbon dioxide adsorption amount of 35.4 kgCO 2 / m 3
  • Sample 2 has a carbon dioxide adsorption amount of 52.1 kgCO 2 / m 3
  • 3 has a carbon dioxide adsorption of 33.1 kgCO 2 / m 3
  • sample 4 has a carbon dioxide adsorption of 58.4 kgCO 2 / m 3
  • sample 5 has a carbon dioxide adsorption of 65.9 kgCO 2 / m 3.
  • the carbon dioxide adsorption amount of these samples is 30 kgCO 2 / m 3 or more, and it can be objectively evaluated that these samples have good carbon dioxide adsorption performance.
  • each of the samples 1 to 5 had excellent adsorptivity. In each sample 1 to 5, no crack of the carbon dioxide adsorbent was found visually.
  • Sample 6 is obtained by supporting DEA having a support solution concentration of 40% on a base material having a pore size of 10 mm, a pore volume of 1.0 ml / g, and an average particle size of 2.7 mm.
  • Sample 7 is obtained by supporting DEA having a supporting solution concentration of 40% on a base material having a pore diameter of 30 mm, a pore volume of 1.0 ml / g, and an average particle diameter of 1.6 mm.
  • Sample 8 is obtained by supporting DEA having a supporting solution concentration of 60% on a base material having a pore diameter of 30 mm, a pore volume of 1.0 ml / g, and an average particle diameter of 1.6 mm.
  • Sample 9 is obtained by supporting DEA having a supporting solution concentration of 40% on a base material having a pore diameter of 70 mm, a pore volume of 1.1 ml / g, and an average particle diameter of 2.7 mm.
  • Sample 10 is obtained by supporting DEA having a supporting solution concentration of 60% on a base material having a pore diameter of 70 mm, a pore volume of 1.1 ml / g, and an average particle diameter of 2.7 mm.
  • Sample 11 is obtained by supporting DEA having a supporting solution concentration of 40% on a base material having a pore diameter of 30 mm, a pore volume of 1.3 ml / g, and an average particle diameter of 2.7 mm.
  • Sample 12 is obtained by supporting DEA having a supporting solution concentration of 60% on a base material having a pore diameter of 30 mm, a pore volume of 1.3 ml / g, and an average particle diameter of 2.7 mm.
  • Sample 13 is obtained by supporting DEA having a supporting solution concentration of 40% on a base material having a pore diameter of 70 mm, a pore volume of 1.3 ml / g, and an average particle diameter of 2.7 mm.
  • Sample 14 is obtained by supporting DEA having a supporting solution concentration of 60% on a base material having a pore diameter of 70 mm, a pore volume of 1.3 ml / g, and an average particle diameter of 2.7 mm.
  • Sample 15 is obtained by supporting DEA having a support solution concentration of 40% on a base material having a pore diameter of 80 mm, a pore volume of 1.0 ml / g, and an average particle diameter of 2.7 mm.
  • the carbon dioxide adsorption amount of the samples 6, 7, 9, 11, 13, and 15 is 34.0 to 39.9 kgCO 2 / m 3
  • the carbon dioxide of the samples 10 and 12 is The adsorption amount was 40.0 to 49.9 kgCO 2 / m 3
  • the carbon dioxide adsorption amount of Samples 3 and 14 was 50.0 to 59.9 kgCO 2 / m 3 . That is, it was found that Samples 6 to 15 all had excellent carbon dioxide adsorption performance.
  • a substrate (silica gel) having a particle diameter of 1 mm to 5 mm, an average pore diameter of 10 nm to 100 nm, and a pore volume of 0.1 cm 3 / g to 1.3 cm 3 / g. It was found that the carbon dioxide adsorbent with an amine compound loaded on the surface has excellent carbon dioxide adsorption performance.
  • ⁇ Rotational wear test> In order to evaluate the wear resistance of the carbon dioxide adsorbent, a rotational wear test was performed according to the following procedures (1) to (2). (1) 245 ml of the sample was put in one cylindrical drum with a partition wall, and the drum was rotated at 60 rpm for 48 hours. (2) The powdering rate was calculated from the change in the weight of the sample before and after rotating the drum. The details of the test procedures other than those described above were in accordance with JIS K1150: 1994 “5.9 Particle strength—5.9.1 when the lower limit of the particle size distribution is 1.4 mm or more”.
  • the carbon dioxide adsorbent is produced when the carbon dioxide adsorbent is produced by the above-described carbon dioxide adsorbent sample production procedure.
  • the adsorbent can withstand use in a continuous process carbon dioxide separation system with a moving bed in the apparatus. Therefore, when the powdering rate of the sample is 5 wt% or less, it is evaluated that the carbon dioxide adsorbent based on the sample has wear resistance that can withstand use in a continuous processing type carbon dioxide treatment system. It was decided.
  • FIG. 5 is a chart showing the results of the rotational wear test of silica gel.
  • the average particle size is about 1 mm to 5 mm
  • the pore size is about 10 nm to 100 nm
  • the pore volume is about 0.1 cm 3 / g to 1. All the samples (silica gel) of 3 cm3 / g or less had a powdering rate of 5 wt% or less.
  • the pore diameter is at about 10nm or 100nm or less, and a pore volume of approximately 0.1 cm 3 / g or more 1.3 cm 3 / g or less of silica gel amine compound
  • the carbon dioxide adsorbent formed by supporting the carbon dioxide adsorbent has abrasion resistance that can withstand use in a continuous processing type carbon dioxide separation system.

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Abstract

二酸化炭素吸着剤の製造方法が、アミン化合物の濃度が５％以上７０％以下、且つ、温度が１０℃以上１００℃以下のアミン水溶液を調製する工程と、前記アミン水溶液にシリカゲルを含浸させる工程と、前記アミン化合物を担持した前記シリカゲルを通気乾燥させる工程とを含む。前記シリカゲルは、粒子径が１ｍｍ以上５ｍｍ以下であり、平均細孔径が１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下である。

Description

二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素処理システム
　本発明は、被処理ガスに含まれる二酸化炭素を可逆的に吸着する二酸化炭素吸着剤及びその製造方法、並びに、この二酸化炭素吸着剤を用いたシステムに関する。
　従来、ボイラ等の燃焼設備から排出されたプロセスガスなどの二酸化炭素を含む被処理ガスから固体の二酸化炭素吸着剤を用いて二酸化炭素を分離し除去するシステムが知られている。特許文献１及び２では、この種の二酸化炭素分離システムが開示されている。
　特許文献１に記載の二酸化炭素分離システム（二酸化炭素除去システム）は、二酸化炭素吸着剤を収容した容器を備え、二酸化炭素吸着剤が容器内に導入された被処理ガスから二酸化炭素を可逆的に吸着するものである。この二酸化炭素吸着剤は、アミン、二酸化炭素活性化触媒、及び、アミン及び触媒を支持する多孔性物質を含んで成る。
　特許文献１のシステムでは、二酸化炭素吸着剤が被処理ガスから二酸化炭素を吸着除去する「吸着工程」と、二酸化炭素吸着剤から吸着した二酸化炭素を脱着する「脱着工程」とを含む１サイクルの処理工程を繰り返す「バッチ処理方式」で処理が行われる。一方、次に示す特許文献２のシステムでは、吸着工程と脱着工程とが並行して連続的に行われる「連続処理方式」で処理が行われる。
　特許文献２に記載の二酸化炭素分離システムは、上下方向に下方へ向けて順に並ぶホッパ、吸着工程が行われる吸着塔、脱着工程が行われる脱着塔（再生塔）、吸着剤を乾燥させる乾燥塔、及び、吸着剤を冷却する冷却塔と、冷却塔からホッパへ吸着剤を移送するコンベアとを備えている。ホッパに収容された二酸化炭素吸着剤は吸着塔、脱着塔、乾燥塔、冷却塔の順に自重で移動し、冷却塔からコンベアによってホッパへ搬送される。吸着塔及び脱着塔では、塔内を降下する二酸化炭素吸着剤と各塔内を上昇する気体とによって移動層が形成されている。特許文献２のシステムにおいて、二酸化炭素吸着剤はアミン化合物を担持した多孔性物質であって、多孔性物質としては、活性炭、活性アルミナなどが例示されている。
特表２０１２－５０１８３１号公報 特開２０１３－１２１５６２号公報
　上記特許文献１のシステムでは、二酸化炭素吸着剤は容器に対し静止している。一方、上記特許文献２のシステムでは、二酸化炭素吸着剤は容器に相対して移動し、二酸化炭素吸着剤と容器との間、及び、二酸化炭素吸着剤同士の間で摩擦や衝突が生じる。そのため、特に連続処理方式では、バッチ処理方式で使用される二酸化炭素吸着剤よりも高度な強度（特に、耐摩耗性）が要求される。
　本発明は以上の事情に鑑みてされたものであり、その目的は、優れた吸着性を備え、且つ、連続処理方式での使用に耐えうる強度を備えた二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素吸着剤を利用したシステムを提供することにある。
　本発明に係る二酸化炭素吸着剤の製造方法は、
アミン化合物の濃度が５％以上７０％以下、且つ、温度が１０℃以上１００℃以下のアミン水溶液を調製する工程と、
前記アミン水溶液にシリカゲルを含浸させる工程と、
前記アミン化合物を担持した前記シリカゲルを通気乾燥させる工程とを含み、
前記シリカゲルは、粒子径が１ｍｍ以上５ｍｍ以下であり、平均細孔径が１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下であることを特徴としている。但し、上記粒子径、細孔容積、及び平均細孔径は、いずれもアミン化合物が担持されていない状態のシリカゲルにおける値である。
　また、本発明に係る二酸化炭素吸着剤は、粒子径が１ｍｍ以上５ｍｍ以下であり、平均細孔径が１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下のシリカゲルにアミン化合物を担持させて成ることを特徴としている。
　また、本発明に係る二酸化炭素処理システムは、上記の二酸化炭素吸着剤により内部に移動層が形成された吸着槽を備え、前記吸着槽の下部に二酸化炭素を含む被処理ガスが供給される被処理ガス供給口が設けられ、前記吸着槽の上部に前記二酸化炭素が前記二酸化炭素吸着剤に吸着除去されたオフガスを排出するオフガス排出口が設けられたものである。
　上記二酸化炭素吸着剤及びその製造方法によれば、二酸化炭素の吸着性能に優れ、且つ、連続処理方式の二酸化炭素処理システムでの利用に耐えうる耐摩耗性を備えた二酸化炭素吸着剤を提供することができる。
　本発明によれば、優れた吸着性を備え、且つ、連続処理方式での使用に耐えうる強度を備えた二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素吸着剤を利用したシステムを提供することができる。
図１は、本発明に係る二酸化炭素吸着剤が使用され得る二酸化炭素処理システムの概略構成を示す図である。 図２Ａは、シリカゲルの粒子径を模式的に示す図である。 図２Ｂはシリカゲルの細孔容積及び細孔径を模式的に示す図である。 図３は、多孔質物質内の二酸化炭素－空気拡散抵抗と細孔径との関係を示す図表である。 図４は、シリカゲルにジエタノールアミンを担持させて成る吸着剤のシリカゲルの細孔容積と二酸化炭素吸着量との関係を示す図表である。 図５は、シリカゲルの回転摩耗試験の結果を示す図表である。
 本発明に係る二酸化炭素吸着剤（以下、単に「吸着剤」ということがある）は、二酸化炭素を含む被処理ガスから二酸化炭素を可逆的に吸着し除去するために利用されるものである。この吸着剤は、優れた二酸化炭素吸着能力及び耐摩耗性を有しており、連続処理方式で被処理ガスから二酸化炭素を吸着除去するシステムで利用するのに適している。
〔二酸化炭素処理システム〕
　図１では、二酸化炭素吸着剤が使用され得る二酸化炭素処理システム１の概略構成が示されている。図１に示す二酸化炭素処理システム１は、吸着剤を用いて被処理ガスに含まれる二酸化炭素を選択的に分離する二酸化炭素分離システム１Ａと、吸着剤から二酸化炭素を脱着(脱離)して回収する二酸化炭素回収システム１Ｂとが複合された連続処理方式のシステムである。
　二酸化炭素処理システム１は、吸着槽１１、脱着槽１２、及び、乾燥槽１３と、乾燥槽１３の出口から吸着槽１１の入口まで吸着剤を搬送するコンベア１５とを備えている。吸着槽１１から乾燥槽１３まで重力によって吸着剤が移動するように、上から吸着槽１１、脱着槽１２、及び、乾燥槽１３の順に上下方向に並んで配置されている。
　吸着槽１１には、コンベア１５によって搬送されてくる吸着剤が、上部に設けられた入口から所定の供給速度で供給される。また、吸着槽１１の下部に設けられた出口から所定の排出速度で吸着剤が排出される。
　吸着槽１１の下部には、被処理ガス源３５で発生した被処理ガスが被処理ガス供給管３６を通じて導入される。被処理ガスは、例えば、燃焼排ガスなどの、１０～３０％の二酸化炭素を含む常圧近傍のガスである。被処理ガス供給管３６には、少なくとも１つの前処理槽３７が設けられていてよい。前処理槽３７では、被処理ガスが二酸化炭素の吸着反応に適切な温度まで冷却される。なお、吸着槽１１に導入される被処理ガスに対し、冷却の他に、脱硫、脱塵、減温、除湿などの前処理が施されてよい。
　吸着槽１１では、上向きに流れる被処理ガスと下向きに移動する吸着剤とが接触する移動層が形成されている。被処理ガスと接触した吸着剤は、被処理ガスに含まれる二酸化炭素を選択的に吸着する。その際の吸着剤の温度は、例えば、４０℃である。二酸化炭素が分離除去された被処理ガス（オフガス）は吸着槽１１の上部から排出される。一方、二酸化炭素を吸着した吸着剤は吸着槽１１の下部から排出されて、脱着槽１２の入口へ自重によって移動する。
　脱着槽１２では、上部に設けられた入口から二酸化炭素を吸着した吸着剤が供給されるとともに、下部に設けられた出口から所定の排出速度で吸着剤が排出されることにより、吸着剤が槽内を上から下へ向かって所定の速度で移動する。また、脱着槽１２の下部には、蒸気発生器３８から送給される脱着用水蒸気が供給される。
　脱着槽１２では、上向きに流れる脱着用水蒸気と下向きに移動する吸着剤とが接触する移動層が形成されている。脱着用水蒸気と吸着剤とが接触すると、脱着用水蒸気が吸着剤の表面で凝縮し、その際に凝縮熱を放出する。この凝縮熱を脱離のエネルギーとして、二酸化炭素が吸着剤から脱離する。
　脱着槽１２の上部には、二酸化炭素回収管３１を介して二酸化炭素ホルダ１７が接続されている。二酸化炭素回収管３１には、脱着槽１２の気体を二酸化炭素ホルダ１７へ送り出すポンプ１６が設けられている。脱着槽１２内の気体（即ち、二酸化炭素）は二酸化炭素回収管３１へ強制的に排気され、ポンプ１６で圧縮されて、二酸化炭素ホルダ１７に貯留される。一方、二酸化炭素の脱着後の凝縮水を含んだ吸着剤は、脱着槽１２の下部から排出されて、乾燥槽１３の入口へ自重によって移動する。
　乾燥槽１３では、上部に設けられた入口から凝縮水を含んだ吸着剤が供給されるとともに、下部に設けられた出口から所定の排出速度で吸着剤が排出されることにより、吸着剤が槽内を上から下へ向かって所定の速度で移動している。吸着剤は、乾燥槽１３を移動するうちに乾燥される。吸着剤の乾燥は、本実施形態では、乾燥用ガス源３９から乾燥槽１３の下部へ供給されて槽内を上向きに流れる乾燥用ガスと、槽内を下向きに移動する吸着剤との接触により行われる。吸着剤の乾燥に利用された乾燥用ガス（乾燥排ガス）は乾燥槽１３の上部から排出される。
　乾燥後の吸着剤は、乾燥槽１３の下部から排出されて、コンベア１５に落下し、コンベア１５によって冷却されながら吸着槽１１へ移送され、二酸化炭素の吸着剤として再利用される。
〔二酸化炭素吸着剤〕
　上記二酸化炭素処理システム１で使用される吸着剤（二酸化炭素吸着剤）は、シリカゲルにアミン化合物を担持させて成るものである。
　上記のアミン化合物は、少なくとも１つのヒドロキシル基を有するアミン類、及び、ポリアミン類よりなる群から選択された少なくとも１種である。即ち、上記のアミン化合物には、アミン類とポリアミン類の混合物が含まれていてもよい。このようなアミン類及びポリアミン類は、二酸化炭素を可逆的に脱着する、つまり、二酸化炭素を吸着及び脱着することが知られている。少なくとも１つのヒドロキシル基を有するアミン類を含むアミン化合物として、モノエタノールアミン、ジエタノールアミン、及び、トリエタノールアミンが例示される。また、ポリアミン類を含むアミン化合物として、ポリエチレンイミン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及び、ペンタエチレンヘキサミンが例示される。
　上記のシリカゲルの粒子径は１ｍｍ以上５ｍｍ以下である。また、シリカゲルの細孔容積は０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下である。更に、シリカゲルの平均細孔径は１０ｎｍ以上１００ｎｍ以下である。なお、上記粒子径、細孔容積、及び平均細孔径は、いずれもアミン化合物が担持されていない状態のシリカゲルにおける値である。
　図２Ａはシリカゲルの粒子径を模式的に示す図であり、図２Ａはシリカゲルの細孔容積及び細孔径を模式的に示す図である。図２Ｂでは、シリカゲルの表面付近の断面が拡大して示されている。図２Ｂに示すように、シリカゲルは球状の粒子である。なお、「球状」の粒子とは必ずしも真球状の粒子を意味するものではなく、水平から約３０°傾斜させた平滑な板上に置かれたときに９０質量％以上が転げ落ちる形状の粒子である。
　上記のように粒子径が１ｍｍ以上５ｍｍ以下のシリカゲルを基材とする二酸化炭素吸着剤もまた、その粒子径が１ｍｍ以上５ｍｍ以下である。なお、シリカゲルはアミン化合物を担持するが、アミン化合物はシリカゲルの内部に形成された細孔に入り込むので、アミン化合物を担持することによってシリカゲルの径はさほど拡張されない。
　二酸化炭素吸着剤の粒子径が１ｍｍよりも小さいと、少ないガス量で吸着剤が流動化してしまい、移動層が成立しなくなる。一方、二酸化炭素吸着剤の粒子径が５ｍｍを超えると、吸着剤の粒子径の増大に伴い重量も増大することから、落下時に受ける衝撃による摩耗が激しくなり、吸着剤の寿命が著しく短くなる。したがって、粒子径が１ｍｍ以上５ｍｍ以下の範囲内の二酸化炭素吸着剤を用いることによって、吸着剤と被処理ガスとが好適に向流接触する移動層を形成することが容易となり、且つ、吸着剤に適切な寿命を与えることができる。
　なお、上記において、二酸化炭素及びシリカゲルの「粒子径」とは、その粒子直径である。二酸化炭素及びシリカゲルの粒子径は、例えば、次の（１）～（４）の工程によって測定することができる。
（１）黒色フェルト上に１００粒以上のシリカゲル試料を、なるべく粒子同士が接触しないように並べる。
（２）シリカゲル試料の粒子を１００ｍｍ×１４０ｍｍの範囲視野で撮影する。
（３）画像処理ソフトウェアＩｍａｇｅＪ（アメリカ国立衛生研究所ＮＩＨ）を用いて、撮影した画像を二値化し、各粒子の面積を求める。
（４）粒子が真球であると仮定し、求めた各粒子の面積から粒子径を求める。
なお、求めた粒子径から、個数平均径（＝Σ（粒子径）／（評価した粒子の数））を求め、この個数平均径を粒子径として用いてもよい。
　図２Ｂに示すように、シリカゲルの平均細孔径は、シリカゲルの表面に開口した細孔の直径の平均値である。また、シリカゲルの細孔容積は、細孔の容積である。
　シリカゲルの細孔容積は水銀圧入法により求めたものである。また、シリカゲルの平均細孔径は、水銀圧入法により細孔径分布を求め、全細孔容積の５０％の容積の水銀が圧入された時点の細孔径を平均細孔径（メディアン径）としたものである。水銀圧入法は、水銀の表面張力が大きいことを利用して粉体の細孔に水銀を浸入させるために圧力を加え、圧力と圧入された水銀量から比表面積や細孔分布を求める方法であり、例えば、Ｔｈｅｒｍｏ　Ｑｕｒｅｓｔ　Ｉｔａｌｉａ社製の水銀ポロシメーター（ＰＡＳＣＬ２４０）を用いて求めることができる。
　シリカゲルの平均細孔径は、吸着剤の吸着速度に重大な影響を与える。吸着剤の吸着速度は、細孔内の二酸化炭素拡散速度と吸着剤の吸着反応速度とに依存する。このうち吸着反応速度は、細孔内の二酸化炭素拡散速度と比較して十分に速いことから、実際は吸着剤の吸着速度は細孔内の二酸化炭素拡散速度に律速される。
　図３は、多孔質物質内の二酸化炭素－空気拡散抵抗と細孔径との関係を示す図表である。図３から、細孔径がおよそ１０ｎｍよりも小さくなると、二酸化炭素－空気拡散抵抗が急激且つ著しく大きくなることが読み取れる。これは、細孔内の全拡散抵抗に占めるクヌーセン拡散の割合が９０％以上となるためと考えられている。したがって、シリカゲルの平均細孔径がおよそ１０ｎｍよりも小さくなると、現実的な処理時間内で吸着剤に二酸化炭素を飽和吸着させることが困難となると考えられる。一方、シリカゲルの平均細孔径が１００ｎｍを超えると、シリカゲルを構成するシリカ一次粒子骨格の強度が低下するため、吸着剤に要求される粒子強度を満足しなくなる。
　以上から、平均細孔径が１０ｎｍ以上１００ｎｍ以下の範囲のシリカゲルを用いることによって、吸着剤の二酸化炭素吸着速度が好適な範囲に維持され、且つ、吸着剤に要求される粒子強度を与えることができる。
　なお、シリカゲルの平均細孔径は、シリカゲルをスチーミング処理することによりコントロールすることが可能である。より詳細には、スチーミング時の圧力及びキセロゲルのｐＨを調整することにより、平均細孔径を１０ｎｍ以上１００ｎｍ以下の間で制御することができる。スチーミング処理は、通常、オートクレーブ中で加圧下、スチームを流通させることにより実施され、その処理時間は通常、１０分～２４時間である。また、この際の圧力は０．５～２０Ｋｇ・ｃｍ２である。更に、このスチーミング処理中におけるキセロゲルのｐＨは５～９に制御されることが望ましい。
　図４は、シリカゲルにジエタノールアミン（アミン溶液濃度４０％）を担持させて成る吸着剤の、シリカゲルの細孔容積と二酸化炭素吸着量との関係を示す図表である。図４からは、シリカゲルの細孔容積がおよそ０．１ｃｍ３／ｇ以上の吸着剤で二酸化炭素の吸着が可能であることが読み取れる。
　また、図４からは、シリカゲルの細孔容積は大きいほど二酸化炭素吸着量が増加することが読み取れる。しかし、シリカゲルの細孔容積が過度に大きくなると、シリカゲルが球状を維持することが困難なまでに強度が低下し、その結果、吸着剤に要求される粒子強度を満たすことができない。そこで、図４に基づけば、二酸化炭素吸着量が飽和する１．３ｃｍ３／ｇをシリカゲルの細孔容積の上限として規定することが好適である。
　以上から、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下のシリカゲルを用いることによって、二酸化炭素を吸着可能であり、且つ、吸着剤に要求される粒子強度を与えることができる。なお、シリカゲルの球状を維持するという観点で、粒子径が１ｍｍ以上５ｍｍのシリカゲルに対し、比表面積が１０ｍ２／ｇ以上３００ｍ２／ｇ以下であるという条件を加えてもよい。シリカゲルの比表面積は、平均細孔径や細孔容積と同様に水銀圧入法により求めることができる。
〔二酸化炭素吸着剤の製造方法〕
　上記の吸着剤は、以下に説明する方法で製造することができる。
　先ず、アミン化合物の濃度が５％以上７０％以下、且つ、温度が１０℃以上１００℃以下のアミン水溶液を調製する。
　アミン水溶液の粘度は温度の上昇に伴って低下することが知られている。そこで、シリカゲルに均一にアミン化合物を担持させるために、アミン水溶液の温度を１０℃以上とすることが望ましい。一方で、アミン水溶液の温度が１００℃を超えると、アミン化合物の酸化や蒸発が生じ易くなる。そこで、アミン水溶液の温度は１０℃以上１００℃以下が好適である。
　アミン水溶液のアミン化合物の濃度は、５％以上７０％以下の範囲においてアミン化合物に応じた適切な値であることが望ましい。例えば、アミン化合物がジエタノールアミンの場合には、アミン水溶液のアミン化合物の濃度は５％以上５５％以下が適切である。また、例えば、アミン化合物がポリエチレンイミンの場合には、粘度が高いため、１０％前後の濃度が好ましい。
　アミン水溶液中のアミン化合物の濃度が下限値よりも少ないと、シリカゲルへのアミン化合物の担持量が十分ではなく、また、担持処理後の排液量が膨大となる。一方、アミン水溶液のアミン化合物の濃度が上限値を超えると、アミン化合物がシリカゲルの細孔を閉塞して、吸着剤の吸着性能を低下させるおそれがある。アミン化合物の濃度が５～７０％の範囲内では、アミン水溶液中のアミン化合物の濃度の増大に伴い、シリカゲルのアミン担持量が増加し、また、吸着剤の比重と吸着剤の二酸化炭素吸着量も比例して増加する。このことから、アミン水溶液中のアミン化合物の濃度を５％以上７０％以下の範囲内で適切に設定することで、吸着剤の設計仕様に応じた二酸化炭素吸着剤を製造することが可能となる。
　次に、上記のように調製したアミン水溶液にシリカゲルを含浸させる。シリカゲルの含浸時間は、例えば、２４時間とすることができる。
　最後に、シリカゲルに付着している余剰の液体を吸引濾過等の方法で除去したのち、アミン化合物を担持したシリカゲルを室温に近い温度で通気乾燥させる。以上の工程で吸着剤を製造することができる。
　ところで、上記吸着剤の製造方法におけるアミン水溶液にシリカゲルを含浸させる工程で、水分吸着によってシリカゲルの一部に割れやヒビが発生することが分かっている。割れやヒビによって球状を成さない吸着剤は、連続処理方式の二酸化炭素処理システムで使用するために十分な強度（耐摩耗性）を備えておらず、使用に適さない。そのため、製造された吸着剤から球状を成すもののみが選択的に取り出されて、二酸化炭素の吸着に使用される。
　そこで、吸着剤製造の歩留まりを向上させるために、上記のシリカゲルとして耐水性を有するシリカゲルを用いてよい。ここで、「耐水性を有するシリカゲル」とは、下記式（１）で定義される耐水性Ｎが４５％以上のシリカゲルと定義する。
Ｎ＝（Ｗ／Ｗ0）×１００…（１）
但し、　Ｎ：シリカゲルの耐水性［％］
　　　　Ｗ0：水に浸漬したシリカゲルの粒子の全個数［個］
　　　　Ｗ：Ｗ0のうち割れの発生しなかったものの個数［個］
　上記のような耐水性を有するシリカゲルは、市販されている耐水性球状シリカを用いてよい。この耐水性球状シリカは、例えば、ケイ酸アルカリ水溶液を中和することにより得たシリカヒドロゲルを、スーパーヒートスチームにより１００～１０００℃の温度で乾燥した球状のシリカキセロゲルを５００～１０００℃で焼成することによって製造可能である。
　上記のような耐水性を有するシリカゲルを材料とした場合には、上記吸着剤の製造方法におけるアミン水溶液にシリカゲルを含浸させる工程で、シリカゲルに割れやヒビが殆ど生じないことが発明者らによって確認されている。　　　
＜二酸化炭素吸着剤の試料作製手順＞
　以下（１）～（５）の手順で二酸化炭素吸着剤の試料を作製した。
（１）基材（シリカゲル）を約３００ｍＬ採取し、重量（Ｗ）を測定する。
（２）薬剤（アミン化合物）を所定の担持溶液濃度（％）に希釈し、瓶に入れる。
（３）（１）の基材を（２）の瓶に入れ、室温で８時間以上放置する。ここで、基材と薬剤の重量比が１:３となるようにした。
（４）（３）から基材を取り出し、遠心分離（１１００ｒｐｍ）を行う。
（５）容器に充填し、乾燥ガス（４０℃，１５Ｌ/ｍｉｎの窒素ガス）を流して、薬剤を担持した基材を通気乾燥させる。なお、薬剤を担持した基材を乾燥する乾燥槽の出口のガス温度が安定した時点より２時間経過後を、薬剤を担持した基材（即ち、二酸化炭素吸着剤）の乾燥終了条件とした。
＜二酸化炭素吸着試験＞
　二酸化炭素吸着剤の二酸化炭素吸着性能を評価するために、以下（１）～（４）の手順で二酸化炭素吸着剤試料の二酸化炭素の吸着試験（カラム試験）を行った。
（１）内径２５ｍｍの吸着槽に３００ｍｍの高さまで試料を固く充填する。ここで、充填された試料は１４７ｍＬであった。
（２）吸着ガスをバイパスラインに流し、濃度が１０．０％であることを確認する。ここで、吸着ガスは、１０体積％の二酸化炭素を含み、湿度が湿度５％ＲＨ以下、且つ、２５℃の空気である。また、吸着ガスの空塔速度は０．０５ｍ／ｓとする。
（３）吸着ガスを吸着槽へ流し、吸着槽の出口のガス濃度を測定する。
（４）出口ガス濃度が１０．０%になったこと（即ち、飽和吸着となったこと）を確認し、吸着工程を終了する。
＜二酸化炭素吸着試験結果１＞
　上記試料作製手順により、各基材の物性は共通するが、薬剤の担持条件（担持溶液濃度及び薬剤種）の相違する試料１～５を作製した。各試料における、基材（シリカゲル）の物性と薬剤の担持条件は次表１に示す通りである。
Figure JPOXMLDOC01-appb-T000001
　試料１及び試料２のアミン化合物はジエタノールアミン（ＤＥＡ）であり、試料２及び試料３のアミン化合物はペンタエチレンヘキサミン（ＰＥＨＡ）であり、試料５のアミン化合物はテトラエチレンペンタミン（ＴＥＰＡ）である。また、試料１、試料４及び試料５の薬剤の担持溶液濃度は４０％であり、試料２の薬剤担持溶液濃度は６０％であり、試料３の薬剤の担持溶液濃度は２０％である。
　そして、上記試料１～５の吸着試験結果は、試料１の二酸化炭素吸着量が３５．４ｋｇＣＯ２／ｍ３であり、試料２の二酸化炭素吸着量が５２．１ｋｇＣＯ２／ｍ３であり、試料３の二酸化炭素吸着量が３３．１ｋｇＣＯ２／ｍ３であり、試料４の二酸化炭素吸着量が５８．４ｋｇＣＯ２／ｍ３であり、試料５の二酸化炭素吸着量が６５．９ｋｇＣＯ２／ｍ３であった。これらの試料の二酸化炭素吸着量はいずれも３０ｋｇＣＯ２／ｍ３以上であり、客観的にこれらの試料の二酸化炭素吸着性能が良好であると評価することができる。
　以上から、各試料１～５が優れた吸着性を備えることが認められた。また、各試料１～５において、二酸化炭素吸着剤の割れは目視で発見されなかった。
＜二酸化炭素吸着試験結果２＞
　上記試料作製手順により、薬剤の担持条件（担持溶液濃度は４０又は６０％、薬剤種はジエタノールアミン（ＤＥＡ））は共通するが、各基材の物性の異なる試料６～１５を作製した。各試料６～１５における、基材（シリカゲル）の物性と薬剤の担持条件は次表２に示す通りである。
Figure JPOXMLDOC01-appb-T000002
　試料６は、細孔径１０ｍｍ、細孔容積１．０ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度４０％のＤＥＡを担持させたものである。試料７は、細孔径３０ｍｍ、細孔容積１．０ｍｌ／ｇ、平均粒子径１．６ｍｍの基材に、担持溶液濃度４０％のＤＥＡを担持させたものである。試料８は、細孔径３０ｍｍ、細孔容積１．０ｍｌ／ｇ、平均粒子径１．６ｍｍの基材に、担持溶液濃度６０％のＤＥＡを担持させたものである。試料９は、細孔径７０ｍｍ、細孔容積１．１ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度４０％のＤＥＡを担持させたものである。試料１０は、細孔径７０ｍｍ、細孔容積１．１ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度６０％のＤＥＡを担持させたものである。試料１１は、細孔径３０ｍｍ、細孔容積１．３ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度４０％のＤＥＡを担持させたものである。試料１２は、細孔径３０ｍｍ、細孔容積１．３ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度６０％のＤＥＡを担持させたものである。試料１３は、細孔径７０ｍｍ、細孔容積１．３ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度４０％のＤＥＡを担持させたものである。試料１４は、細孔径７０ｍｍ、細孔容積１．３ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度６０％のＤＥＡを担持させたものである。試料１５は、細孔径８０ｍｍ、細孔容積１．０ｍｌ／ｇ、平均粒子径２．７ｍｍの基材に、担持溶液濃度４０％のＤＥＡを担持させたものである。
　上記試料６～１５の吸着試験結果では、試料６，７，９，１１，１３，１５の二酸化炭素吸着量が３４．０～３９．９ｋｇＣＯ２／ｍ３であり、試料１０，１２の二酸化炭素吸着量が４０．０～４９．９ｋｇＣＯ２／ｍ３であり、試料３，１４の二酸化炭素吸着量が５０．０～５９．９ｋｇＣＯ２／ｍ３であった。即ち、試料６～１５はいずれも優れた二酸化炭素吸着性能を有していることがわかった。
　以上から、粒子径が１ｍｍ以上５ｍｍ以下であり、平均細孔径が１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下での基材（シリカゲル）にアミン化合物を担持下二酸化炭素吸着剤が、優れた二酸化炭素吸着性能を有することがわかった。
＜回転摩耗試験＞
　二酸化炭素吸着剤の耐摩耗性を評価するために、次の（１）～（２）の手順で、回転摩耗試験を行った。
（１）１枚の隔壁付円筒状ドラムに試料２４５ｍｌを入れ、ドラムを６０ｒｐｍで４８ｈｒ回転させた。
（２）ドラムを回転させる前後での試料の重量変化から粉化率を算出した。
　上記以外の試験手順の詳細については、ＪＩＳ　Ｋ１１５０：１９９４「５．９　粒子強度－５．９．１粒度分布の下限が１．４ｍｍ以上の破砕粒子の場合」に準拠した。
　回転摩耗試験において、試料の粉化率が「５ｗｔ％」以下であれば、その試料を用いて前述の二酸化炭素吸着剤の試料の作製手順で二酸化炭素吸着剤を作製したときに、その二酸化炭素吸着剤は装置内に移動層を備える連続処理方式の二酸化炭素分離システムでの使用に耐えうることが経験的に分かっている。そこで、試料の粉化率が５ｗｔ％以下である場合に、その試料を基材とする二酸化炭素吸着剤が連続処理方式の二酸化炭素処理システムでの使用に耐えうる耐摩耗性を備えると評価することとした。
　図５は、シリカゲルの回転摩耗試験の結果を示す図表である。回転摩耗試験の結果から明らかなように、平均粒子径がおよそ１ｍｍ以上５ｍｍ以下であり、細孔径がおよそ１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積がおよそ０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下の試料（シリカゲル）は、いずれも粉化率が５ｗｔ％以下であった。よって、粒子径がおよそ１ｍｍ以上５ｍｍ以下であり、細孔径がおよそ１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積がおよそ０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下のシリカゲルにアミン化合物を担持させて成る二酸化炭素吸着剤は、連続処理方式の二酸化炭素分離システムでの使用に耐えうる耐摩耗性を備える。

Claims (8)

  1. 　アミン化合物の濃度が５％以上７０％以下、且つ、温度が１０℃以上１００℃以下のアミン水溶液を調製する工程と、
    　前記アミン水溶液にシリカゲルを含浸させる工程と、
    　前記アミン化合物を担持した前記シリカゲルを通気乾燥させる工程とを含み、
    　前記シリカゲルは、粒子径が１ｍｍ以上５ｍｍ以下であり、平均細孔径が１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下である、
    二酸化炭素吸着剤の製造方法。
  2. 　前記シリカゲルは、次式（１）で定義される耐水性Ｎが４５％以上である、
    Ｎ＝（Ｗ／Ｗ0）×１００…（１）
    （但し、Ｎ：シリカゲルの耐水性［％］、Ｗ0：水に浸漬したシリカゲルの粒子の全個数［個］、Ｗ：Ｗ0のうち割れの発生しなかったものの個数［個］）
    請求項１に記載の二酸化炭素吸着剤の製造方法。
  3. 　前記アミン化合物が、少なくとも１つのヒドロキシル基を有するアミン類、及びポリアミン類よりなる群から選ばれる少なくとも１種である、
    請求項１又は２に記載の二酸化炭素吸着剤の製造方法。
  4. 　粒子径が１ｍｍ以上５ｍｍ以下であり、平均細孔径が１０ｎｍ以上１００ｎｍ以下であり、且つ、細孔容積が０．１ｃｍ３／ｇ以上１．３ｃｍ３／ｇ以下であるシリカゲルに、アミン化合物を担持させて成る、
    二酸化炭素吸着剤。
  5. 　前記シリカゲルは、次式（１）で定義される耐水性Ｎが４５％以上である、
    Ｎ＝（Ｗ／Ｗ0）×１００…（１）
    （但し、Ｎ：シリカゲルの耐水性［％］、Ｗ0：水に浸漬したシリカゲルの粒子の全個数［個］、Ｗ：Ｗ0のうち割れの発生しなかったものの個数［個］）
    請求項４に記載の二酸化炭素吸着剤。
  6. 　前記アミン化合物が、少なくとも１つのヒドロキシル基を有するアミン類、及びポリアミン類よりなる群から選ばれる少なくとも１種である、
    請求項４又は５に記載の二酸化炭素吸着剤。
  7. 　請求項４～６のいずれか一項に記載の二酸化炭素吸着剤により内部に移動層が形成された吸着槽を備え、前記吸着槽の下部に二酸化炭素を含む被処理ガスが供給される被処理ガス供給口が設けられ、前記吸着槽の上部に前記二酸化炭素が前記二酸化炭素吸着剤に吸着除去されたオフガスを排出するオフガス排出口が設けられている、二酸化炭素処理システム。
  8. 　前記吸着槽から排出された前記二酸化炭素吸着剤により内部に移動層が形成された脱着槽を備え、前記脱着槽の下部に脱着用水蒸気が供給される水蒸気供給口が設けられ、前記脱着槽の上部に前記二酸化炭素吸着剤から脱離した二酸化炭素を排出する二酸化炭素排出口が設けられている、
    請求項７に記載の二酸化炭素処理システム。
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