JPH0280315A - Granulated active carbon - Google Patents
Granulated active carbonInfo
- Publication number
- JPH0280315A JPH0280315A JP63233092A JP23309288A JPH0280315A JP H0280315 A JPH0280315 A JP H0280315A JP 63233092 A JP63233092 A JP 63233092A JP 23309288 A JP23309288 A JP 23309288A JP H0280315 A JPH0280315 A JP H0280315A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- granulated
- carbon
- active carbon
- binder
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910052799 carbon Inorganic materials 0.000 title abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 239000002931 mesocarbon microbead Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 5
- 239000005011 phenolic resin Substances 0.000 claims abstract description 5
- 239000000440 bentonite Substances 0.000 claims abstract description 4
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 4
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000012461 cellulose resin Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 18
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000011295 pitch Substances 0.000 abstract description 7
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 3
- 239000004917 carbon fiber Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- -1 polyimdes Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 34
- 238000001179 sorption measurement Methods 0.000 description 24
- 239000002904 solvent Substances 0.000 description 18
- 238000011084 recovery Methods 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 13
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000011859 microparticle Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000012216 bentonite Nutrition 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、各種ガスの吸着剤、有ｆｉ溶剤の回収剤等と
して有用な造粒活性炭に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to granulated activated carbon useful as an adsorbent for various gases, a recovery agent for fi-containing solvents, and the like.
［従来の技術と発明が解決しようとする課題］活性炭は
比表面積が大きく、吸着能に潰れているため、種々の気
体および液体からの不純物の除去、気体および液体の精
製および有用物質の回収等に利用されている。より具体
的には、大気汚染、悪臭、水質汚濁等の防除材料、ガス
の精製、上水の脱臭脱色による浄化、食品の脱色、有機
溶剤の除去または回収、貴金属溶液からの貴金属の回収
、触媒の担体、タバコフィルタ等の広い分野で利用され
ている。[Prior art and problems to be solved by the invention] Activated carbon has a large specific surface area and is limited in adsorption capacity, so it is useful for removing impurities from various gases and liquids, purifying gases and liquids, recovering useful substances, etc. It is used for. More specifically, materials for controlling air pollution, bad odors, water pollution, etc., purification of gas, deodorization and decolorization of clean water, decolorization of foods, removal or recovery of organic solvents, recovery of precious metals from precious metal solutions, and catalysts. It is used in a wide range of fields such as carriers for tobacco products and cigarette filters.
活性炭は、通常、粒状の形態で使用されている。Activated carbon is usually used in granular form.
この粒状活性炭としては、例えば、■カーボンブラック
と炭化性バインダーとを混合またはグラフト重合させ、
加圧下で成形した後、所望の粒径に破砕し炭化焼成した
り、または炭化焼成後、所望の粒径に破砕した多孔性炭
素材料（例えば、特公昭４８−４３５５４号公報、特開
昭５１−１１６１９３号公報）、■造粒カーボンブラッ
クにタールまたはピッチを加熱溶融し、加圧下または減
圧下で浸透した後、焼成し賦活した粒状活性炭（特開昭
５０−８３２８６号公報）や、■１００〜１００ＯＡ単
位の粒子径を有するカーボンブラックを球状体に造粒し
、該球状体に、有機溶剤に溶かした炭化性バインダーを
含浸させ、不活性雰囲気下で炭化焼成し、次いで賦活処
理を施す多孔性炭素粒子の製造方法（特開昭５７−１４
５０１７号公報）が提案されている。This granular activated carbon can be produced by mixing or graft polymerizing carbon black and a carbonizable binder, for example;
After forming under pressure, the porous carbon material is crushed to a desired particle size and carbonized and fired, or after carbonized and fired, the porous carbon material is crushed to a desired particle size (for example, Japanese Patent Publication No. 48-43554, Japanese Patent Laid-Open Publication No. 1983-1999). -116193 Publication), ■ Granular activated carbon made by heating and melting tar or pitch into granulated carbon black, impregnating it under pressure or reduced pressure, and then firing and activating it (Japanese Unexamined Patent Publication No. 50-83286), ■100 Porous carbon black having a particle size of ~100 OA is granulated into spherical bodies, the spherical bodies are impregnated with a carbonizable binder dissolved in an organic solvent, carbonized and fired in an inert atmosphere, and then activated. Method for producing carbon particles (Japanese Unexamined Patent Publication No. 57-14
No. 5017) has been proposed.
しかしながら、前記■■の多孔性炭素材料および粒状活
性炭は、比表面積が小さく、未だ吸着能が十分でない、
また前記■の多孔性炭素材料は破砕により得られるため
、粒子の破砕面の角が鋭角であり、使用時に牽砕され易
く、しかも流動性が十分でなく、前記■の粒状活性炭は
、タールなどを加熱溶融し、浸透させる必要があるため
、工程が複雑化する。さらには、前記■の製造方法によ
り得られた多孔性炭素粒子は、流動性および機械的強度
に優れると共に、ミクロポアーとマクロボアーとを有し
ているので、前記■■の多孔性炭素材料等よりも比表面
積を大きくすることができるものの、末だ吸着能が十分
でない。より具体的には、上記多孔性炭素粒子等は、Ｂ
ＥＴ法による比表面積が数百〜１５００ｍ’／ｇ程度、
全細孔容積が０．２〜１゜Ｏｍｌ／ｇ程度であり、いず
れも比表面積が小さく、吸着能が十分でないという問題
がある。However, the porous carbon material and granular activated carbon described above have a small specific surface area and do not yet have sufficient adsorption capacity.
In addition, since the porous carbon material (2) is obtained by crushing, the edges of the crushed surfaces of the particles are acute, making it easy to be crushed during use, and it does not have sufficient fluidity. The process is complicated because it requires heating, melting, and infiltration. Furthermore, the porous carbon particles obtained by the manufacturing method of (1) above have excellent fluidity and mechanical strength, and have micropores and macropores, so they are better than the porous carbon materials of (2) above. Although the specific surface area can be increased, the adsorption capacity is still insufficient. More specifically, the porous carbon particles and the like are B
The specific surface area by ET method is about several hundred to 1500 m'/g,
The problem is that the total pore volume is about 0.2 to 1° Oml/g, the specific surface area is small, and the adsorption capacity is not sufficient.
また近年、特異な性能および形状を有する活性炭として
、セルロース系、ポリアクリロニトリル系、フェノール
樹脂系、ピッチ系等の材料を原料とする繊維状活性炭が
提案されているものの、未だ吸着容量が十分でなく、上
記と同様の問題がある。In recent years, fibrous activated carbon made from materials such as cellulose, polyacrylonitrile, phenolic resin, and pitch has been proposed as an activated carbon with unique performance and shape, but the adsorption capacity is still insufficient. , there is a similar problem as above.
例えば、上記従来の多孔性炭素粒子や繊維状活性炭など
を溶剤回収装置に適用した場合、回収装置への充填量を
多くする必要があり、溶剤回収装置が大型化するという
問題がある。より具体的には、近年、半導体の洗浄工程
などで発生し、オゾン層を破壊する原因物質とされるフ
ロンガスの効率約回収が要望されている。このフロンガ
スは、流量ｉｎ’／分程度の排気ガス中に６００ Ｄｌ
ｌ１１程度の濃度で含まれており、一般に、他の発生源
と比較して発生源の規模が非常に小さい、このような発
生源に溶剤回収装置を設けた場合、その回収量は通常１
日あたり２〜３ｋｉ程度である。For example, when the above-mentioned conventional porous carbon particles, fibrous activated carbon, etc. are applied to a solvent recovery device, it is necessary to increase the amount of filling into the recovery device, and there is a problem that the solvent recovery device becomes larger. More specifically, in recent years, there has been a demand for efficient recovery of fluorocarbon gas, which is generated in semiconductor cleaning processes and is considered to be a substance that destroys the ozone layer. This fluorocarbon gas has a flow rate of 600 Dl in the exhaust gas at a flow rate of about in'/min.
If a solvent recovery device is installed at such a source, where the size of the source is generally very small compared to other sources, the amount recovered is usually about 1.
It is about 2 to 3 ki per day.
一方、前記従来の多孔質炭素粒子等は、フロンガスに対
して平衡吸着量０．５ｇ／ｇ程度、破過吸着量０．２ｇ
／ｇ程度であり、吸着能が著しく小さい、従って、従来
の回収装置においては活性炭フィルタを２塔設けると共
に、スチーム切替弁、エアー切替弁を設け、水蒸気を脱
着用熱源として利用している。このように溶剤回収装置
を用いて、フロンを回収する場合、例えば、粒状活性炭
では、通常２〜３時間毎に、繊維状活性炭では、１０〜
２０分毎に吸脱着を繰返す必要があるので、装置が後胤
になり、イニシャルコストが高く、溶剤回収の経済的メ
リットがなくなる。また多量の吸着剤を充填する必要が
あるなめ、通常高さ２００゜Ｉｎ１ｌｌＸ幅１３００ｍ
ｍＸ奥行き８００ ｎ＋ｍ程度の溶剤回収装置を必要と
し、回収装置が大型化するという問題がある。On the other hand, the conventional porous carbon particles etc. have an equilibrium adsorption amount of about 0.5 g/g and a breakthrough adsorption amount of 0.2 g for fluorocarbon gas.
/g, and the adsorption capacity is extremely small.Therefore, in conventional recovery equipment, two towers of activated carbon filters are provided, as well as a steam switching valve and an air switching valve, and water vapor is used as a heat source for desorption. When recovering fluorocarbons using a solvent recovery device in this way, for example, for granular activated carbon, it is usually done every 2 to 3 hours, and for fibrous activated carbon, it is collected every 2 to 3 hours.
Since it is necessary to repeat adsorption and desorption every 20 minutes, the device becomes an afterthought, the initial cost is high, and there is no economic advantage of solvent recovery. In addition, since it is necessary to fill a large amount of adsorbent, the height is usually 200゜In1ll x width 1300m.
This requires a solvent recovery device with a size of about m x depth 800 n+m, which poses a problem of increasing the size of the recovery device.
本発明の目的は、比表面積が大きく、吸着能に優れた造
粒活性炭を提供することにある。An object of the present invention is to provide granulated activated carbon having a large specific surface area and excellent adsorption ability.
［発明の構成コ
本発明は、細孔を有する活性炭であって、（ｉ）光学的
に異方性であり、
（ｉ１）全体の９０％以りが粒径８０μ日以下の粒子か
らなり、
（ｉｉｉ）全細孔容積の８５％以上が細孔直径２０八以
下のミクロポアーにより構成されている粒状の活性炭と
、バインダーとからなる造粒活性炭により、上記課題を
解決するものである。[Structure of the Invention] The present invention is an activated carbon having pores, which (i) is optically anisotropic, (i1) 90% or more of the total consists of particles with a particle size of 80 μdays or less, (iii) The above problem is solved by a granulated activated carbon comprising granular activated carbon in which 85% or more of the total pore volume is constituted by micropores with a pore diameter of 208 or less, and a binder.
また本発明は、賦活したメソカーボンマイクロビーズが
バインダーを用いて造粒されている造粒活性炭により、
上記課題を解決するものである。Furthermore, the present invention uses granulated activated carbon in which activated mesocarbon microbeads are granulated using a binder.
This solves the above problem.
上記構成の造粒活性炭によれば、粒状の活性炭が、従来
の活性炭と異なり、光学的に異方性の多孔質炭素微小粒
子であるため、吸着能が著しく大きい。According to the granulated activated carbon having the above configuration, unlike conventional activated carbon, the granular activated carbon is optically anisotropic porous carbon microparticles, and therefore has a significantly high adsorption capacity.
本発明の造粒活性炭に含有される活性炭は、光学的異方
性の多孔質炭素微小粒子である。The activated carbon contained in the granulated activated carbon of the present invention is optically anisotropic porous carbon microparticles.
先ず、この光学的異方性の多孔質炭素微小粒子について
説明する。上記光学的異方性の多孔質炭素微小粒子は、
ピッチを原料とするニードルコークス、炭素繊維の開発
に際し、石油系および石炭系ピッチを加熱していく過程
において、ピッチ中に炭素六員環網面が平行に積層した
球晶が生成することにより見出されたものである。これ
らの球晶は、マトリックスピッチとは異なる相を形成し
ており、アンチソルベント法、遠心分離法等により単離
される。単離された球晶は、一般にメソカーボンマイク
ロビーズと呼ばれており、直径２〜８０μｍ程度の球体
で、光学的異方性の組織を有している。このメソカーボ
ンマイクロビーズは、その特異な形状および特性から、
高機能性材料用の新たな原料として期待されているが、
現在のところ、高密度炭素材の原料として実用化されて
いるにすぎない。First, the optically anisotropic porous carbon microparticles will be explained. The optically anisotropic porous carbon microparticles described above are
During the development of pitch-based needle coke and carbon fiber, during the process of heating petroleum-based and coal-based pitches, it was observed that spherulites with six-membered carbon ring network planes stacked parallel to each other were formed in the pitch. It was issued. These spherulites form a phase different from the matrix pitch, and are isolated by an antisolvent method, a centrifugation method, or the like. The isolated spherulites are generally called mesocarbon microbeads, are spheres with a diameter of about 2 to 80 μm, and have an optically anisotropic structure. Due to its unique shape and characteristics, this mesocarbon microbead is
It is expected to be a new raw material for highly functional materials.
At present, it has only been put into practical use as a raw material for high-density carbon materials.
本出願人は、上記メソカーボンマイクロビーズを賦活す
ることにより、新たな微細構造および特性を有する活性
炭が得られることを見出し、先に特許出願した（特願昭
６３−１５８５１０号）、この活性炭は、光学的に異方
性であり、全体の９０％以上が粒径８０μ以下の粒子か
らなり、全ｍｌ孔容積の８５％以上が細孔直径２ＯＡ以
下のミクロポアーにより構成されている。また活性炭の
比表面積は５００〜４６００ ｒｎ２／ ｇの範囲内で
あり、全細孔容積は０，５〜３．０＋ｍｌ／ｇ程度であ
る。The present applicant discovered that activated carbon with a new microstructure and characteristics could be obtained by activating the mesocarbon microbeads, and previously filed a patent application (Japanese Patent Application No. 158510/1983) for this activated carbon. , is optically anisotropic, 90% or more of the total consists of particles with a particle size of 80μ or less, and 85% or more of the total pore volume in ml is composed of micropores with a pore diameter of 2OA or less. Further, the specific surface area of activated carbon is within the range of 500 to 4600 rn2/g, and the total pore volume is approximately 0.5 to 3.0+ml/g.
粒状の活性炭は、メソカーボンマイクロビーズをそのま
ま又はその表面に賦活助剤を付与した後、賦活すること
により得られる。賦活したメソカーボンマイクロビーズ
は、クリーンパウダー状、炭化パウダー状、黒鉛化パウ
ダー状のいずれであってもよい。賦活助剤としては、例
えば、ＫＯＨｌＮａＯＨ，ＣｓＯＨ，ＺｎＣｌ２、Ｈ３
ＰＯ４、Ｋｚ ＳＯ４、Ｋｚ Ｓ等が例示され、これら
の賦活助剤の少なくとも一種を使用する。賦活助剤の付
与量は、メソカーボンマイクロビーズ重量の１〜１０＠
量程度とするのが好ましい。賦活の程度は、賦活助剤の
付与量に略比例するので、付与量により活性炭の比表面
積を調整することができる。なお、賦活助剤は、通常、
液状で使用される。すなわちＫＯＨなどの常温で固体の
賦活助剤は、水溶液の形態で使用され、Ｈ３ＰＯ４など
の常温で液体の賦活助剤は、必ずしも水溶液とする必要
はない。Granular activated carbon can be obtained by activating mesocarbon microbeads as they are or after applying an activation aid to the surface of the mesocarbon microbeads. The activated mesocarbon microbeads may be in the form of clean powder, carbonized powder, or graphitized powder. Examples of the activation aid include KOHlNaOH, CsOH, ZnCl2, H3
Examples include PO4, Kz SO4, Kz S, etc., and at least one of these activation aids is used. The amount of activation aid applied is 1 to 10@ of the weight of mesocarbon microbeads.
It is preferable to set it to about the amount. Since the degree of activation is approximately proportional to the amount of the activation aid applied, the specific surface area of the activated carbon can be adjusted by the amount applied. In addition, the activation aid is usually
Used in liquid form. That is, an activation aid that is solid at room temperature, such as KOH, is used in the form of an aqueous solution, and an activation aid that is liquid at room temperature, such as H3PO4, is not necessarily in the form of an aqueous solution.
またメソカーボンマイクロビーズ表面に対する賦活助剤
の濡れ性を改善するため、アセトン、メチルアルコール
、エチルアルコール等の表面活性剤を併用してもよい０
表面活性剤の使用量は、通常、メソカーボンマイクロビ
ーズと賦活助剤または賦活助剤を含む溶液との総量の５
〜１０重量％重量上程るのが好ましい。In addition, in order to improve the wettability of the activation aid to the surface of mesocarbon microbeads, a surface active agent such as acetone, methyl alcohol, or ethyl alcohol may be used in combination.
The amount of surfactant used is usually 5% of the total amount of mesocarbon microbeads and the activation aid or the solution containing the activation aid.
Preferably, it is 10 to 10% by weight.
賦活は、賦活助剤を付与し若しくは付与しないメソカー
ボンマイクロビーズを適宜の温度、例えば、４００〜１
２００’Ｃ程度に昇温することにより行なわれる。昇温
速度および加熱保持時間は、特に限定されず、広い範囲
で選択することができるが、通常、上記の温度範囲に到
達後、直ちに冷却するか、同温度範囲内で最大３時間程
度保持することにより行なわれる。Activation is carried out by heating mesocarbon microbeads with or without an activation aid at an appropriate temperature, e.g.
This is done by raising the temperature to about 200'C. The heating rate and heating holding time are not particularly limited and can be selected within a wide range, but usually, after reaching the above temperature range, it is immediately cooled or held within the same temperature range for a maximum of about 3 hours. This is done by
賦活時の雰囲気は、窒素、ヘリウム、アルゴンなどの不
活性雰囲気であってもよく、水蒸気、酸化炭素、酸素な
どが存在する酸化性雰囲気であってもよい。不活性雰囲
気中で賦活すると収率がより高くなる。The atmosphere during activation may be an inert atmosphere such as nitrogen, helium, or argon, or may be an oxidizing atmosphere containing water vapor, carbon oxide, oxygen, or the like. Activation in an inert atmosphere gives higher yields.
不活性雰囲気中で賦活するには、賦活助剤を使用して、
通常、昇温速度３００〜６００°Ｃ／時間程度で温度４
００〜１２００″Ｃ程度に加熱し、同温度で３０分乃至
１時間程度保持するのが好ましい。To activate in an inert atmosphere, use an activation aid,
Normally, the temperature is 4 at a heating rate of 300 to 600°C/hour.
It is preferable to heat to about 00 to 1200''C and hold at the same temperature for about 30 minutes to 1 hour.
酸化性雰囲気中で賦活する場合、通常、賦活助剤は不要
であるが、併用してもよい。賦活助剤を使用せずに賦活
する場合、通常、６００〜９００°Ｃ程度の温度に、賦
活助剤を使用して賦活する場合、通常、３００〜９００
’Ｃ程度の温度に、昇温速度３００〜６００’Ｃ／時
間程度で加熱し、同温度で２〜３時間程度保持するのが
好ましい、なお、賦活助剤を使用する場合、突沸する場
合があるので留意する必要がある。When activating in an oxidizing atmosphere, an activation aid is usually not required, but may be used in combination. When activated without using an activation aid, the temperature is usually around 600 to 900°C, and when activated with an activation aid, the temperature is usually around 300 to 900°C.
It is preferable to heat the product to a temperature of about 300°C at a rate of temperature increase of 300 to 600°C/hour and hold it at the same temperature for about 2 to 3 hours.Please note that if an activation aid is used, bumping may occur. There is a need to keep this in mind.
なお、賦活助剤の種類に応じて最適賦活温度が存在して
いる。！＆適賦活温度は、例えば、ＫＯＨ１Ｋ２ ＳＯ
２及びＫｚ Ｓの場合、８００〜１０００℃程度、Ｎａ
ＯＨ及びＣｓＯＨの場合、６００°Ｃ程度、Ｚｎ０．１
２の場合、４５０℃程度である。Note that there is an optimum activation temperature depending on the type of activation aid. ! & Appropriate activation temperature is, for example, KOH1K2 SO
2 and Kz S, about 800 to 1000℃, Na
For OH and CsOH, about 600°C, Zn0.1
In case of No. 2, the temperature is about 450°C.
賦活を終えたメソカーボンマイクロビーズを室温まで冷
却した後、必要に応じて水洗により未反応の賦活助剤お
よび賦活助剤反応物を除去し、乾燥することにより、本
発明で使用される活性炭が得られる。After the activated mesocarbon microbeads are cooled to room temperature, the unreacted activation aid and activation aid reactant are removed by washing with water as necessary, and the activated carbon used in the present invention is dried. can get.
上記賦活助剤は、メソカーボンマイクロビーズ中の炭素
の酸化によるガス化を促進するものと推測される。すな
わち、賦活助剤が、メソカーボンマイクロビーズを構成
する炭素六員環網面の炭素原子と反応し、生成した一酸
化炭素または二酸化炭素が系外に排出されるものと推測
される。It is presumed that the above-mentioned activation aid promotes gasification by oxidation of carbon in the mesocarbon microbeads. That is, it is presumed that the activation aid reacts with the carbon atoms on the six-membered carbon ring network surface constituting the mesocarbon microbeads, and the generated carbon monoxide or carbon dioxide is discharged to the outside of the system.
また不活性雰囲気中で賦活する場合、反応に関与しなか
った部分は炭素化が進むので、反応部分と未反応部分と
の構造上の差異が大きくなり細孔が形成される。この場
合、メソカーボンマイクロビーズが規則的な層状構造を
有しているので、生成した孔は、２０人未満のミクロポ
アーが多い。Furthermore, when activation is performed in an inert atmosphere, carbonization progresses in the portions that did not participate in the reaction, so the structural difference between the reacted portions and the unreacted portions increases and pores are formed. In this case, since the mesocarbon microbeads have a regular layered structure, many of the generated pores have less than 20 micropores.
また反応雰囲気が、不活性雰囲気である場合、表面ガス
反応の選択性が高くなり、収率も著しく大きくなる。Further, when the reaction atmosphere is an inert atmosphere, the selectivity of the surface gas reaction becomes high and the yield also becomes significantly high.
なお、賦活助剤と炭素との反応は、非常に激しく進行す
るので、メソカーボンマイクロビーズに代えて炭素繊維
を用い、上記と同様に賦活すると、その形状は原形をと
どめない程度に変形しかつ強度も著しく低下する。一方
、メソカーボンマイクロビーズの場合には、賦活後も、
その球形の形状が略維持されており、強度の著しい低下
は認められない。Note that the reaction between the activation aid and carbon proceeds very violently, so if carbon fibers are used instead of mesocarbon microbeads and activated in the same manner as above, the shape will deform to the extent that it will no longer retain its original shape. Strength also decreases significantly. On the other hand, in the case of mesocarbon microbeads, even after activation,
The spherical shape is substantially maintained, and no significant decrease in strength is observed.
上記のようにして得られた活性炭は、原料として使用す
るメソカーボンマイクロビーズと路間−の寸法および形
状を有しており、光学的に異方性であって、細孔容積の
８５％以上が２０人未満のミクロポアーにより占められ
ている０、ｔた活性炭の比表面積は５００〜４６００ｍ
’／ｇの範囲内であり、全細孔容積は０．５〜３．０＋
ｎｌ／ｇ程度である。The activated carbon obtained as described above has the same size and shape as the mesocarbon microbeads used as a raw material, is optically anisotropic, and has 85% or more of the pore volume. The specific surface area of activated carbon is occupied by less than 20 micropores from 500 to 4600 m
'/g, and the total pore volume is 0.5-3.0+
It is about nl/g.
従って、本発明で使用する活性炭は、従来の活性炭に比
べて著しく小さな細孔径を有しており、ＪＩＳ Ｋ
１４７４に準拠したベンゼン吸着能は０．２〜１．０
ｇ／ｇ程度、ＪＩＳ Ｋ １４７０に準拠したメチ
レンブルー吸着能は１００〜６５０ ｍｌ ／ ｇ程度
であり、従来の活性炭に比べて、著しく大きな吸着能を
有している。上記活性炭のうち、比表面積１０００〜４
６００ｎ’／ｇ、特に２０００〜４６００ ｍ’／ ｇ
、全細孔容積０．８〜３．０ｍｌ／ｇのものが好ましい
。Therefore, the activated carbon used in the present invention has a significantly smaller pore diameter than conventional activated carbon, and is compliant with JIS K
Benzene adsorption capacity according to 1474 is 0.2 to 1.0
g/g, and the methylene blue adsorption capacity based on JIS K 1470 is about 100 to 650 ml/g, which is significantly greater than that of conventional activated carbon. Among the above activated carbons, the specific surface area is 1000 to 4
600n'/g, especially 2000-4600 m'/g
, a total pore volume of 0.8 to 3.0 ml/g is preferred.
本発明の造粒活性炭は、上記特性を有する粒状の活性炭
とバインダーとで構成されている。The granulated activated carbon of the present invention is composed of granular activated carbon having the above characteristics and a binder.
バインダーは、造粒可能であり、しかも活性炭の吸着能
に悪影響を及ぼさないものであればいずれも使用できる
。このようなバインダーとしては、例えば、ポリ酢酸ビ
ニル、ポリビニルアルコール、アクリル系樹脂、スチレ
ン系樹脂、飽和ポリエステル、ポリアミド、ポリウレタ
ン、ポリカーボネート、エポキシ樹脂、フラン樹脂、尿
素樹脂、メラミン樹脂、不飽和ポリエステル、ジアリル
フタレートｌｌ！）Ｉ詣、シリコーン樹脂、ポリアセタ
ール、メチルセルロース、エチルセルロース、酢酸セル
ロース、ニトロセルロース、カルボキシメチルセルロー
ス、などのセルロース系樹脂、フェノール樹脂、ポリイ
ミド、ベントナイト、コールタールピッチ、澱粉等が例
示され、これらのバインダーの少なくとも一種が使用さ
れる。これらバインダーのうちセルロース系樹脂、フェ
ノール樹脂、ポリイミド、ベントナイト、コールタール
ピッチが好ましい。Any binder can be used as long as it can be granulated and does not adversely affect the adsorption ability of activated carbon. Examples of such binders include polyvinyl acetate, polyvinyl alcohol, acrylic resins, styrene resins, saturated polyesters, polyamides, polyurethanes, polycarbonates, epoxy resins, furan resins, urea resins, melamine resins, unsaturated polyesters, and diallyl resins. Phthalate ll! ) Cellulose resins such as silicone resin, polyacetal, methyl cellulose, ethyl cellulose, cellulose acetate, nitrocellulose, carboxymethyl cellulose, phenolic resin, polyimide, bentonite, coal tar pitch, starch, etc. are exemplified, and at least one of these binders is One type is used. Among these binders, cellulose resins, phenolic resins, polyimides, bentonites, and coal tar pitch are preferred.
造粒活性炭中のバインダーの含有量は、バインダーの種
類により最適量が変化するので、バインダーの種類およ
び所望する吸着能に応じて適宜選択することができ、例
えば、バインダーがメチルセルロースであるとき、メチ
ルセルロース含有量は、通常、１０〜４０重量％、好ま
しくは１５〜３０重量％程度である。なお、バインダー
の含有量は、通常、１０〜５０重量％、好ましくは１５
〜３０重量％程度で十分である。バインダーの含有量が
１０重量％未満であると造粒活性炭の機械的強度が低下
し、５０重量％を越えると造粒活性炭の比表面積が小さ
くなる。The optimal amount of binder content in the granulated activated carbon varies depending on the type of binder, so it can be selected appropriately depending on the type of binder and the desired adsorption capacity. For example, when the binder is methylcellulose, methylcellulose The content is usually about 10 to 40% by weight, preferably about 15 to 30% by weight. The content of the binder is usually 10 to 50% by weight, preferably 15% by weight.
About 30% by weight is sufficient. When the binder content is less than 10% by weight, the mechanical strength of the granulated activated carbon decreases, and when it exceeds 50% by weight, the specific surface area of the granulated activated carbon decreases.
上記造粒活性炭は、用途等に応じて適宜の形状および大
きさに造粒されていればよい、造粒活性炭の形状は、破
砕などによる不定形状であってもよいが、流動性および
機械的強度などに優れる球状、断面多角形状、円柱状で
あるのが好ましい。The above-mentioned granulated activated carbon may be granulated into an appropriate shape and size depending on the application, etc. The shape of the granulated activated carbon may be an irregular shape due to crushing, etc., but the fluidity and mechanical Preferably, it has a spherical shape, a polygonal cross-sectional shape, or a cylindrical shape because of its excellent strength.
また造粒活性炭の大きさは、通常、代表寸法０゜１〜５
ｍｍφ、好ましくは０．５〜４＋ｎｍφ、より好まし
くは１〜３１Ｔｌｌ！＋φ程度である。In addition, the size of granulated activated carbon is usually a typical dimension of 0°1 to 5.
mmφ, preferably 0.5 to 4+nmφ, more preferably 1 to 31 Tll! It is about +φ.
造粒活性炭は、種々の造粒法により製造することができ
る０例えば、前記活性炭とバインダーとを、通常溶媒の
存在下で混合し、押出し成形機により混合物を押出し、
所定の形状および大きさに成形した後、乾燥することに
より製造することができる。溶媒としては、揮発性を有
し、前記バインダーを溶解するものであれば、いずれも
使用できる。溶媒としては、例えば、水、メタノール、
エタノール、イソプロパツールなどのアルコール類、ヘ
キサン、オクタン、シクロヘキサンなどの脂環族炭化水
素、ベンゼン、トルエン、キシレンなどの芳香族炭化水
素、アセトン、メチルエチルケトン、ジオキサンなどの
ケトン類、ジメチルエーテル、ジエチルエーテル、テト
ラヒドロフランなどのエーテル類、酢酸エチルなどのエ
ステル類など種々の溶媒が例示される。また混合機とし
ては、ミキサ、リボンプレンダー ニーダなど種々の混
合機が使用できる。Granulated activated carbon can be produced by various granulation methods. For example, the activated carbon and a binder are mixed, usually in the presence of a solvent, and the mixture is extruded using an extruder.
It can be manufactured by forming it into a predetermined shape and size and then drying it. As the solvent, any solvent can be used as long as it has volatility and dissolves the binder. Examples of solvents include water, methanol,
Alcohols such as ethanol and isopropanol, alicyclic hydrocarbons such as hexane, octane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, and dioxane, dimethyl ether, diethyl ether, Various solvents include ethers such as tetrahydrofuran and esters such as ethyl acetate. Various types of mixers such as mixers, ribbon blenders, and kneaders can be used as the mixer.
また前記押出し成形機を使用することなく、混合物を乾
煙し、粉砕したり、混合物を噴霧乾燥機などにより造粒
してもよい。Alternatively, the mixture may be dried and pulverized, or the mixture may be granulated using a spray dryer, etc., without using the extruder.
なお、乾燥は適宜の条件下で行なうことができるが、減
圧下で行なうのが好ましい。Note that drying can be carried out under appropriate conditions, but it is preferably carried out under reduced pressure.
上記の方法によると、粒状活性炭とバインダーとを混合
して造粒するだけでよいため、従来のように、炭化焼成
したり、賦活処理する必要がなく、比表面積が大きく、
吸着能に優れた造粒活性炭を簡便かつ効率よく製造する
ことができる。According to the above method, it is only necessary to mix granular activated carbon and a binder and granulate it, so there is no need for carbonization firing or activation treatment as in the past, and the specific surface area is large.
Granulated activated carbon with excellent adsorption ability can be produced simply and efficiently.
なお、造粒活性炭は、必要に応じて炭化焼成してもよい
、またバインダーにより塞がれた細孔を開孔し、比表面
積を増加させたり、あるいは造粒活性炭の表面に付着し
ている不純物を除去するため、軽度の賦活処理を施して
らよい、炭化焼成は、ロータリーキルンや電気炉などを
用いて不活性雰囲気または真空下、適宜の温度、例えば
、５００〜１５００℃程度で行なうことができる。また
賦活処理は、ロータリーキルン、流動床炉等を用いて、
水蒸気雰囲気または二酸化炭素雰囲気下で、適宜の温度
、例えば、８００〜１５００°Ｃ程度の温度で行なうこ
とができる。In addition, the granulated activated carbon may be carbonized and fired as necessary, or the pores blocked by the binder may be opened to increase the specific surface area, or the granulated activated carbon may be attached to the surface of the granulated activated carbon. In order to remove impurities, a mild activation treatment may be performed. Carbonization firing can be performed at an appropriate temperature, for example, about 500 to 1500°C, in an inert atmosphere or vacuum using a rotary kiln or electric furnace. . In addition, activation treatment is performed using a rotary kiln, fluidized bed furnace, etc.
It can be carried out at an appropriate temperature, for example, about 800 to 1500°C, in a steam atmosphere or a carbon dioxide atmosphere.
本発明の造粒活性炭は、通常、ＢＥＴ法による比表面積
８００〜３５００ｍ’／ｇ程度、全細孔容積０．５〜２
．５ａ＋Ｉ／ｇ程度を有しており、吸着能に優れている
。また造粒されているため、充填密度を大きくすること
ができ、使用量が少なくても長期間に亘り吸着能を保持
できる。さらには、フロンガスなどの溶剤を回収する場
合、カートリッジに造粒活性炭を充填し、フロン溶媒な
どの洗浄装置に取付けるだけで多量の溶媒を吸着させ回
収できるので、従来使用されていたスチーム切替弁およ
びエアー切替弁等が必要でなくなり、イニシャルコスト
を大幅に低減できる。また従来設けられていた大型の溶
剤回収装置が必要でなくなり、装置を小型化することが
できる。また上記カートリッジを取替るだけでよいため
、取扱いが容易である。The granulated activated carbon of the present invention usually has a specific surface area of about 800 to 3500 m'/g and a total pore volume of 0.5 to 2
．． It has an excellent adsorption capacity of about 5a+I/g. Furthermore, since it is granulated, the packing density can be increased, and even if the amount used is small, the adsorption capacity can be maintained for a long period of time. Furthermore, when recovering solvents such as fluorocarbon gas, a large amount of solvent can be absorbed and recovered by simply filling a cartridge with granulated activated carbon and attaching it to a cleaning device for fluorocarbon solvents. There is no need for air switching valves, etc., and initial costs can be significantly reduced. Furthermore, the conventionally provided large-scale solvent recovery device is no longer necessary, and the device can be downsized. Further, since it is only necessary to replace the cartridge, handling is easy.
本発明の造粒活性炭は、各種悪臭成分の除去、各種ガス
の精製、フロン系、塩素系溶剤等の有機溶剤の除去およ
び回収、上水の浄化などに用いられる吸着剤、触媒担体
など、従来活性炭が使用されていた分野で好適に使用さ
れる。The granulated activated carbon of the present invention can be used as an adsorbent or catalyst carrier for removing various malodorous components, purifying various gases, removing and recovering organic solvents such as fluorocarbons and chlorinated solvents, and purifying tap water. It is suitable for use in fields where activated carbon was used.
［実施例］
以下に、実施例に基づいて、本発明をより詳細に説明す
る。[Examples] The present invention will be described in more detail below based on Examples.
実施例１
活性炭としてメソカーボンマイクロビーズを賦活して得
られた光学的異方性の多孔質炭素微小粒子（比表面積４
４５０ｆｆ＋’／ｇ、全細孔容積２．８ｍｌ ／ ｇ、
全体の９０％以上が粒径３〜４０μｍ以下の球状粒子か
らなり、全細孔容積の８５％以上が細孔直径２ＯＡ以下
のミクロポアーにより構成されている活性炭）を用いた
。この活性炭１００重量部と５０重量％のメチルセルロ
ース水溶液３５重量部とをニーダ−にて均一に混合し、
押出し成形機を用いて、２．５〜３ｍｗ１φの円柱状の
ベレット１０Ｊを作製した０次いで、上記ベレットを、
真空乾燥機を用いて減圧度１０ ｔｏｒｒ、温度１２０
゛Ｃで乾燥し、造粒活性炭を作製した。Example 1 Optically anisotropic porous carbon microparticles obtained by activating mesocarbon microbeads as activated carbon (specific surface area: 4
450ff+'/g, total pore volume 2.8ml/g,
Activated carbon (activated carbon) in which 90% or more of the total consists of spherical particles with a particle size of 3 to 40 μm or less, and 85% or more of the total pore volume is constituted by micropores with a pore diameter of 2OA or less was used. 100 parts by weight of this activated carbon and 35 parts by weight of a 50% by weight methylcellulose aqueous solution were uniformly mixed in a kneader,
Using an extrusion molding machine, a cylindrical pellet 10J of 2.5 to 3 mw1φ was produced. Then, the above pellet was
Using a vacuum dryer, the pressure is reduced to 10 torr and the temperature is 120.
It was dried at C to produce granulated activated carbon.
得られた造粒活性炭の比表面積をＢＥＴ法により測定し
たところ、比表面積３５００ｍ’／ｇであった。また全
細孔容積は２．３ｍｌ／ｇであった。When the specific surface area of the obtained granulated activated carbon was measured by the BET method, it was found to be 3500 m'/g. Moreover, the total pore volume was 2.3 ml/g.
またＪＩＳ Ｋ １４７０に規定するメチレンブル
ー脱色法によりメチレンブルー吸着能を測定したところ
、５６０ｍ１／ｇであった。Furthermore, when the methylene blue adsorption capacity was measured by the methylene blue decolorization method specified in JIS K 1470, it was 560 ml/g.
実施例２
活性炭としてメソカーボンマイクロビーズを賦活して得
られた光学的異方性の多孔質炭素微小粒子（比表面積４
０００ｍ’／ｇ、全細孔容積２．６ｍｌ／ｇ）８．５に
’ｊを、ベントナイト１，５−と水１．５−とからなる
水溶液に添加し、常温にてリボンブレンダを用いて、均
一に混合し、押出し成形機を用いて、円柱状に成形し、
乾燥することにより、３關φＸ５ＴＩ＋ｍの造粒活性炭
を作製した。Example 2 Optically anisotropic porous carbon microparticles obtained by activating mesocarbon microbeads as activated carbon (specific surface area: 4
000 m'/g, total pore volume 2.6 ml/g) 8.5'j was added to an aqueous solution consisting of 1,5- bentonite and 1.5- water, and was mixed using a ribbon blender at room temperature. , mixed uniformly and molded into a cylindrical shape using an extruder,
By drying, granulated activated carbon of 3 mm diameter x 5 TI+m was produced.
得られた造粒活性炭は、ＢＥＴ法による比表面積３００
０ｍ’／ｇ、全細孔容積２ ｃｎｌ ／ ｇであった。The obtained granulated activated carbon has a specific surface area of 300 by the BET method.
0 m'/g, and the total pore volume was 2 cnl/g.
比較例１
実施例１の活性炭に代えて粉末状の活性炭（比表面積１
４５０ｍ’／ｇ、ｌ孔容積０．６７ｍ１／ｇ、武田薬品
工業■製、商品名白鷺）を用い、上記実施例１と同様に
して造粒活性炭を作製した。Comparative Example 1 Powdered activated carbon (specific surface area 1
Granulated activated carbon was produced in the same manner as in Example 1 using 450 m'/g, pore volume 0.67 m1/g, manufactured by Takeda Pharmaceutical Co., Ltd. (trade name: Shirasagi).
得られた造粒活性炭は、ＢＥＴ法による比表面Ｗ１１０
８０ ｍ’ ／ ｇ、全細孔容積０．５ｍｌ／ｇであっ
た。The obtained granulated activated carbon has a specific surface W110 according to the BET method.
80 m'/g, total pore volume 0.5 ml/g.
比較例２
実施例１の活性炭に代えて、繊維状活性炭（比表面積２
０５Ｏｎ＋’／ｇ、細孔容積１ 、１ ｍｌ／ ｇ、大
阪瓦斯■製、商品名Ａ−２０）を用い、上記実施例１と
同様にして造粒活性炭を作製した。Comparative Example 2 Fibrous activated carbon (specific surface area 2
Granulated activated carbon was produced in the same manner as in Example 1 using 05On+'/g, pore volume 1, 1 ml/g, manufactured by Osaka Gas Co., Ltd., trade name A-20).
得られた造粒活性炭は、ＢＥＴ法による比表面積１５４
０ｍ’／ｇ、全細孔容１０．８ｍｌ／ｇであった。The obtained granulated activated carbon has a specific surface area of 154 by BET method.
0 m'/g, and the total pore volume was 10.8 ml/g.
そして、実施例１、実施例２、比較例１および２の造粒
活性炭を用いてフロンガスに対する平衡吸着量および破
過吸着量を測定したところ、表に示す結果を得た。Then, when the equilibrium adsorption amount and breakthrough adsorption amount for fluorocarbon gas were measured using the granulated activated carbons of Example 1, Example 2, and Comparative Examples 1 and 2, the results shown in the table were obtained.
表
表より明らかなように、比較例１および比較例２の造粒
活性炭に比べて、実施例１および実施例２の造粒活性炭
は、フロンガスに対する吸着能が大きい。As is clear from the table, compared to the granulated activated carbons of Comparative Examples 1 and 2, the granulated activated carbons of Examples 1 and 2 have a greater adsorption capacity for fluorocarbon gas.
また実施例１、実施例２、比較例１および２の造粒活性
炭をカートリッジ式の円筒状フロンガス回収装置（高さ
６００ｍｍ、直径３６０１１１１１Ｔφ）に充填し、フ
１７ン溶媒による洗浄装置に取付けた。そして、排気ガ
スの流量１ｍ１／分、排気ガス中のフロン濃度６００１
）ｉｌｌの条件で、フロンガスを回収したところ、比較
例１および２の造粒活性炭では、１日あたり２〜４回取
換える必要があるのに対して、実施例１および実施例２
の造粒活性炭では、１日に発生するフロンガス全てを吸
着させ、回収することができた。Further, the granulated activated carbons of Examples 1, 2, and Comparative Examples 1 and 2 were filled into a cartridge-type cylindrical fluorocarbon gas recovery device (height: 600 mm, diameter: 36011111Tφ), which was attached to a cleaning device using a fluorocarbon solvent. Then, the flow rate of exhaust gas is 1 m1/min, and the concentration of fluorocarbons in exhaust gas is 6001
)ill conditions, the granulated activated carbons of Comparative Examples 1 and 2 needed to be replaced 2 to 4 times per day, whereas the granulated activated carbons of Examples 1 and 2
The granulated activated carbon was able to adsorb and recover all the fluorocarbon gas generated in a day.
［発明の効果］
以上のように、本発明の造粒活性炭によれば、吸着能に
潰れる光学的異方性の多孔質炭素微小粒子とバインダー
とからなるので、比表面積が大きく、吸着能に優れてい
る。[Effects of the Invention] As described above, the granulated activated carbon of the present invention is composed of a binder and optically anisotropic porous carbon microparticles that can be crushed by adsorption capacity, so it has a large specific surface area and has a high adsorption capacity. Are better.
Claims (1)
なり、 （ｉｉｉ）全細孔容積の８５％以上が細孔直径２０Å以
下のミクロポアーにより構成されている粒状の活性炭と
、バインダーとからなることを特徴とする造粒活性炭。 ２、賦活したメソカーボンマイクロビーズがバインダー
を用いて造粒されていることを特徴とする造粒活性炭。 ３、バインダーが、セルロース系樹脂、フェノール樹脂
、ポリイミド、ベントナイトおよびコールタールピッチ
からなる群から選択された少なくとも一種である請求項
１または請求項２記載の造粒活性炭。[Claims] 1. Activated carbon having pores, which (i) is optically anisotropic, (ii) 90% or more of the total consists of particles with a particle size of 8 μm or less, (iii) Granulated activated carbon comprising granular activated carbon in which 85% or more of the total pore volume is constituted by micropores with a pore diameter of 20 Å or less, and a binder. 2. Granulated activated carbon, characterized in that activated mesocarbon microbeads are granulated using a binder. 3. The granulated activated carbon according to claim 1 or 2, wherein the binder is at least one selected from the group consisting of cellulose resin, phenolic resin, polyimide, bentonite, and coal tar pitch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233092A JPH0280315A (en) | 1988-09-17 | 1988-09-17 | Granulated active carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233092A JPH0280315A (en) | 1988-09-17 | 1988-09-17 | Granulated active carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0280315A true JPH0280315A (en) | 1990-03-20 |
Family
ID=16949659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63233092A Pending JPH0280315A (en) | 1988-09-17 | 1988-09-17 | Granulated active carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0280315A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR1001479B (en) * | 1992-05-27 | 1994-02-28 | Ioannis Simitzis | Manufacture and application of absorption agents based on lignite -cellulose that originate from olive stone or stone wood and phenolic resins. |
| EP0587293A1 (en) * | 1992-08-12 | 1994-03-16 | Courtaulds Textiles (Holdings) Limited | Anti-fogging coating |
| EP0645346A1 (en) * | 1993-09-24 | 1995-03-29 | Corning Incorporated | Activated carbon bodies having phenolic resin binder |
| JPH08158248A (en) * | 1994-12-03 | 1996-06-18 | Kensho Muramoto | Activated carbon for cleaning, cleaning method and reprocessing apparatus for activated carbon |
| WO2001036326A1 (en) * | 1999-11-19 | 2001-05-25 | Centre National De La Recherche Scientifique | Activated carbons and method for obtaining same from a partly mesophase and partly mesogenic pitch |
| KR20230100471A (en) | 2021-12-28 | 2023-07-05 | 한국화학연구원 | Granulated activated charcoal and preparation method thereof |
-
1988
- 1988-09-17 JP JP63233092A patent/JPH0280315A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR1001479B (en) * | 1992-05-27 | 1994-02-28 | Ioannis Simitzis | Manufacture and application of absorption agents based on lignite -cellulose that originate from olive stone or stone wood and phenolic resins. |
| EP0587293A1 (en) * | 1992-08-12 | 1994-03-16 | Courtaulds Textiles (Holdings) Limited | Anti-fogging coating |
| EP0645346A1 (en) * | 1993-09-24 | 1995-03-29 | Corning Incorporated | Activated carbon bodies having phenolic resin binder |
| JPH08158248A (en) * | 1994-12-03 | 1996-06-18 | Kensho Muramoto | Activated carbon for cleaning, cleaning method and reprocessing apparatus for activated carbon |
| WO2001036326A1 (en) * | 1999-11-19 | 2001-05-25 | Centre National De La Recherche Scientifique | Activated carbons and method for obtaining same from a partly mesophase and partly mesogenic pitch |
| FR2801297A1 (en) * | 1999-11-19 | 2001-05-25 | Centre Nat Rech Scient | ACTIVE CARBONS AND THEIR PROCESS FOR OBTAINING A PARTIALLY MESOPHASE AND PARTIALLY MESOGENIC PIT |
| JP2003514741A (en) * | 1999-11-19 | 2003-04-22 | サーントル ナスィヨナル ドゥ ラ ルシェルシュ スイヤンティフィック | Method for obtaining activated carbon from activated carbon and partially mesophased and partially mesogenicized pitch |
| US7105083B1 (en) | 1999-11-19 | 2006-09-12 | Centre National De La Recherche Scientifique | Activated carbons and method for obtaining same from a partly mesophase and partly mesogenic pitch |
| KR20230100471A (en) | 2021-12-28 | 2023-07-05 | 한국화학연구원 | Granulated activated charcoal and preparation method thereof |
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