WO2021210386A1 - 潜熱蓄熱材一体型活性炭及びその製造方法 - Google Patents

潜熱蓄熱材一体型活性炭及びその製造方法 Download PDF

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Publication number
WO2021210386A1
WO2021210386A1 PCT/JP2021/013531 JP2021013531W WO2021210386A1 WO 2021210386 A1 WO2021210386 A1 WO 2021210386A1 JP 2021013531 W JP2021013531 W JP 2021013531W WO 2021210386 A1 WO2021210386 A1 WO 2021210386A1
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latent heat
heat storage
storage material
activated carbon
integrated
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English (en)
French (fr)
Japanese (ja)
Inventor
邦寿 岩崎
建司 関
一樹 坂井
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Osaka Gas Chemicals Co Ltd
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Osaka Gas Chemicals Co Ltd
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Priority to JP2022515283A priority Critical patent/JP7769604B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to an activated carbon integrated with a latent heat storage material and a method for producing the same.
  • the organic solvent recovery system that liquefies and recovers the organic solvent has advantages that the amount of carbon dioxide emitted is smaller than that of the combustion device that burns and detoxifies the organic solvent, and that the recovered organic solvent can be reused.
  • the organic solvent recovery system executes an adsorption step of adsorbing and removing the organic solvent in the gas to be treated with the adsorbent and a desorption step of desorbing the organic solvent adsorbed on the adsorbent by an inert gas such as heated air. It is configured by providing a switching means or a means for continuously performing the adsorption step and the desorption step alternately in time.
  • Exhaust gas emitted to the atmosphere by automobiles which is one of the sources of air pollutants, includes exhaust gas from fuel burned by an engine, hoisting dust that tires wind up while driving, fuel mounted on automobiles, and solvents for automobile materials. There is exhaust gas etc. generated from such as.
  • the canister which is an automobile part, temporarily adsorbs (collects) the gasoline vapor evaporated in the fuel tank to the activated carbon and suppresses the discharge to the outside of the vehicle.
  • the vapor temporarily adsorbed (collected) on the activated carbon is purged (scavenged) by using the negative pressure of the intake pipe of the engine during running, and is configured so that the performance can be maintained repeatedly by burning the engine. ..
  • the adsorbent is required to have high-quality adsorption / desorption performance, but the adsorbent itself has the property that the lower the temperature, the higher the adsorption capacity, and the higher the temperature, the higher the desorption ability.
  • One of the important factors when sought is temperature.
  • the heat that goes in and out of the adsorbent when various gases, liquids, vapors, etc. are attached to and detached from the adsorbent is controlled by flowing a medium such as water from the outside, or a substance with high thermal conductivity is inserted. Although it is possible to suppress the temperature rise by mixing substances with high heat capacity, the equipment becomes heavier and larger.
  • Patent Documents 1 and 2 describe a latent heat storage type adsorbent for canisters, which includes an adsorbent that adsorbs vaporized fuel and a latent heat storage material in which a phase change substance that absorbs and releases latent heat depending on the temperature is encapsulated in microcapsules. Proposed. According to this adsorbent, the adsorption-desorption performance of the transpired fuel is significantly superior to that of the conventional one due to the temperature control during adsorption and desorption, so there is an advantage that a small and high-performance adsorption tower and canister can be supplied. There is.
  • Durability against solvent vapor is important to maintain high level of adsorption / desorption performance for a long period of time.
  • the surface of the latent heat storage material is physically damaged, and when exposed to VOC steam, the latent heat substance in the microcapsules constituting the latent heat storage material leaks out. Therefore, the original performance of the adsorbent cannot be brought out due to the decrease in the amount of heat of the latent heat storage material and the blockage of the pores of the activated charcoal.
  • an object of the present invention is to integrate the latent heat storage material and the activated carbon while suppressing damage to the latent heat storage material, rather than simply mixing the latent heat storage material and the pellets of the activated carbon. It is an object of the present invention to provide an adsorbent which can prevent heat transfer loss in intergranular voids and can maintain a high level of adsorption / desorption performance and durability by effectively controlling the heat of adsorption.
  • the present inventors coated the surface of the microcapsules containing the phase-changing substance with an organic binder-containing layer containing a thermosetting organic binder A, and further. It has been found that by coating with an activated carbon-containing layer containing activated carbon, an adsorbent capable of maintaining a high level of adsorption / desorption performance and durability can be obtained. Based on such findings, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.
  • a latent heat storage material integrated activated carbon containing microcapsules containing a phase-changing substance that absorbs and releases latent heat depending on the temperature and activated carbon In the latent heat storage material, the surface of the microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the latent heat storage material is coated with an organic binder-containing layer.
  • Item 2 The latent heat storage material integrated activated carbon according to Item 1, wherein the microcapsules have an average particle size of 0.1 to 500 ⁇ m.
  • Item 3 The latent heat storage material integrated activated carbon according to Item 1 or 2, wherein the activated carbon has an average particle size of 1 ⁇ m to 10 mm.
  • Item 4. The latent heat storage material integrated activated carbon according to any one of Items 1 to 3, wherein the activated carbon-containing layer further contains an organic binder B.
  • Item 5 The latent heat storage material integrated activated carbon according to any one of Items 1 to 4, wherein the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is 4.5 or more. ..
  • Item 6 The latent heat storage material integrated activated carbon according to any one of Items 1 to 5, wherein the latent heat storage material has an average cross-sectional diameter of 0.75 to 1.80 mm.
  • Item 7 The latent heat storage material integrated activated carbon according to any one of Items 1 to 6, wherein the content of the latent heat storage material is 7 to 30% by mass, where the total amount of the latent heat storage material integrated activated carbon is 100% by mass. ..
  • Item 8 The latent heat storage material integrated activated carbon according to any one of Items 1 to 7, which has a calorific value of 10 to 100 J / g.
  • Item 9 The latent heat storage material integrated activated carbon according to any one of Items 1 to 8, which has an ASTM hardness of 45% or more.
  • Item 10 The method for producing a latent heat storage material-integrated activated carbon according to any one of Items 1 to 9.
  • Step of mixing the microcapsules and the thermosetting organic binder A (2) The microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above.
  • the process of obtaining latent heat storage material (3) A production method comprising a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
  • Item 11 The production method according to Item 10, wherein the step (1) is a step of mixing the microcapsules and the thermosetting organic binder A, then extruding and granulating, and then sizing.
  • Item 12 The production method according to Item 10 or 11, wherein in the step (3), the composition containing the activated carbon further contains the organic binder B.
  • Item 13 The production method according to any one of Items 10 to 12, wherein in the step (3), the composition containing the activated carbon further contains a pH adjuster.
  • Item 14 An automobile canister containing the latent heat storage material integrated activated carbon according to any one of Items 1 to 9.
  • Item 15 An automobile canister connected to a closed gasoline tank containing the latent heat storage material integrated activated carbon according to any one of Items 1 to 9.
  • an activated carbon with a latent heat storage material that can maintain a high level of adsorption / desorption performance and durability.
  • the latent heat storage material integrated activated charcoal of the present invention contains a latent heat storage material having microcapsules encapsulating a phase change substance that absorbs and releases latent heat depending on the temperature, and an activated charcoal.
  • the surface of the microcapsule is coated with an organic binder-containing layer containing a thermosetting organic binder A, and the surface of the latent heat storage material contains activated charcoal. It is coated with an activated charcoal-containing layer.
  • the latent heat storage material integrated activated charcoal having such a configuration can be produced without physical damage to the latent heat storage material, elution of inclusions from the latent heat storage material is suppressed when exposed to a solvent. It is stable for a long period of time, and its structure is such that the surface of one latent heat storage material is coated with activated charcoal, and the temperature rise due to heat of adsorption can be efficiently suppressed by the latent heat storage material, so that it exhibits high solvent absorption / desorption performance.
  • phase-changing substance encapsulated in the microcapsules is not particularly limited as long as it is a compound capable of absorbing and releasing latent heat as the phase changes.
  • phase change for example, a phase change between a solid and a liquid can be exemplified.
  • the temperature at which the phase-changing substance can undergo a phase change (for example, melting point, freezing point, etc.) can be appropriately selected depending on the use of the canister, but is usually about 0 to 50 ° C.
  • phase change material preferred compounds, for example, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, aliphatic hydrocarbon straight, such as docosane, natural wax; petroleum waxes; LiNO 3 ⁇ 3H Hydrate of inorganic compounds such as 2 O, Na 2 SO 4 ⁇ 10H 2 O, Na 2 HPO 4 ⁇ 12H 2 O; Fatty acids such as capric acid and lauric acid; Higher alcohols having 12 to 15 carbon atoms; Palmitic acid Examples thereof include ester compounds such as methyl and methyl stearate.
  • the phase change substance can be used alone or in combination of two or more for the purpose of adjusting the melting point.
  • a combination is preferable in which the difference in temperature at which the phase-changing substances of each phase-changing substance occurs is about 0 to 15 ° C.
  • a compound having a melting point higher than the melting point of the phase-changing substance in order to prevent the supercooling phenomenon of the phase-changing substance, a compound having a melting point higher than the melting point of the phase-changing substance can be contained.
  • refractory compound examples include aromatic compounds, esters, carboxylic acids, alcohols, amides and the like.
  • the refractory compound may be used alone or in combination of two or more.
  • Examples of the aromatic compound include halogen-substituted benzene and naphthalene.
  • the halogen-substituted benzene include dihalogenated benzene such as dibromobenzene and dichlorobenzene.
  • esters examples include fatty acid esters of monoalcohols such as methyleicosanoic acid; fatty acid esters of glycerin such as linoleic acid glyceride.
  • carboxylic acids examples include aliphatic carboxylic acids such as myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadesyl acid, eicosanoic acid, henicosanoic acid and bechenic acid; and aromatic carboxylic acids such as benzoic acid. It can be exemplified.
  • alcohols include monoalcohols having 16 to 30 carbon atoms such as cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, and eikosanol.
  • amides include fatty acid amides such as icosane acid amide, nonadecylic acid amide, stearic acid amide, and oleic acid amide.
  • the content thereof is preferably 0.5 to 30 parts by mass and 1 to 15 parts by mass with respect to 100 parts by mass of the content of the phase change substance from the viewpoint of solvent adsorption / desorption performance. More preferred.
  • a known material can be used, and for example, a polymer compound such as a resin can be exemplified.
  • the polymer compound include formaldehyde-melamine resin, melamine resin, formaldehyde-urea resin, urea resin, urea-formaldehyde-polyacrylic acid copolymer, polystyrene, polyvinyl acetate, polyacrylonitrile, polyethylene, polybutyl methacrylate, gelatin and the like.
  • These materials can be used alone or in combination of two or more.
  • the weight ratio of the microcapsule material to the phase-changing substance is not particularly limited, but the total amount of the microcapsule material and the phase-changing substance is 100% by mass, and from the viewpoint of solvent adsorption / desorption performance, the material of the microcapsule is usually used.
  • the content of the phase changing substance can be 10 to 30% by mass, and the content of the phase changing substance can be 70 to 90% by mass.
  • a high melting point compound is used, the total amount of the microcapsule material, the phase change substance, and the high melting point compound is set to 100% by mass, and the content of the microcapsule material is usually set from the viewpoint of solvent adsorption / desorption performance. It can be 10 to 30% by mass, and the total content of the phase change substance and the refractory compound can be 70 to 90% by mass.
  • the method for microencapsulating the phase-changing substance used in the present invention existing techniques such as a core selvation method, an interfacial polymerization method, an in-situ method, and a method using yeast can be used, and any of the methods can be used. However, the effect of the present invention can be achieved.
  • a phase change substance (and a refractory compound if necessary) is emulsified in a liquid medium using an emulsifier or the like, an initial condensate (prepolymer) corresponding to the desired resin is added thereto, and then the temperature is raised. Then, by advancing the polymerization reaction, a microcapsule dispersion (slurry) having a resin wall and containing a phase change substance (and a refractory compound if necessary) can be prepared.
  • Water is particularly preferable as the liquid medium, but alcohols such as methanol, ethanol and propanol, and water-miscible solvents such as acetone can also be used.
  • the above solvent may be used alone or in combination of two or more.
  • the shape of the microcapsules is usually spherical particles (powder or granules), and the particle size of the particles is controlled by the type and concentration of the emulsifier at the time of encapsulation, the temperature and time at the time of emulsification, the emulsification method, etc. Since it varies depending on the factors of, the optimum conditions can be set by experiments.
  • the average particle size of the microcapsules is preferably about 0.1 to 500 ⁇ m, more preferably about 1 to 100 ⁇ m, and even more preferably about 2 to 10 ⁇ m.
  • the average particle size of the microcapsules was measured by a laser diffraction type particle size distribution measuring device (manufactured by Microtrac Bell: Microtrac MT3300EXII), and the particle size when the cumulative volume of the volume standard was 50% was taken as the average particle size.
  • the measurement sample shall be obtained by irradiating 30 min of ultrasonic waves to crush the secondary particles into primary particles.
  • the surface of the above-mentioned microcapsules is coated with an organic binder-containing layer containing a thermosetting organic binder A.
  • the number of microcapsules coated with the organic binder-containing layer containing the thermosetting organic binder A is not particularly limited, and may be one or a plurality (for example, 2 to 10). According to the production method, one microcapsule is usually coated with an organic binder-containing layer containing a thermosetting organic binder A.
  • thermosetting organic binder A a general one can be used and is not particularly limited.
  • a thermosetting resin such as a phenol resin, an acrylic resin, an epoxy resin, an isocyanate resin, a melamine resin, a urethane resin, or an amide ester resin is used.
  • a thermosetting resin in which the JIS hardness (JIS K1474 (2014)) of the obtained latent heat storage material tends to be high is preferable.
  • the thermosetting organic binder A is preferably a resin having high solvent resistance (water resistance, organic solvent resistance, etc.) after molding.
  • the latent heat storage material can easily prevent the dispersion and swelling of the microcapsules by the solvent that can be used in the production method described later, and the latent heat storage material is hard. Easy to maintain. Further, since the hardness of the latent heat storage material tends to be high, it is easy to suppress the pulverization of the latent heat storage material at the time of molding, and it is easy to suppress the destruction of powdered microcapsules by activated carbon.
  • the content of the thermosetting organic binder A in the latent heat storage material easily suppresses the temperature rise due to the heat of adsorption of the activated charcoal, easily improves the amount of latent heat, improves the adsorption performance, and also improves the durability. From the viewpoint of ease, 5 to 20 parts by mass is preferable, 8 to 18.5 parts by mass is more preferable, and 14.5 to 18.5 parts by mass is further preferable with respect to 100 parts by mass of the microcapsule containing the phase change substance.
  • the organic binder-containing layer containing the thermosetting organic binder A may be composed of only the above-mentioned thermosetting organic binder A, or may be a curing accelerator, a coloring agent, a plasticizing agent, a stabilizer, and a release agent.
  • Additives such as a mold agent (metal soap such as zinc stearate) may be contained.
  • the content of such an additive is preferably in a range that does not impair the effects of the present invention, and is preferably 0 to 10% by mass, preferably 0 to 5% by mass, with the total amount of the organic binder-containing layer being 100% by mass. More preferably, 0 to 3% by mass is further preferable.
  • the shape of the latent heat storage material including the organic binder-containing layer is not particularly limited, and any of pellet shape (cylindrical shape, spherical shape, etc.), disk shape, block shape, etc. can be adopted.
  • the average cross-sectional diameter of the latent heat storage material including the organic binder-containing layer is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, and it is easy to improve the latent heat amount to improve the adsorption performance. From the viewpoint of easy improvement and easy improvement of durability, 0.75 to 1.80 mm is preferable, 0.78 to 1.50 mm is more preferable, and 0.80 to 1.20 mm is further preferable. When passing through a hole such as a die of a molding machine, it is preferable to make the hole smaller than the hole because it is easy to suppress performance deterioration due to cracking of the microcapsules.
  • the average cross-sectional diameter of the latent heat storage material is calculated by calipers.
  • the JIS hardness of the latent heat storage material-integrated activated carbon in the latent heat storage material-integrated activated carbon is from the viewpoint of easily suppressing cracking and pulverization due to contact between the latent heat storage material and the activated carbon, the latent heat storage material-integrated activated carbon of the present invention. Is preferably larger than.
  • the JIS hardness of the latent heat storage material is, for example, preferably 90% or more, and more preferably 95 to 100%.
  • the JIS hardness of the latent heat storage material is measured according to JIS K1474 (2014).
  • the surface of the latent heat storage material having an organic binder-containing layer formed on the surface of the above-mentioned microcapsules further contains activated carbon containing activated carbon. It is covered with a layer.
  • the number of latent heat storage materials coated with the activated carbon-containing layer containing activated carbon is not particularly limited and may be one or a plurality (for example, 2 to 10), but according to the production method of the present invention described later.
  • one latent heat storage material is often coated with an activated carbon-containing layer containing activated carbon.
  • activated carbon used in the present invention a commonly used activated carbon for canisters can be used.
  • activated carbon those obtained from various raw materials such as coal-based, coconut shell-based, wood-based, and lignin-based can be used, and steam activated products; carbon dioxide gas activated products; chemical activated products using phosphoric acid, zinc chloride, alkali metals, etc. Activated carbon products can be used.
  • the activated carbon applied to the present invention may be in any form such as powder, granular, crushed charcoal, etc., but when used for canister applications, it is preferably in the form of powder having pores in order to increase the adsorption capacity of the evaporated fuel. ..
  • the average particle size of the activated carbon powder is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and the durability is also improved. From the viewpoint of easy acclimation, 1 ⁇ m to 10 mm is preferable, 5 ⁇ m to 1 mm is more preferable, and 10 to 100 ⁇ m is further preferable.
  • the average particle size of the activated carbon powder is measured by a laser diffraction type particle size distribution measuring device (Microtrac Bell: Microtrac MT3300EXII), and the average particle size is defined as a volume-based cumulative particle size of 50%.
  • the specific surface area of the activated carbon is not particularly limited, but it is easy to suppress the temperature rise due to the heat of adsorption of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. From the viewpoint, 500 to 2500 m 2 / g is preferable, 600 to 2400 m 2 / g is more preferable, and 800 to 2000 m 2 / g is further preferable.
  • the specific surface area of activated carbon having a diameter of 30 nm or less is measured by a specific surface area / pore distribution measuring device (manufactured by Microtrac Bell Co., Ltd .: Belsorb miniII), and a nitrogen adsorption isotherm of activated carbon at liquid nitrogen temperature is created. Then, it is calculated by the Cranston-Inkley (CI) method.
  • CI Cranston-Inkley
  • the pore volume of the activated carbon is not particularly limited, and from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability, for example, 0.10. It is preferably ⁇ 1.00 mL / g, more preferably 0.20 to 0.90 mL / g, and even more preferably 0.30 to 0.80 mL / g.
  • the pore volume of activated carbon with a diameter of 30 nm or less is measured by a specific surface area / pore distribution measuring device (manufactured by Microtrac Bell Co., Ltd .: Belsolp miniII), and the nitrogen adsorption isotherm of activated carbon at liquid nitrogen temperature is measured. It is prepared and calculated by the Cranston-Inkley (CI) method.
  • the pH of the activated carbon is, for example, a carboxylate state under neutral or basic conditions, and the binder is easily dissolved in water. Therefore, the uniformity of the binder on the surface of the activated carbon is easily improved, and the hardness is improved.
  • the pH of the aqueous suspension of activated carbon measured in accordance with JIS K 1474 (2014) is preferably 4.0 or higher, more preferably 4.5 or higher. 5.0 or more is more preferable.
  • the upper limit of the pH of the aqueous suspension of activated carbon measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
  • the content of the latent heat storage material in the latent heat storage material integrated activated coal is from the viewpoint that the amount of temperature change is easily suppressed, the latent heat amount is easily improved, the adsorption performance is easily improved, and the durability is also easily improved.
  • the total amount of the latent heat storage material integrated activated charcoal is 100% by mass, it is preferably 7 to 30% by mass, more preferably 9 to 29% by mass, still more preferably 14 to 19% by mass.
  • the content of activated carbon in the activated carbon integrated with the latent heat storage material is easy to suppress the amount of temperature change, easily improve the latent heat amount, improve the adsorption performance, and easily improve the durability.
  • the total amount of the material-integrated activated carbon as 100% by mass, 62 to 86% by mass is preferable, 63 to 84% by mass is more preferable, and 73 to 79% by mass is further preferable.
  • the activated carbon-containing layer contained in the activated carbon integrated with the latent heat storage material of the present invention may be composed of only the above-mentioned activated carbon, but may further contain an organic binder B.
  • a binder of a thermoplastic resin or a thermosetting resin generally used for molding an adsorbent such as activated charcoal can be used, as well as a paint / adhesive, a fiber treatment binder, and the like.
  • Cross-linking / adhesion improving agents, thermoplastic resins, and additives for coating agents such as films can be used.
  • commonly used ones such as cellulose derivatives such as methyl cellulose and carboxylmethyl cellulose, phenol resins, melamine resins, epoxy resins, urethane resins, polyvinyl alcohols, vinyl acetate, vinylidene chloride resins, and oxazoline-containing polymers can be used without limitation.
  • These organic binders B can be used alone or in combination of two or more. Further, the same one as the above-mentioned thermosetting organic binder A may be used, or a different one may be used.
  • the content of the organic binder B in the activated carbon integrated with the latent heat storage material makes it difficult to block the pores of the activated carbon, easily suppresses the amount of temperature change, easily improves the latent heat amount, and easily improves the adsorption performance and is durable.
  • the total amount of the latent heat storage material integrated activated carbon is 100% by mass, preferably 5 to 10% by mass, more preferably 6 to 9% by mass, still more preferably 7 to 8% by mass.
  • the activated carbon-containing layer contained in the activated carbon integrated with the latent heat storage material of the present invention may be composed of only the above-mentioned activated carbon and, if necessary, the organic binder B. As described above, under neutral or basic conditions, the uniformity of the binder on the surface of the activated carbon is easily improved and the hardness is easily improved, so that the pH can be adjusted with a pH adjuster.
  • Acid, base, salt, buffer solution, etc. can be used as the pH adjuster.
  • bases such as sodium hydroxide, potassium hydroxide, potassium hydroxide, barium hydroxide, ammonia, magnesium hydroxide, calcium hydroxide, aluminum hydroxide; hydrochloric acid, nitrate, phosphoric acid, boric acid, acetic acid, citric acid, Acids such as carbonic acid; salts such as sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium hydrogen sulfate and the like; buffer solutions combining these can be mentioned.
  • the content of the pH adjuster in the latent heat storage material integrated activated carbon is the total amount of the latent heat storage material integrated activated carbon from the viewpoint of easily improving the uniformity of the binder on the surface of the activated carbon and easily improving the hardness.
  • 100% by mass 0 to 10% by mass is preferable, and 0 to 5% by mass is more preferable.
  • the activated carbon-containing layer containing activated carbon may be composed of only the above-mentioned activated carbon and, if necessary, organic binder B, or a cross-linking agent, a coloring agent, a plasticizing agent, a stabilizer, and a mold release agent (stearic acid).
  • Additives such as (metal soap such as zinc acid acid) may be contained.
  • the content of such an additive is preferably in a range that does not impair the effects of the present invention, and is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, with the total amount of the activated carbon-containing layer being 100% by mass. It is preferable, and 0 to 3% by mass is more preferable.
  • the pH of the activated carbon-containing layer is, for example, in the state of a carboxylate under neutral and basic conditions and is easily dissolved in water, so that it is easy to improve the uniformity of the binder on the surface of the activated carbon and improve the hardness.
  • the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is preferably 4.5 or higher, more preferably 5.5 or higher. It is preferable, and 6.0 or more is more preferable.
  • the upper limit of the pH of the aqueous suspension of the activated carbon-containing layer measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
  • the thickness of the activated carbon-containing layer containing activated carbon is not particularly limited, but it is easy to suppress the temperature rise due to the heat of adsorption of the activated carbon, it is easy to improve the latent heat amount, and it is easy to improve the adsorption performance and durability. From the viewpoint of easy improvement, 180 to 2050 ⁇ m is preferable, 250 to 900 ⁇ m is more preferable, and 350 to 780 ⁇ m is further preferable.
  • the thickness of the activated carbon-containing layer is measured with a caliper after breaking the monolithic coal and removing the heat storage material.
  • the shape of the latent heat storage material-integrated activated carbon of the present invention described above is not particularly limited, but for example, according to the manufacturing method described later, it tends to be spherical or elliptical spherical.
  • the average particle size of the activated carbon integrated with the latent heat storage material of the present invention is not particularly limited, but it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is durable. From the viewpoint of easily improving the property, easily lowering the ventilation resistance, and easily improving the air flow in the canister, 1.0 to 4.0 mm is preferable, 1.2 to 3.4 mm is more preferable, and 1. 7 to 2.8 mm is more preferable.
  • the average particle size of the latent heat storage material-integrated activated carbon of the present invention is sieved using a low tap and a sieve according to JIS K1474 (2014), and the mass average particle size is calculated.
  • the calorific value of the latent heat storage material-integrated activated carbon of the present invention can be 10 to 100 J / g, preferably 11 to 80 J / g, and more preferably 12 to 60 J / g. Therefore, the activated carbon integrated with the latent heat storage material of the present invention can easily suppress the temperature rise due to the heat of adsorption of the activated carbon, and can easily improve the adsorption / desorption performance, durability, hardness, and the like.
  • the calorific value of the latent heat storage material is measured by DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Inc.).
  • the pH of the activated carbon integrated with the latent heat storage material of the present invention is, for example, in the state of a carboxylic acid salt under neutral and basic conditions and is easily dissolved in water. Easy to improve. Therefore, although not particularly limited, the pH of the aqueous suspension of the latent heat storage material-integrated activated carbon of the present invention measured in accordance with JIS K 1474 (2014) is preferably 4.5 or more. 5.5 or more is more preferable, and 6.0 or more is further preferable.
  • the upper limit of the pH of the aqueous suspension of the latent heat storage material-integrated activated carbon of the present invention measured in accordance with JIS K 1474 (2014) is not particularly limited, but is usually about 14.0.
  • the latent heat storage material integrated activated carbon of the present invention thus obtained can have a high hardness.
  • the ASTM hardness of the latent heat storage material-integrated activated carbon of the present invention is preferably 45% or more, more preferably 48 to 80%, and even more preferably 50 to 80%.
  • the ASTM hardness of the latent heat storage material integrated activated carbon of the present invention is measured according to ASTM-D5228.
  • the latent heat storage material-integrated activated carbon of the present invention thus obtained can increase the butane activity (BA) indicating the fuel evaporation gas adsorption performance.
  • the butane activity (BA) of the latent heat storage material-integrated activated carbon of the present invention is preferably 42% or more, more preferably 43 to 60%, still more preferably 44 to 53%. It is known that when butane activity (BA) is 42% or more, the fuel evaporation gas adsorption performance is excellent.
  • the butane activity (BA) of the latent heat storage material-integrated activated carbon of the present invention is measured according to ASTM-D5228.
  • the latent heat storage material-integrated activated charcoal of the present invention as described above can be filled in a canister container, and the vaporized fuel gas from the fuel tank is introduced into the container to form a canister and adsorb the vaporized fuel gas.
  • the canister that adsorbs the evaporated fuel generated in the fuel tank is not particularly limited, and an existing one can be used.
  • automobile applications include closed fuel tanks and canisters connected to ordinary fuel tanks. The connection between the closed fuel tank or the normal fuel tank and the canister can be directly connected or indirectly connected via a blocking valve or an opening valve between them.
  • the temperature of the gas and the container is preferably equal to or lower than the phase change temperature (usually the melting point) of the phase change substance. That is, the latent heat storage material integrated activated carbon of the present invention is useful as a latent heat storage material integrated activated carbon for canisters.
  • Examples of the vaporized fuel gas to which the latent heat storage material-integrated spherical activated carbon of the present invention can be applied include hydrocarbon-based, ketone, halogen-based, alcohol, ester, and gasoline for automobiles, which are often used in solvent recovery.
  • the method for producing activated carbon integrated with latent heat storage material of the present invention is not particularly limited, but for example.
  • the microcapsule composition obtained in step (1) is coated with the thermosetting organic binder A and heat-treated to obtain the above.
  • the process of obtaining latent heat storage material, (3) It can be produced by a method including a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing the activated carbon.
  • Step (1) In the step (1), first, the microcapsules and the thermosetting organic binder A are mixed. Specifically, in step (1), it is preferable that the microcapsules and the thermosetting organic binder A are mixed, then extruded and granulated, and then granulated. The thermosetting organic binder A at this time is not coated on the surface of the microcapsules, but is used for mixing with the microcapsules.
  • the amount of the heat-curable organic binder A added makes it easy to improve the binding force of the latent heat storage material obtained in the step (2), easily improves the hardness and solvent resistance, and makes it difficult for the microcapsules to be broken.
  • 5 to 30 parts by mass is preferable with respect to 100 parts by mass of the microcapsules. 8 to 25 parts by mass is more preferable, and 10 to 20 parts by mass is further preferable.
  • the method of mixing the microcapsules and the thermosetting organic binder A is not particularly limited.
  • microcapsules and a thermosetting organic binder A may be mixed in a solvent in a conventional manner to form a slurry.
  • the solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof.
  • a solvent may not be used.
  • the amount of the solvent added is preferably 3 to 50 parts by mass with respect to 100 parts by mass of the microcapsules from the viewpoint of easily suppressing cracks and powdering after molding and increasing the packing density of the microcapsules. By mass is more preferred, and 10 to 20 parts by mass is even more preferred.
  • the total amount including the solvent present in the thermosetting organic binder A can be within the above range. ..
  • the extrusion granulation is not particularly limited and can be performed by a conventional method, and a general granulation machine such as a stirring granulation machine, a compression granulation machine, an extrusion granulation machine, or a rolling granulation machine is used.
  • a general granulation machine such as a stirring granulation machine, a compression granulation machine, an extrusion granulation machine, or a rolling granulation machine is used.
  • a die such as a screen die, a disk die, or a dome-shaped die is used to granulate the latent heat storage material to a desired size, and further, a pan-type granulator or a drum mixer. , It can be sized by rolling at about 50 to 1000 rpm using a mulmerizer or the like.
  • Step (2) is a step of coating the microcapsule composition obtained in the step (1) with a thermosetting organic binder A and heat-treating the microcapsule composition to obtain a latent heat storage material.
  • thermosetting organic binder A used at this time may be the same as the thermosetting organic binder A used in the step (1), or may be different.
  • the latent heat storage material after the thermosetting organic binder A is cured uses the thermosetting organic binder A having high solvent resistance (water resistance, organic solvent resistance, etc.).
  • solvent resistance water resistance, organic solvent resistance, etc.
  • the cured latent heat storage material does not become turbid even when immersed in water at 50 ° C. for 24 hours, and further, it does not become turbid even when immersed in water at 70 ° C. for 24 hours. More preferred.
  • the organic solvent resistance after the cured latent heat storage material is immersed in an organic solvent at 30 ° C.
  • the amount of the phase change substance exuded into the organic solvent is the latent heat. It is preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total amount of the phase changing substance in the heat storage material.
  • a thermosetting resin binder having water resistance such as a phenol resin, an acrylic resin, a melamine resin, and an amide ester resin is preferable.
  • the amount of the heat-curable organic binder A added to coat the microcapsule composition obtained in the step (1) is likely to suppress a temperature rise due to the heat of adsorption of the activated charcoal, easily improve the amount of latent heat, and easily improve the adsorption performance.
  • the total amount of the microcapsule composition obtained in the step (1) is 100 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. .5 to 3 parts by mass is more preferable.
  • the method of coating the microcapsule composition obtained in the step (1) with the thermosetting organic binder A is not particularly limited.
  • it can be coated in a solvent using a one-fluid nozzle, a two-fluid nozzle, or the like.
  • the solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof.
  • a solvent may not be used.
  • the amount of the solvent added is from the viewpoint that it is easy to suppress cracking and pulverization after molding, it is easy to suppress the temperature rise due to the adsorption heat of activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Therefore, the total amount of the microcapsule composition obtained in the step (1) is 100 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, and further 1.5 to 3 parts by mass. preferable.
  • the thermosetting organic binder A is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the thermosetting organic binder A can be within the above range. ..
  • the heating temperature during the heat treatment is not particularly limited, and is 100 to 300 ° C. from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Is preferable, and 150 to 250 ° C. is more preferable.
  • the heating time during the heat treatment is not particularly limited, and it is easy to complete the curing reaction and improve the durability. Therefore, 30 to 180 minutes is preferable, and 60 to 150 minutes is more preferable.
  • thermosetting organic binder A can be cured to obtain a latent heat storage material.
  • Step (3) is a step of mixing and granulating the latent heat storage material obtained in the step (2) and the composition containing activated carbon. Thereby, the latent heat storage material obtained in the step (2) can be coated with the activated carbon-containing layer to produce the latent heat storage material integrated activated carbon of the present invention.
  • the composition containing activated carbon can form the above-mentioned activated carbon-containing layer, and can contain the above-mentioned organic binder B and pH adjuster, if necessary, in addition to the activated carbon.
  • the content of the organic binder B is such that the temperature rise due to the heat of adsorption of the activated carbon can be easily suppressed, the amount of latent heat can be easily improved, the adsorption performance can be easily improved, and the durability can be easily improved.
  • 100 parts by mass 0.5 to 20 parts by mass is preferable, and 6 to 11 parts by mass is more preferable.
  • the content of the pH adjuster is preferably 0 to 10 parts by mass with respect to 100 parts by mass of activated carbon from the viewpoint of easily improving the uniformity of the binder on the surface of the activated carbon and easily improving the hardness. , 0-5 parts by mass is more preferable.
  • the washing method may be a general washing method of chemical-activated charcoal.
  • phosphoric acid-activated charcoal it can be washed with hot water or cold water and dried.
  • a basic aqueous solution such as an ammonium carbonate aqueous solution may be used instead of hot water or cold water.
  • the composition containing activated carbon may contain a solvent from the viewpoint of easily suppressing cracking and pulverization after molding.
  • the solvent that can be used at this time is not particularly limited, and general solvents can be used, and examples thereof include water, alcohol (methanol, ethanol, etc.), and a mixed solution thereof.
  • a solvent may not be used.
  • the amount of the solvent added is easy to suppress cracking and pulverization after molding, easy to suppress the temperature rise due to the adsorption heat of activated carbon, easy to improve the latent heat amount, easy to improve the adsorption performance, and easy to improve the durability. Therefore, 50 to 1500 parts by mass is preferable, 100 to 500 parts by mass is more preferable, and 300 to 650 parts by mass is further preferable with respect to 100 parts by mass of activated carbon.
  • the organic binder B is in the form of a solution, a dispersion, a suspension, or the like, the total amount including the solvent present in the organic binder B can be in the above range.
  • the latent heat storage material obtained in the step (2) and the composition containing activated carbon are mixed and granulated (the latent heat storage material obtained in the step (2) is coated with the activated carbon-containing layer).
  • the extrusion granulation method is a method in which a binder is added to a composition containing a latent heat storage material and activated charcoal obtained in step (2) and kneaded, and the kneaded product is extruded from a screen to form and granulate.
  • the crushing and granulating method which is a method in which the kneaded mass prepared by kneading in the above method is cut with a rotary blade of a granulator and ejected from the outer screw eyes by centrifugal force; obtained in step (2).
  • Rolling granulation method which is a method of obtaining particles close to spheres by applying a rotating motion or vibration to a humidified powder by adding a binder to a composition containing a latent heat storage material and activated charcoal to agglomerate the powder.
  • the fluidized layer granulation method is a method in which the obtained composition containing the latent heat storage material and the activated charcoal is flowed from below by a hot air stream, and a binder is sprayed onto the composition to granulate the composition; the latent heat obtained in the step (2).
  • An unlimited example of a stirring granulation method in which a composition containing a heat storage material and activated charcoal is put into a container and water or a granulating liquid is added while stirring with a rotating blade to agglomerate raw material powders and granules into a spherical shape. be able to. At this time, it can be molded by using a mulmerizer, spray granulation, fluidized bed granulation, stirring granulation machine, bread type granulation machine and the like.
  • the amount of the composition containing activated carbon to be used is not particularly limited, and it is easy to suppress cracking and pulverization after molding, it is easy to suppress the temperature rise due to the heat of adsorption of activated carbon, and it is easy to improve the amount of latent heat to improve the adsorption performance. From the viewpoint of easy improvement and easy improvement of durability, 200 to 1000 parts by mass is preferable, and 250 to 600 parts by mass is more preferable with respect to 100 parts by mass of the latent heat storage material obtained in the step (2).
  • the binder is not particularly limited, and for example, cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hypromellose, and carboxymethyl cellulose; crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone (povidone), and vinylpyrrolidone are used. Examples thereof include polymers (copolyvidone), acrylic acid-based polymers, gelatin, gum arabic, purulan, canten, tragant, sodium alginate, propylene glycol alginate, pregelatinized starch, dextrin, macrogol, and sucrose. These binders can also be used in the form of a solution such as an aqueous solution. These binders can be used alone or in combination of two or more.
  • the amount of the above binder used is 15 to 100 parts by mass in terms of solid content with respect to 100 parts by mass of the latent heat storage material obtained in step (2) from the viewpoint of easily suppressing cracks and powdering after molding. Preferably, 17 to 85 parts by mass is more preferable.
  • the heating temperature during the heat treatment is not particularly limited, and is 80 to 250 ° C. from the viewpoint that it is easy to suppress the temperature rise due to the adsorption heat of the activated carbon, it is easy to improve the latent heat amount, it is easy to improve the adsorption performance, and it is easy to improve the durability. Is preferable, and 100 to 200 ° C. is more preferable.
  • the heating time during the heat treatment is not particularly limited, and can be set to a time during which a spherical activated carbon having a sufficiently small particle size and high sphericity can be obtained. From the viewpoint of easy improvement, easy improvement of adsorption performance and easy improvement of durability, 10 minutes to 12 hours is preferable, and 30 minutes to 6 hours is more preferable. At this time, it is preferable to adjust the water content of the obtained latent heat storage material-integrated activated carbon of the present invention to be 10% by mass or less, particularly 5% by mass or less.
  • the average particle size of the microcapsules was measured by a laser diffraction type particle size distribution measuring device (Microtrack Bell Co., Ltd .: Microtrack MT3300EXII), and the average cross section of the latent heat storage material was measured.
  • the diameter was measured for 10 pellets with a caliper, and the calorific value of the latent heat storage material was measured with a DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Co., Ltd.).
  • the "existing method” is an in-situ method using an initial condensate of a formalin condensation type resin. It means that the microcapsules were prepared by the above operation: The sodium salt aqueous solution of the styrene anhydride maleic acid copolymer whose pH was adjusted to 4.5 was vigorously stirred with a homomixer, and the phase change substance was twice that of the above emulsion. A predetermined phase transition substance having a predetermined phase transition temperature was gradually added so as to have the number of moles of the above, and emulsification was performed until the average particle size became 3.0 to 4.0 ⁇ m.
  • melamine formaldehyde: water was mixed so as to have a molar number of 1: 2: 7, adjusted to pH 10, and heated to 60 ° C. with stirring to obtain an initial condensate.
  • the above emulsion is transferred to a separate container, the melamine formalin initial condensate is added, and the mixture is reacted at 80 ° C. for 3 hours to obtain a microcapsule aqueous dispersion in which the ratio of the melamine film to the microcapsules is 17%. Solid content (40% by weight) was obtained, the pH was adjusted to 9, and encapsulation was performed.
  • Polyvinyl alcohol was added so as to be 0.5% by mass with respect to the aqueous dispersion of the microcapsules, the mixture was stirred again, and then dried by a spray-drying method to obtain microcapsules.
  • the activated carbon weighs 1.0 g
  • the latent heat storage material integrated activated carbon and the molded products of the production example and the comparative production example are 3 0.0 g was added to 100 mL of water, heated for 5 minutes so that boiling continued, cooled to room temperature, and the pH of the aqueous suspension obtained by adding water to 100 mL was measured using a pH meter.
  • Example 1 Microcapsules covered with a melamine membrane prepared by an existing method containing a linear aliphatic hydrocarbon having a phase transition temperature of 50 to 52 ° C. were used.
  • thermosetting phenol-based organic binder phenolite 1480 manufactured by DIC Corporation; solid content 68.7% by mass
  • 18 parts by mass of water were added. And mixed. Then, the mixture was molded by an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.). At this time, the opening of the screen die was finely divided using 1.0 mm. Then, using Malmerizer (QJ-400 type manufactured by Dalton Co., Ltd.), the granules were sized for 2 minutes at 275 rpm to obtain a microcapsule composition.
  • the obtained microcapsule composition was used and coated with a thermosetting phenolic binder similar to the above. Specifically, 1.5 parts by mass of the heat-curable phenolic binder and an equal amount of water as a solvent were added to 100 parts by mass of the obtained microcapsule composition, and a one-fluid nozzle was used. The microcapsules were coated with a heat-curable phenolic solvent, the material temperature was set to 160 ° C. or higher, and the cells were dried for 2 hours to obtain a latent heat storage material.
  • the activated carbon, the organic binder and water were kneaded in advance and crushed to obtain a mixture (composition containing activated carbon).
  • the organic binder carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), ADEKA Resin (ADEKA Corporation) Made of water-based epoxy resin EM-0180) was selected, and the solid content was 7.2 parts by mass, 1.2 parts by mass, and 2.1 parts by mass, for a total of 10.5 parts by mass with respect to 100 parts by mass of activated carbon. 160.5 parts by mass of water was added to 100 parts by mass of activated charcoal.
  • Example 2 A latent heat storage material as in Example 1, except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 45 to 47 ° C. were used. Got Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 2 was obtained.
  • Example 3 Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is 0.
  • Example 4 Same as in Example 1 except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 22) having a phase transition temperature of 42 to 45 ° C. were used as inclusions. In addition, a latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 4 was obtained.
  • a linear aliphatic hydrocarbon carbon number 22 having a phase transition temperature of 42 to 45 ° C.
  • Example 5 Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is 1.
  • Example 6 Same as in Example 1 except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 20) having a phase transition temperature of 32 to 37 ° C. were used as inclusions. In addition, a latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 6 was obtained.
  • Example 7 Similar to Example 1, except that microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (16 carbon atoms) having a phase transition temperature of 18 ° C. as an inclusion were used. A latent heat storage material was obtained. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Example 7 was obtained.
  • Comparative Example 1 The microcapsules used in Example 1 were used as microcapsules covered with a melamine membrane prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 50 to 52 ° C. as an inclusion. A microcapsule composition was produced in the same manner as in Example 1 and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 1 was obtained.
  • Comparative Example 2 A microcapsule composition was prepared in the same manner as in Example 1 using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon having a phase transition temperature of 45 to 47 ° C. as an inclusion. Manufactured and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 2 was obtained.
  • Comparative Example 3 Similar to Example 1, using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 22) having a phase transition temperature of 42 to 45 ° C. as an inclusion. A microcapsule composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 3 was obtained.
  • a linear aliphatic hydrocarbon carbon number 22
  • Comparative Example 4 Similar to Example 1, using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (carbon number 20) having a phase transition temperature of 32 to 37 ° C. as an inclusion. A microcapsule composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 4 was obtained.
  • a linear aliphatic hydrocarbon carbon number 20
  • Comparative Example 5 Using a microcapsule covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (16 carbon atoms) having a phase transition temperature of 18 ° C., the microcapsule is the same as in Example 1. The composition was produced and used as a latent heat storage material. That is, the surface of the microcapsules was not coated with a thermosetting organic binder. Then, in the same manner as in Example 1, the latent heat storage material integrated activated carbon of Comparative Example 5 was obtained.
  • Comparative Example 6 Using microcapsules covered with a melamine film prepared by an existing method using a linear aliphatic hydrocarbon (22 carbon atoms) having a phase transition temperature of 42 to 45 ° C., the opening of the screen die is opened.
  • a latent heat storage material was obtained in the same manner as in Example 1 except that the particles were finely divided using 0.7 mm.
  • the activated carbon integrated with the latent heat storage material was obtained.
  • Test Example 1 3 g of the latent heat storage material integrated activated carbon obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was charged into a portable reactor pressure-resistant container (TVS-1 type manufactured by Pressure-Resistant Glass Industry Co., Ltd.), and 10 mL of gasoline was charged. .. Then, after heat-treating at 70 ° C. for 48 hours, the activated carbon integrated with the latent heat storage material was taken out on a petri dish, washed with 30 mL of hexane (special grade reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and then blown. It was dried at 40 ° C. for 2 hours using a low temperature dryer (DK340S manufactured by Yamato Scientific Co., Ltd.).
  • a portable reactor pressure-resistant container (TVS-1 type manufactured by Pressure-Resistant Glass Industry Co., Ltd.)
  • 10 mL of gasoline was charged. ..
  • the activated carbon integrated with the latent heat storage material was taken out on a pe
  • the calorific value was measured using DSC7020 (differential scanning calorimeter, manufactured by Seiko Instruments Inc.). The calorific value after gasoline treatment was divided by the calorific value at the time of untreatment to calculate the calorific value residual ratio. The results are shown in Table 1.
  • thermosetting organic binder By comparing Examples 1 to 7 and Comparative Examples 1 to 5, the outer surface of the microcapsules is coated with a thermosetting organic binder, so that the residual rate of the amount of heat possessed by the latent heat storage material after the gasoline immersion test Is as high as 93% or more, and it can be seen that the residual amount of heat is significantly reduced without coating (53 to 56%). From this, it can be seen that the effect of coating the microcapsules with a thermosetting organic binder is high. Furthermore, the same tendency was obtained regardless of the type of phase change substance.
  • the latent heat storage material in the latent heat storage material integrated activated carbon coated with the thermosetting organic binder (Example 4) and the latent heat storage material integrated activated carbon not coated with the heat curable organic binder (Comparative Example 3).
  • 1 and 2 show a comparison of SEM images of the latent heat storage material in).
  • the one in which the activated carbon-containing layer on the surface was peeled off from each latent heat storage material integrated activated carbon by hitting with a hammer was evaluated. It can be seen that those coated with a thermosetting organic binder have less cracks, and those not coated with a thermosetting organic binder have more cracks, and the inclusions inside are removed by the solvent, reducing the amount of residual heat. ..
  • Example 8 A mixture (composition containing activated carbon) was obtained by kneading activated carbon, an organic binder, and water in advance and crushing the mixture.
  • the organic binder carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), ADEKA Resin Co., Ltd.
  • ADEKA Made of water-based epoxy resin EM-0180 was selected, and the solid content was 7.2 parts by mass, 1.2 parts by mass, and 2.1 parts by mass, for a total of 10.5 parts by mass with respect to 100 parts by mass of activated carbon. 160.5 parts by mass of water was added to 100 parts by mass of activated charcoal.
  • BA butane activity representing fuel evaporation gas adsorption performance: Measured in accordance with ASTM-D5228 (hereinafter abbreviated as BA).
  • the spherical activated carbon integrated with the latent heat storage material to be provided was limited to those having an average particle size of 2.36 mm or more and less than 2.80 mm. The results are shown in Tables 2 and 3.
  • Example 11 The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and the activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 1000 ⁇ m) so that the entire amount of 2854 g was used (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 2583: 270 (mass ratio))
  • the latent heat storage material integrated activated charcoal of Example 11 was obtained in the same manner as in Example 8.
  • sieving is performed using a sieve having a size of 3.5 (opening 5.6 mm) to 10Mesh (opening 1.7 mm) (JIS standard), and is arbitrary except for a section larger than the target particle size and a section finer than 10Mesh. Spherical activated carbon integrated with latent heat storage material was obtained.
  • Example 12 The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and an activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 840 ⁇ m) so that the entire amount of 2000 g was used (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 1811: 189 (mass ratio))
  • the latent heat storage material integrated activated charcoal of Example 12 was obtained in the same manner as in Example 11.
  • Example 13 The latent heat storage material obtained in Example 4 was used as the core as the latent heat storage material, and the activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 680 ⁇ m) so that the entire amount of 1347 g was used (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 1220: 127 (mass ratio))
  • a latent heat storage material-integrated activated charcoal of Example 12 was obtained.
  • Example 14 The latent heat storage material obtained in Example 5 was used as the core as the latent heat storage material, and an activated charcoal mixture (composition containing active charcoal) was applied to a coating (thickness 560 ⁇ m) so that 691 g of the mixture was used in its entirety (latent heat storage material).
  • Material: Activated charcoal: Organic binder 250: 625: 65 (mass ratio))
  • the latent heat storage material integrated activated charcoal of Example 12 was obtained in the same manner as in Example 11.
  • Reference example 1 An existing activated carbon (BAX1100 manufactured by Industry Corporation) that does not use a latent heat storage material was used.
  • Reference example 2 An existing activated carbon (BAX1700 manufactured by Industry Corporation) that does not use a latent heat storage material was used.
  • Test Example 4 The ASTM hardness was measured with reference to ASTM-D5228. The results are shown in Table 3.
  • the activated carbon As the activated carbon, activated carbon having a pH of 4.19 in an aqueous suspension measured according to JIS K 1474 (2014) was used. This activated carbon, an organic binder, and water are mixed and molded with a die having a hole diameter of 2.2 mm and a thickness of 15 mm using an extruder (disc pelleter F5 type manufactured by Dalton Co., Ltd.), and a malmerizer (Dalton, By finely granulating with Q-400T), a molded product having the same material composition as the activated carbon-containing layer of the heat storage material-integrated activated carbon was obtained. The pH of the obtained molded product was 4.97, which was the pH of the aqueous suspension measured according to JIS K 1474 (2014).
  • the organic binder examples include carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), and ADEKA Resin (manufactured by ADEKA Corporation).
  • Aqueous epoxy resin EM-0180 was selected, and the solid content was 6.8 parts by mass, 1.2 parts by mass, and 1.9 parts by mass, for a total of 9.9 parts by mass and water, respectively, with respect to 100 parts by mass of activated carbon. Added 220.0 parts by mass with respect to 100 parts by mass of activated charcoal.
  • Manufacturing example 2 Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated carbon having a pH of 4.50 in the aqueous suspension is used. A molded product having a pH of 5.87 was obtained.
  • the pH of the obtained molded product was 10.43, which was the pH of the aqueous suspension measured according to JIS K 1474 (2014).
  • the organic binder include carboxymethyl cellulose sodium salt (F30MC manufactured by Nippon Paper Co., Ltd.), Epocross WS-700 (oxazoline group-containing water-soluble polymer manufactured by Nippon Catalyst Co., Ltd.), and ADEKA Resin (manufactured by ADEKA Corporation).
  • Aqueous epoxy resin EM-0180 was selected, and the solid content was 6.8 parts by mass, 1.2 parts by mass, and 1.9 parts by mass, for a total of 9.9 parts by mass and water with respect to 100 parts by mass of activated carbon. Added 215.0 parts by mass with respect to 100 parts by mass of activated charcoal.
  • Comparative manufacturing example 1 Measured in accordance with JIS K 1474 (2014) Measured in accordance with JIS K 1474 (2014) in the same manner as in Production Example 1 except that activated charcoal having a pH of 2.92 in the aqueous suspension is used. A molded product having a pH of 2.88 was obtained.
  • Test Example 5 The ASTM hardness was measured with reference to ASTM-D5228. The results are shown in Table 4. In Table 4, the case where the pH of each molded product was 4.5 or more was designated as A, and the case where the pH was less than 4.5 was designated as B.

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JP5462765B2 (ja) 2010-10-26 2014-04-02 大阪瓦斯株式会社 蓄熱機能付吸着材の製造方法及び蓄熱機能付吸着材並びにキャニスター
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WO2009145020A1 (ja) * 2008-05-27 2009-12-03 大阪ガスケミカル株式会社 蓄熱材の製造方法、蓄熱材、蓄熱機能付吸着材、キャニスター
US20130139995A1 (en) * 2011-12-06 2013-06-06 Korea Institute Of Construction Technology Porous material having micropores capable of storing and releasing heat by phase change and preparation method thereof
JP2014196380A (ja) * 2013-03-29 2014-10-16 大阪ガスケミカル株式会社 被覆蓄熱マイクロカプセルの製造方法、蓄熱材の製造方法、蓄熱機能付吸着材

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WO2023080208A1 (ja) * 2021-11-05 2023-05-11 大阪ガスケミカル株式会社 キャニスタ、及びそれを備えた自動車両

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