WO2019244630A1 - 自動車キャニスタ用活性炭素繊維シート - Google Patents
自動車キャニスタ用活性炭素繊維シート Download PDFInfo
- Publication number
- WO2019244630A1 WO2019244630A1 PCT/JP2019/022296 JP2019022296W WO2019244630A1 WO 2019244630 A1 WO2019244630 A1 WO 2019244630A1 JP 2019022296 W JP2019022296 W JP 2019022296W WO 2019244630 A1 WO2019244630 A1 WO 2019244630A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- activated carbon
- carbon fiber
- fiber sheet
- sheet
- canister
- Prior art date
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000011148 porous material Substances 0.000 claims abstract description 72
- 239000000835 fiber Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000011282 treatment Methods 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 6
- 238000007596 consolidation process Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 abstract description 46
- 238000001179 sorption measurement Methods 0.000 description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 35
- 238000002336 sorption--desorption measurement Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 239000002737 fuel gas Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 16
- 230000004913 activation Effects 0.000 description 14
- 238000003763 carbonization Methods 0.000 description 12
- 238000003795 desorption Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 229920000297 Rayon Polymers 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- 239000002759 woven fabric Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000002964 rayon Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005315 distribution function Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- DDYHLQYSGDGSED-UHFFFAOYSA-N 2-dimethoxyphosphorylpropanamide Chemical compound COP(=O)(OC)C(C)C(N)=O DDYHLQYSGDGSED-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000006716 Broussonetia kazinoki Nutrition 0.000 description 1
- 240000006248 Broussonetia kazinoki Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZHGASCUQXLPSDT-UHFFFAOYSA-N cyclohexanesulfonic acid Chemical compound OS(=O)(=O)C1CCCCC1 ZHGASCUQXLPSDT-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- -1 for example Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- FAUOSXUSCVJWAY-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium Chemical class OC[P+](CO)(CO)CO FAUOSXUSCVJWAY-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
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- 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
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- 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
- F02M25/0854—Details of the absorption canister
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/16—Pore diameter
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Definitions
- the present invention relates to an activated carbon fiber sheet, and more particularly, to an activated carbon fiber sheet suitable for use in a canister of an automobile.
- a gasoline-powered vehicle the pressure in the fuel tank fluctuates due to changes in the outside temperature, etc., and the evaporated fuel gas filled in the fuel tank is released from the fuel tank.
- the released vaporized fuel gas is considered to be one of the causative substances of PM2.5 and photochemical smog, and a canister provided with an adsorbent such as activated carbon is provided to prevent the release of the vaporized fuel gas into the atmosphere.
- a canister mounted on an automobile may be abbreviated as “automobile canister” or simply “canister”.
- Activated carbon fibers may be referred to as third activated carbon, as opposed to powdered, granular, or pelletized activated carbon that has been around for a long time.
- Activated carbon fiber is said to have a relatively high specific surface area, a large adsorption capacity, and a high adsorption / desorption speed, among activated carbons in a broad sense.
- activated carbon fibers have not yet been put to practical use in canisters, and research and development have not yet sufficiently proceeded on what characteristics of activated carbon fibers are suitable for practical use of canisters.
- an object of the present invention is to provide a new form of adsorbent suitable for an automobile canister.
- the present inventors have conducted intensive research and found that in an automobile canister, it is necessary to fix the adsorbent so that it does not wear due to vibration or the like. Was found to be practically suitable. However, in automobiles, the capacity of the canister is limited, and it is difficult to achieve the required performance per unit volume of the canister simply by storing the activated carbon fiber sheet in the housing of the canister. Was found. As a result of further intensive studies, the present inventors have found that an activated carbon fiber sheet suitable for an automobile canister can be obtained by the following means, and have completed the present invention.
- the specific surface area is 1400 to 2200 m 2 / g, When the pore volume of the pores having a pore diameter larger than 0.7 nm and not more than 2.0 nm is 0.20 to 1.20 cm 3 / g and the sheet density is 0.030 to 0.200 g / cm 3 , is there, Activated carbon fiber sheet for automobile canister.
- Activated carbon fiber sheet for automobile canister [2] The activated carbon fiber sheet for an automobile canister according to the above [1], wherein the total pore volume is 0.50 to 1.20 cm 3 / g.
- An automobile canister comprising the activated carbon fiber sheet for an automobile canister according to any one of [1] to [3].
- an activated carbon fiber sheet which is easy to handle, has high adsorption / desorption performance at a low concentration, and is suitable for use in a canister of an automobile. Further, according to the present invention, it is possible to provide an automobile canister having excellent adsorption / desorption performance at a low concentration.
- AA to BB means “AA or more and BB or less” (here, “AA” and “BB” represent arbitrary numerical values).
- the activated carbon fiber sheet for automobile canister of the present invention is a sheet-like molded product formed of activated carbon fibers, and is used as an adsorbent to be stored in a canister mounted on an automobile. It is preferably used.
- the activated carbon fiber sheet for an automobile canister of the present invention may be abbreviated as the activated carbon fiber sheet of the present invention.
- the activated carbon fiber sheet of the present invention includes at least one of the following predetermined items. It satisfies the condition consisting of one or any combination of two or more.
- the lower limit of the specific surface area of the activated carbon fiber sheet of the present invention is preferably 1400 m 2 / g or more, more preferably 1500 m 2 / g or more, and further preferably 1600, 1700 or 1800 m 2 / g.
- the specific surface area of the activated carbon fiber sheet of the present invention is preferably wider from the viewpoint of adsorption performance.
- the upper limit of the specific surface area may be approximately 2200 or 2000 m 2 / g or less.
- the lower limit of the total pore volume of the activated carbon fiber sheet of the present invention is preferably 0.50 cm 3 / g or more, more preferably 0.60 cm 3 / g or more, and still more preferably 0.70, 0. 80 or 0.85 cm 3 / g or more.
- the upper limit of the total pore volume of the activated carbon fiber sheet of the present invention is preferably 1.20 cm 3 / g or less, more preferably 1.10 cm 3 / g or less, and still more preferably 1.00 cm 3 / g. It is as follows. By setting the total pore volume in the above range, a sheet having more excellent adsorption / desorption performance with respect to the evaporated fuel gas can be obtained.
- the lower limit of the average pore diameter of the activated carbon fiber sheet of the present invention is preferably 1.69 nm or more, more preferably 1.70 nm or more, and still more preferably 1.72, 1.75, 1.78 or 1.80 nm or more.
- the upper limit of the average pore diameter of the activated carbon fiber sheet of the present invention may be arbitrary, but is preferably 4.00 nm or less, more preferably 3.50 nm or less, and further preferably 3.00 nm or less.
- the term “ultra micropore” means a pore having a pore diameter of 0.7 nm or less.
- pore diameter refers to the diameter or width of the pore, not the radius of the pore, unless otherwise specified.
- the lower limit of the ultra-micro pore volume of the activated carbon fiber sheet of the present invention is preferably 0.10 cm 3 / g or more, more preferably 0.20 cm 3 / g or more, and still more preferably 0.22 or 0. It is 25 cm 3 / g or more.
- the upper limit of the ultra-micro pore volume of the activated carbon fiber sheet of the present invention is preferably 0.30 cm 3 / g or less, more preferably 0.29 cm 3 / g or less, and still more preferably 0.28 or 0.18 cm 3 / g. It is not more than 27 cm 3 / g.
- micropore means a pore having a pore diameter of 2.0 nm or less.
- the lower limit of the micropore volume of the activated carbon fiber sheet of the present invention is preferably 0.45 cm 3 / g or more, more preferably 0.50 cm 3 / g or more, and still more preferably 0.55 or 0.60. Or it is 0.70 cm 3 / g or more.
- the upper limit of the micropore volume of the activated carbon fiber sheet of the present invention is preferably 1.00 cm 3 / g or less, more preferably 0.90 cm 3 / g or less, and still more preferably 0.80 cm 3 / g or less. It is. By setting the micropore volume in the above range, a sheet having more excellent adsorption / desorption performance with respect to the evaporated fuel gas can be obtained.
- V 0.7-2.0 ⁇ Pore volume of pores having pore diameters larger than 0.7 nm and 2.0 nm or less.
- the pore volume V 0.7-2.0 of the pores having a pore diameter larger than 0.7 nm and not more than 2.0 nm can be obtained by the following equation 1 using the value a of the ultra micropore volume and the value b of the micropore volume. it can.
- V 0.7-2.0 ba ⁇ ⁇ ⁇ Equation 1
- the lower limit of the pore volume V 0.7-2.0 of the pores having a pore diameter of greater than 0.7 nm and 2.0 nm or less is preferably 0.20 cm 3 / g or more, more preferably Is 0.30 cm 3 / g or more, more preferably 0.36, 0.40 or 0.43 cm 3 / g or more.
- the upper limit of the pore volume V 0.7-2.0 of the pores having a pore diameter larger than 0.7 nm and 2.0 nm or less is preferably 1.20 cm 3 / g or less.
- R 0.7 / 2.0 The abundance ratio R 0.7 / 2.0 of the pore volume of the micropores having a pore diameter of 0.7 nm or less in the pore volume of the micropores having a pore diameter of 2.0 nm or less is the value a of the ultramicropore volume.
- the value b of the micropore volume can be determined by the following equation 2.
- R 0.7 / 2.0 a / b ⁇ 100 (%) ⁇ ⁇ ⁇ Equation 2
- the lower limit of the existence ratio R 0.7 / 2.0 of the ultra micropore volume in the micropore volume is preferably 25% or more, more preferably 30% or more, and further preferably 32% or more. % Or more.
- the upper limit of the existence ratio R 0.7 / 2.0 of the ultra micropore volume in the micropore volume is preferably 60% or less, more preferably 55% or less, and further preferably 50% or less. , 45 or 40% or less.
- the lower limit of the basis weight of the activated carbon fiber sheet of the present invention is preferably 30 g / m 2 or more, more preferably 35 g / m 2 or more, and further preferably 37 or 40 g / m 2 or more.
- the upper limit of the activated carbon fiber sheet having a basis weight of the present invention is preferably not 400 g / m 2 or less, and more preferably not more than 380 g / m 2, more preferably 360,350,340 or 330 g / m 2 or less is there.
- the lower limit of the sheet thickness of the activated carbon fiber sheet of the present invention is preferably 0.3 mm or more, more preferably 0.5 mm or more, further preferably 1.0 mm or 1.5 mm or more.
- the upper limit of the sheet thickness of the activated carbon fiber sheet of the present invention is preferably 8.0 mm or less, more preferably 7.0 mm or less, even more preferably 4.0 mm or 3.0 mm or less.
- the lower limit of the density of the activated carbon fiber sheet of the present invention is preferably 0.030 g / cm 3 or more, more preferably 0.035 g / cm 3 or more, more preferably is 0.040 g / cm 3 or more .
- the upper limit of the sheet density of the activated carbon fiber sheet of the present invention is preferably not 0.200 g / cm 3 or less, more preferably 0.190 g / cm 3 or less, more preferably 0.180 or 0.170 g / cm 3 or less.
- the lower limit of the tensile strength (MD) of the activated carbon fiber sheet of the present invention is preferably at least 0.05 kN / m, more preferably at least 0.06 kN / m.
- the upper limit of the tensile strength (MD) of the activated carbon fiber sheet of the present invention is not particularly limited and may be arbitrary, but is preferably 2.50 kN / m or less, more preferably 2.40 kN / m or less, More preferably, it is 2.30, 2.20, 2.10 or 2.00 kN / m or less.
- the lower limit of the tensile strength (CD) of the activated carbon fiber sheet of the present invention is preferably at least 0.05 kN / m, more preferably at least 0.06 kN / m, even more preferably at least 0.07 kN / m. is there.
- the upper limit of the tensile strength (CD) of the activated carbon fiber sheet of the present invention is not particularly limited and may be arbitrary, but is preferably 2.50 kN / m or less, more preferably 2.40 kN / m or less, and further preferably 2 kN / m or less. .30, 2.20, 2.10 or 2.00 kN / m or less.
- the activated carbon fiber sheet of the present invention preferably has a predetermined water content.
- the lower limit of the water content under the conditions of 23 ° C. and 50% relative humidity is preferably 1% or more, more preferably 2% or more, and still more preferably 3% or more.
- the upper limit of the water content under the conditions of 23 ° C. and 50% relative humidity is preferably 25% or less, more preferably 22% or less, and further preferably 15 or 10% or less.
- the activated carbon fiber sheet of the present invention preferably has a predetermined methylene blue adsorption performance as an adsorbent.
- the methylene blue absorption performance can be shown as the amount of methylene blue adsorbed per activated carbon fiber sheet weight.
- the methylene blue adsorption performance of the activated carbon fiber sheet of the present invention is preferably at least 60 ml / g, more preferably at least 70 ml / g, even more preferably at least 80, 90 or 100 ml / g.
- the activated carbon fiber sheet of the present invention preferably has a predetermined iodine adsorption performance as an adsorbent.
- the iodine absorption performance can be represented as an iodine adsorption amount per activated carbon fiber sheet weight.
- the iodine adsorption performance of the activated carbon fiber sheet of the present invention is preferably at least 800 mg / g, more preferably at least 900 mg / g, further preferably at least 1,000, 1100 or 1200 mg / g.
- the activated carbon fiber sheet of the present invention preferably has a predetermined n-butane adsorption / desorption performance as an adsorbent. Since the n-butane adsorption / desorption performance is an index of the evaporation gas adsorption / desorption performance, those having excellent n-butane adsorption / desorption performance are suitable for use in automobile canisters.
- the n-butane adsorption / desorption performance is determined by measuring the amount of adsorption when repeating adsorption after adsorbing and desorbing the n-butane sufficiently under predetermined desorption conditions after sufficient absorption and breakthrough. It can be shown as an effective adsorption amount of n-butane per carbon fiber sheet weight.
- the effective adsorption / desorption amount of n-butane (the second adsorption amount, the desorption amount, and the third adsorption amount, desorption amount) determined according to the measurement method shown in the following Examples Is preferably 0.380 mmol / g or more, more preferably 0.420 mmol / g or more, and still more preferably 0.450, 0.500, or 0.550 mmol / g.
- the effective adsorption / desorption rate of n-butane determined according to the measuring method shown in the following examples is preferably 29.0% or more, more preferably 31% or more. 0.0% or more, and more preferably 32.0 or 34.0%.
- the activated carbon fiber sheet of the present invention satisfies the condition of at least one or any combination of two or more of the above-mentioned items relating to physical properties or performance. Examples of preferable combinations are shown below.
- the activated carbon fiber sheet of the present invention is not limited to the following combinations.
- An activated carbon fiber sheet for an automobile canister satisfying the following requirements (1) to (3).
- the specific surface area is from 1400 to 2200 m 2 / g.
- the pore volume of pores having a pore diameter larger than 0.7 nm and not larger than 2.0 nm is 0.20 to 1.20 cm 3 / g.
- the sheet density is 0.030 to 0.200 g / cm 3 .
- the main object to be adsorbed by the adsorbent for the automobile canister is the evaporated fuel gas. It is preferable that the specific surface area and the pore volume V 0.7-2.0 as described above are satisfied from the viewpoint of the adsorption performance for the evaporated fuel gas. Further, since the size of the automobile canister is limited, it is preferable that the sheet density requirement of the above (3) is further satisfied from the viewpoint of securing the adsorbable amount using the activated carbon fiber sheet.
- the activated carbon fiber sheet may be formed by carbonizing a raw fiber sheet, and generally has a tendency to be slightly bulky and low in density.
- the activated carbon fiber sheet is subjected to a pressure treatment or the like in a manufacturing process and is consolidated.
- the seat of the first embodiment is in a suitable form from the viewpoint of the suction performance and the suction capacity required for the automobile canister.
- a sheet of a more preferred embodiment can be obtained from the viewpoint of securing the adsorption capacity required for the canister.
- the activated carbon fiber sheet of the present invention is suitable as an adsorbent housed in an automobile canister. That is, the present invention can also provide an automobile canister as another embodiment.
- the automobile canister of the present invention has an activated carbon fiber sheet as an adsorbent.
- the structure of the automobile canister is not particularly limited, and a general structure can be employed.
- an automobile canister includes one having the following structure.
- a housing An adsorbent chamber for storing the adsorbent in the housing; A first delivery inlet for allowing gas to be sucked or delivered between the adsorbent chamber and the engine; A second delivery inlet for allowing gas to be sucked or delivered between the adsorbent chamber and the fuel tank; A third delivery inlet that opens when a predetermined pressure is applied from the adsorbent chamber or the outside air, and communicates with the adsorbent chamber and the outside air so that the gas can be sucked or discharged;
- a canister comprising:
- each delivery inlet is not particularly limited
- the third delivery inlet is located at a position where the gas sufficiently passes through the adsorbent when the gas moves between the first and second delivery inlets.
- they are arranged.
- the first and second delivery ports are provided on the first side face of the housing, and the third delivery port is provided on the second side face located opposite to the first side face. Can be taken.
- the adsorbent chamber may be divided into a plurality of chambers.
- the adsorbent chamber may be divided into two or more sections by partition walls.
- a porous plate having air permeability or the like can be used.
- an external second housing is provided separately from the first housing, and the first housing and the second housing are connected to each other via a gas passage, and an adsorbent chamber is additionally provided. May be.
- the evaporated fuel gas delivery inlet side (first delivery inlet side) is connected to the outside air port side (second delivery port side).
- the adsorbent or the adsorbent chamber may be arranged so that the adsorption capacity is gradually reduced.
- a composite canister having a main body canister (a first housing) and a second canister (a second housing) provided near the outside air opening may be used.
- the compartment or housing closest to the evaporated fuel gas delivery inlet side is a main body (first compartment or first housing) having the largest storage volume, and the main body is a conventional one.
- the activated carbon fiber sheet of the present invention which has a high n-butane adsorption ability at a low concentration of about 0.2%, is housed in the adsorbent chamber after the second compartment or the second housing located near the outside air port. It is suitable as an adsorbent.
- the activated carbon fiber sheet of the present invention when used in an adsorbent chamber close to the outside air, the activated carbon fiber sheet of the present invention has a high effective adsorption / desorption amount by purging, so that the evaporated fuel gas when the automobile is stopped for a long time is used. It is also suitable as an adsorbent for use in automobile canisters in that it can reduce the amount of leakage.
- a preferred form of the canister includes, for example, the following forms.
- An automotive canister having two or more adsorbent chambers An automobile in which the activated carbon fiber sheet of the present invention is stored in a second or later adsorbent chamber provided closer to the outside air port than the first adsorbent chamber provided closest to the vaporized fuel gas delivery inlet.
- the activated carbon fiber sheet for example, in an automobile canister having two or more adsorbent chambers as described above, an activated carbon fiber sheet for the second or subsequent adsorbent chamber It is also preferable that In the above embodiment, the number of the adsorbent chambers may be two or more. When there are three or more adsorbent chambers, the activated carbon fiber sheet of the present invention only needs to be accommodated in at least one adsorbent chamber after the second adsorbent chamber.
- the activated carbon fiber sheet of the present invention is produced so as to satisfy the requirements selected from the predetermined items described above.
- the activated carbon fiber sheet of the present invention can be produced, for example, as follows.
- Carbonizing and activating the raw material sheet holding one or both of the phosphoric acid catalyst and the organic sulfonic acid catalyst, and the density of the activated carbon fiber sheet is 0.030 to 0.200 g / cm 3 .
- Pressure treatment so that (Hereinafter, referred to as production method embodiment 1).
- the fibers constituting the raw material sheet include, for example, cellulosic fibers, pitch fibers, PAN fibers, phenol resin fibers, and the like, and preferably cellulosic fibers.
- the cellulosic fiber is a fiber mainly composed of cellulose and / or a derivative thereof.
- Cellulose and cellulose derivatives may be of any origin, such as chemically synthesized products, plant-derived, regenerated cellulose, and cellulose produced by bacteria.
- the cellulosic fiber preferably, for example, a fiber formed of a plant cellulosic substance obtained from a tree or the like, or a long fibrous material obtained by dissolving a plant cellulosic substance (cotton, pulp, etc.) by performing a chemical treatment. Fibers made of the regenerated cellulosic material can be used.
- the fiber may contain components such as lignin and hemicellulose.
- Raw materials for cellulosic fibers include, for example, cotton (short fiber cotton, medium fiber cotton, long fiber cotton, super long cotton, super / super long cotton, etc.), hemp, bamboo, Vegetable cellulosic fibers such as kozo, honey, banana, and tunicate; regenerated cellulose fibers such as cuprammonium rayon, viscose rayon, polynosic rayon, bamboo-based cellulose; organic solvent (N-methylmorpholine) N oxide) purified cellulose fibers to be spun; and acetate fibers such as diacetate and triacetate.
- cotton short fiber cotton, medium fiber cotton, long fiber cotton, super long cotton, super / super long cotton, etc.
- hemp such as kozo, honey, banana, and tunicate
- regenerated cellulose fibers such as cuprammonium rayon, viscose rayon, polynosic rayon, bamboo-based cellulose
- organic solvent (N-methylmorpholine) N oxide) purified cellulose fibers to be spun and acetate fibers such as
- the diameter of the single fiber constituting the cellulosic fiber is preferably 5 to 75 ⁇ m, and the density is 1.4 to 1.9 m 3 / g.
- the form of the cellulosic fiber is not particularly limited, and may be prepared into a raw yarn (unprocessed yarn), a false twisted yarn, a dyed yarn, a single yarn, a ply twisted yarn, a covering yarn, or the like according to the purpose. Can be.
- the cellulosic fiber may contain two or more types of raw materials, it may be a blended yarn, a twisted yarn, or the like.
- the above-mentioned raw materials in various forms may be used alone or in combination of two or more. Among them, a non-twisted yarn is preferable from the viewpoint of compatibility between the moldability and mechanical strength of the composite material.
- the fiber sheet is obtained by processing a large number of fibers into a thin and wide sheet, and includes a woven fabric, a knitted fabric, and a nonwoven fabric.
- the method of weaving the cellulosic fiber is not particularly limited, and a general method can be used.
- the woven structure of the woven fabric is not particularly limited, and a three woven structure of plain weave, twill weave, and satin weave can be used.
- the gap between the warp and the weft of the cellulosic fiber is preferably 0.1 to 0.8 mm, more preferably 0.2 to 0.6 mm, and still more preferably 0.25 to 0.5 mm.
- the basis weight of the woven fabric composed of cellulosic fibers is preferably from 50 to 500 g / m 2 , more preferably from 100 to 400 g / m 2 .
- the carbon fiber woven fabric obtained by heat-treating this woven fabric can have excellent strength.
- the method for producing the nonwoven fabric is also not particularly limited, for example, a method of obtaining a fiber sheet using a dry method or a wet method using the above-described fiber cut into an appropriate length as a raw material, or using an electrospinning method or the like.
- a method of directly obtaining a fiber sheet from a solution may, for example, be mentioned.
- treatments such as resin bond, thermal bond, spunlace, and needle punch may be added for the purpose of bonding the fibers.
- the catalyst is held on the raw material sheet prepared as described above.
- a carbonization treatment is performed by holding the catalyst on the raw material sheet, and activated by using steam, carbon dioxide, air gas, or the like, to obtain a porous activated carbon fiber sheet.
- the catalyst for example, a phosphoric acid catalyst, an organic sulfonic acid catalyst, or the like can be used.
- phosphoric acid-based catalyst for example, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphorus oxyacids such as phosphinic acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, Triammonium phosphate, dimethylphosphonopropanamide, ammonium polyphosphate, polyphosphonitrile chloride, and phosphoric acid, tetrakis (hydroxymethyl) phosphonium salt or tris (1-aziridinyl) phosphine oxide and urea, thiourea, melamine, guanine, Examples thereof include cyanamide, hydrazine, dicyandiamide, and condensates thereof with a methylol derivative thereof, and preferably include diammonium hydrogen phosphate.
- phosphinic acid ammonium dihydrogen phosphate, diammonium hydrogen phosphate, Triammonium phosphate, di
- the phosphoric acid-based catalyst one type may be used alone, or two or more types may be used in combination.
- its concentration is preferably 0.05 to 2.0 mol / L, more preferably 0.1 to 1.0 mol / L.
- Organic sulfonic acid an organic compound having one or a plurality of sulfo groups can be used.
- a compound in which a sulfo group is bonded to various carbon skeletons such as an aliphatic system and an aromatic system can be used.
- the organic sulfonic acid catalyst those having a low molecular weight are preferable from the viewpoint of handling.
- organic sulfonic acid-based catalyst examples include, for example, R-SO 3 H (where R is a linear / branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, And an aryl group having 6 to 20 atoms, and the alkyl group, cycloalkyl group and aryl group may be substituted with an alkyl group, a hydroxyl group and a halogen group, respectively.
- R-SO 3 H where R is a linear / branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, And an aryl group having 6 to 20 atoms, and the alkyl group, cycloalkyl group and aryl group may be substituted with an alkyl group, a hydroxyl group and a halogen group, respectively.
- organic sulfonic acid catalyst examples include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 1-hexanesulfonic acid, vinylsulfonic acid, cyclohexanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, and naphthalenesulfonic acid. Acids, benzenesulfonic acid, camphorsulfonic acid and the like. Of these, methanesulfonic acid can be preferably used. In addition, one kind of the organic sulfonic acid-based catalyst may be used alone, or two or more kinds may be used in combination.
- the organic sulfonic acid When used as an aqueous solution, its concentration is preferably 0.05 to 2.0 mol / L, and more preferably 0.1 to 1.0 mol / L.
- ⁇ Mixed catalyst> The above-mentioned phosphoric acid catalyst and organic sulfonic acid catalyst may be mixed and used as a mixed catalyst.
- the mixing ratio may be appropriately adjusted.
- the catalyst is held on the raw material sheet.
- “holding” means keeping the catalyst in contact with the raw material sheet, and may be in various forms such as adhesion, adsorption, and impregnation.
- the method for retaining the catalyst is not particularly limited, and includes, for example, a method of dipping in an aqueous solution containing a catalyst, a method of sprinkling an aqueous solution containing a catalyst on a raw material sheet, a method of contacting with a vaporized catalyst vapor, and a method including a catalyst.
- a method of mixing the fibers of the raw material sheet with the aqueous solution to make paper is exemplified.
- a method in which the raw material sheet is immersed in an aqueous solution containing a catalyst to impregnate the inside of the fiber with the catalyst can be used.
- the temperature for immersion in the aqueous solution containing the catalyst is not particularly limited, but is preferably room temperature.
- the immersion time is preferably from 10 seconds to 120 minutes, more preferably from 20 seconds to 30 minutes.
- immersion for example, 1 to 150% by mass, preferably 5 to 60% by mass of the catalyst is adsorbed on the fibers constituting the raw material sheet.
- a drying method for example, any method such as standing at room temperature or introduction into a dryer may be used.
- Drying may be performed until the sample is taken out of the aqueous solution containing the catalyst and the excess water evaporates and the sample weight no longer changes.
- the drying time may be 0.5 days or more. After the mass change is almost eliminated by drying, the process proceeds to a step of carbonizing the raw material sheet holding the catalyst.
- Carbonization treatment After preparing the raw material sheet holding the catalyst, it is subjected to carbonization treatment.
- the carbonization treatment for obtaining the activated carbon fiber sheet can be performed according to a general method for carbonizing activated carbon, but as a preferred embodiment, it can be performed as follows.
- Carburization treatment is usually performed in an inert gas atmosphere.
- the inert gas atmosphere means an oxygen-free or low-oxygen atmosphere in which carbon hardly undergoes a combustion reaction and is carbonized, and may preferably be a gas atmosphere of, for example, argon or nitrogen.
- the lower limit of the heating temperature is preferably 300 ° C. or higher, more preferably 350 ° C. or higher, even more preferably 400 ° C. or higher or 750 ° C. or higher.
- the upper limit of the heating temperature is preferably 1400 ° C. or lower, more preferably 1300 ° C. or lower, even more preferably 1200 ° C. or lower or 1000 ° C. or lower.
- the lower limit of the heat treatment time is preferably 10 minutes or more, more preferably 11 minutes or more, further preferably 12 minutes or more, and more preferably 30 minutes or more.
- the upper limit of the heat treatment time may be arbitrary, but is preferably 180 minutes or less, more preferably 160 minutes, and still more preferably 140 minutes or less.
- a reheat treatment can be further performed in a predetermined gas atmosphere. That is, the carbonization treatment may be performed by dividing the heat treatment having different conditions such as the temperature into a plurality of stages.
- the primary heat treatment and the reheat treatment are performed under predetermined conditions, the physical properties are adjusted, carbonization and subsequent activation can be advanced more favorably, and an activated carbon fiber sheet having excellent adsorption and desorption properties can be obtained. There is.
- the activation treatment can be performed, for example, continuously after the above-mentioned heat treatment, by supplying steam and holding at an appropriate activation temperature for a predetermined time to obtain an activated carbon fiber sheet. .
- the lower limit of the activation temperature is preferably 300 ° C. or higher, more preferably 350 ° C. or higher, and further preferably 400 or 750 ° C. or higher.
- the upper limit of the activation temperature is preferably 1400 ° C. or lower, more preferably 1300 ° C. or lower, and further preferably 1200 or 1000 ° C. or lower. Note that when the activation treatment is performed continuously after the heat treatment, it is desirable to adjust the activation treatment temperature to approximately the same temperature.
- the lower limit of the activation time is preferably 1 minute or more, more preferably 5 minutes or more.
- the upper limit of the activation time may be arbitrary, but is preferably 180 minutes or less, more preferably 160 minutes or less, and still more preferably 140 minutes or less, 100 minutes or less, 50 minutes or less, and 30 minutes or less.
- the activated carbon fiber sheet of the present invention preferably has a sheet density adjusted.
- a consolidation treatment can be performed, for example, by subjecting the sheet to a pressure treatment to increase the density.
- Embodiments of the consolidation process include, for example, the following four types.
- a raw material sheet containing a binder such as a resin is subjected to a heating and pressurizing treatment to prepare a raw material sheet having a high density, and carbonized.
- the sheet is subjected to a pressure treatment while performing the carbonization treatment.
- the activated carbon fiber sheet is heated and pressurized by adding a binder such as a resin.
- the activated carbon fiber sheet is defibrated and mixed with pulp or the like.
- This adsorption isotherm was analyzed by the BET method in which the analytical relative pressure range was automatically determined under the conditions of the adsorption isotherm type I (ISO 9277), and the BET specific surface area per unit weight (unit: m 2 / g) was determined. This was defined as a specific surface area (unit: m 2 / g).
- Total pore volume (unit: cm 3 / g) was calculated by the one-point method from the results obtained at the relative pressure of 0.990 of the isotherm adsorption line obtained in the above specific surface area.
- ⁇ Sheet weight> The activated carbon fiber sheet was allowed to stand for 12 hours or more in an environment at a temperature of 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5%, and the sheet basis weight (unit: g / m 2 ) was determined from the weight and the vertical and horizontal dimensions.
- ⁇ Sheet thickness> The activated carbon fiber sheet was allowed to stand for at least 12 hours under an environment of a temperature of 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5%, and was then measured for 0 hours using a digital small-side thick plate FS-60DS (Daei Kagaku Seiki Seisakusho Co., Ltd.). The sheet thickness (unit: mm) when a load of 0.3 KPa was applied was measured.
- Elongation rate (unit:%) Elongation amount at maximum load (unit: mm) ⁇ 40 mm
- ⁇ Moisture content> The activated carbon fiber sheet is allowed to stand for at least 12 hours in an environment of a temperature of 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5%, and then 0.5 to 1.0 g of a sample is collected and dried at 115 ⁇ 5 ° C. for 3 hours. The moisture (unit:%) was determined from the change in weight upon drying.
- methylene blue adsorption performance The result of measurement according to the methylene blue decolorizing power (unit: ml / g) of powdered activated carbon for water service (JWWA K113) specified by the Japan Water Supply Association was defined as methylene blue adsorption performance (unit: ml / g).
- Effective adsorption and desorption is the average of the second adsorption amount, the second desorption amount, the third adsorption amount and the third desorption amount, the effective adsorption and desorption amount (mmol / g), and the effective adsorption and desorption ratio of the effective adsorption and desorption amount divided by the first adsorption amount. Rate (%).
- Example 1 A needle-punched nonwoven fabric having a basis weight of 300 g / m 2 made of rayon fiber (1.7 dtex, fiber length 40 mm) is impregnated with a 5 to 8% diammonium hydrogen phosphate aqueous solution, squeezed, dried, and dried to 8 to 10 wt. %.
- the obtained pretreated nonwoven fabric was heated in a nitrogen atmosphere to 900 ° C. in 50 minutes while being pressurized, and kept at this temperature for 4 minutes. Subsequently, an activation treatment was performed at that temperature for 10 minutes in a nitrogen stream containing steam having a dew point of 60 ° C.
- Example 2 A needle-punched nonwoven fabric made of rayon fiber (3.3 dtex, fiber length: 76 mm) and having a basis weight of 300 g / m 2 is impregnated with a 5 to 8% diammonium hydrogen phosphate aqueous solution, squeezed, dried, and dried to 8 to 10 wt. %.
- the temperature of the obtained pretreated nonwoven fabric was increased to 900 ° C. in a nitrogen atmosphere in 50 minutes, and kept at this temperature for 12 minutes. Subsequently, an activation treatment was performed at that temperature for 10 minutes in a nitrogen stream containing steam having a dew point of 60 ° C.
- Example 3 An activated carbon fiber sheet of Example 3 was produced in the same manner as in Example 2, except that the activation treatment time in Example 2 was changed to 23 minutes.
- Comparative Example 1 The activity of Comparative Example 1 was changed in the same manner as in Example 2 except that the heating time to 900 ° C. was changed to 25 minutes, the 900 ° C. holding time was changed to 2 minutes, and the activation treatment time was changed to 6 minutes. A carbon fiber sheet was produced.
- ⁇ Comparative Example 2 Granular activated carbon> The granular activated carbon filled in a commercially available canister was taken out and used as an adsorbent in Comparative Example 2.
- a canister having a product number of 77740-48220 (Toyota Parts Yamaguchi Kyohan Co., Ltd.) was used.
- Table 1 shows the results of measuring the physical properties and performance of Examples 1 to 3 and Comparative Examples 1 and 2.
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Abstract
Description
細孔径が0.7nmより大きく2.0nm以下である細孔の細孔容積が、0.20~1.20cm3/gであり、且つ
シート密度が0.030~0.200g/cm3である、
自動車キャニスタ用活性炭素繊維シート。
〔2〕全細孔容積が0.50~1.20cm3/gである、上記〔1〕に記載の自動車キャニスタ用活性炭素繊維シート。
〔3〕該活性炭素繊維シートは、セルロース系繊維の炭化処理物である、上記〔1〕または〔2〕に記載の自動車キャニスタ用活性炭素繊維シート。
〔4〕上記1~3のいずれか一項に記載の自動車キャニスタ用活性炭素繊維シートを備えた自動車キャニスタ。
〔5〕自動車キャニスタ用活性炭素繊維シートの製造方法であって、
リン酸系触媒若しくは有機スルホン酸系触媒のいずれか一方または双方を保持させた原料シートを、炭化及び賦活化すること、並びに
当該活性炭素繊維シートの密度が0.030~0.200g/cm3となるように圧密化処理することを含む、製造方法。
また、本発明によれば、低濃度での吸脱着性能に優れた自動車キャニスタを提供することができる。
本発明の自動車キャニスタ用活性炭素繊維シートは、賦活化された炭素繊維で形成されているシート状の成形物であり、自動車に搭載されるキャニスタに収納する吸着材として好適に用いられる。(なお、以下、本発明の自動車キャニスタ用活性炭素繊維シートを、本発明の活性炭素繊維シートと略称する場合がある。)本発明の活性炭素繊維シートは、下記の所定の項目のうち、少なくとも1つ又は任意の2つ以上の組合せからなる条件を満たすものである。
本発明の活性炭素繊維シートの比表面積の下限は、好ましくは1400m2/g以上であり、より好ましくは1500m2/g以上であり、更に好ましくは1600、1700又は1800m2/g以上である。
本発明の活性炭素繊維シートの比表面積は、一般に広い方が吸着性能の観点からは好ましいが、活性炭素繊維シートの場合、比表面積の上限は、概ね2200又は2000m2/g以下でありうる。
比表面積を上記のような範囲とすることによって、蒸散燃料ガスについて、吸脱着性能についてより優れたシートとすることができる。
本発明の活性炭素繊維シートの全細孔容積の下限は、好ましくは0.50cm3/g以上であり、より好ましくは0.60cm3/g以上であり、更に好ましくは0.70、0.80又は0.85cm3/g以上である。
本発明の活性炭素繊維シートの全細孔容積の上限は、好ましくは1.20cm3/g以下であり、より好ましくは1.10cm3/g以下であり、更に好ましくは1.00cm3/g以下である。
全細孔容積を上記のような範囲とすることによって、蒸散燃料ガスに対する吸脱着性能についてより優れたシートとすることができる。
本発明の活性炭素繊維シートの平均細孔直径の下限は、好ましくは1.69nm以上であり、より好ましくは1.70nm以上であり、更に好ましくは1.72、1.75、1.78又は1.80nm以上である。
本発明の活性炭素繊維シートの平均細孔直径の上限は任意でありうるが、好ましくは4.00nm以下であり、より好ましくは3.50nm以下であり、更に好ましくは3.00nm以下である。
平均細孔直径を上記のような範囲とすることによって、蒸散燃料ガスに対する吸脱着性能についてより優れたシートとすることができる。
本発明において「ウルトラマイクロ孔」との用語は、細孔径が0.7nm以下の細孔を意味する。(なお、「細孔径」との用語は、特に明示しない限り、細孔の半径ではなく、細孔の直径又は幅のことをいう。)
本発明の活性炭素繊維シートのウルトラマイクロ孔容積の下限は、好ましくは0.10cm3/g以上であり、より好ましくは0.20cm3/g以上であり、更に好ましくは0.22又は0.25cm3/g以上である。
本発明の活性炭素繊維シートのウルトラマイクロ孔容積の上限は、好ましくは0.30cm3/g以下であり、より好ましくは0.29cm3/g以下であり、更に好ましくは0.28又は0.27cm3/g以下である。
ウルトラマイクロ孔容積を上記のような範囲とすることによって、蒸散燃料ガスに対する吸脱着性能についてより優れたシートとすることができる。
本発明において「マイクロ孔」との用語は、細孔径が2.0nm以下の細孔を意味する。
本発明の活性炭素繊維シートのマイクロ孔容積の下限は、好ましくは0.45cm3/g以上であり、より好ましくは0.50cm3/g以上であり、更に好ましくは0.55、0.60又は0.70cm3/g以上である。
本発明の活性炭素繊維シートのマイクロ孔容積の上限は、好ましくは1.00cm3/g以下であり、より好ましくは0.90cm3/g以下であり、更に好ましくは0.80cm3/g以下である。
マイクロ孔容積を上記のような範囲とすることによって、蒸散燃料ガスに対する吸脱着性能についてより優れたシートとすることができる。
細孔径が0.7nmより大きく2.0nm以下の細孔の細孔容積V0.7-2.0は、ウルトラマイクロ孔容積の値aとマイクロ孔容積の値bとを用い、下記式1によって求めることができる。
V0.7-2.0=b-a ・・・式1
本発明の本発明の活性炭素繊維シートにおいて、細孔径が0.7nmより大きく2.0nm以下の細孔の細孔容積V0.7-2.0の上限は、好ましくは1.20cm3/g以下であり、より好ましくは1.00cm3/g以下であり、更に好ましくは、0.90、0.80、0.75又は、0.70cm3/g以下である。
当該細孔容積V0.7-2.0を上記のような範囲とすることによって、蒸散燃料ガスに対する吸脱着性能についてより優れたシートとすることができる。
細孔径が2.0nm以下であるマイクロ孔の細孔容積に占める、細孔径が0.7nm以下であるウルトラマイクロ孔の細孔容積の存在比率R0.7/2.0は、ウルトラマイクロ孔容積の値aとマイクロ孔容積の値bとを用い、下記式2によって求めることができる。
R0.7/2.0=a/b×100(%) ・・・式2
本発明の活性炭素繊維シートにおいて、マイクロ孔容積に占めるウルトラマイクロ孔容積の存在比率R0.7/2.0の上限は、好ましくは60%以下であり、より好ましくは55%以下であり、更に好ましくは50、45又は40%以下である。
当該ウルトラマイクロ孔容積の存在比率R0.7/2.0を上記のような範囲とすることによって、蒸散燃料ガスに対する吸脱着性能についてより優れたシートとすることができる。
本発明の活性炭素繊維シートの坪量の下限は、好ましくは30g/m2以上であり、より好ましくは35g/m2以上であり、更に好ましくは37又は40g/m2以上である。
本発明の活性炭素繊維シートの坪量の上限は、好ましくは400g/m2以下であり、より好ましくは380g/m2以下であり、更に好ましくは360、350、340又は330g/m2以下である。
坪量を上記のような範囲とすることによって、キャニスタ内に収納できる吸着材の容量の範囲内において、キャニスタ用に要求される吸脱着性能についてより優れたシートとすることができる。
本発明の活性炭素繊維シートのシート厚みの下限は、好ましくは0.3mm以上であり、より好ましくは0.5mm以上、さらに好ましくは1.0mm又は1.5mm以上である。
本発明の活性炭素繊維シートのシート厚みの上限は、好ましくは8.0mm以下であり、より好ましくは7.0mm以下、さらに好ましくは4.0mm又は3.0mm以下である。
シート厚みを上記のような範囲とすることによって、キャニスタ内に収納できる吸着材の容量の範囲内において、キャニスタ用に要求される吸脱着性能についてより優れたシートとすることができる。
本発明の活性炭素繊維シートの密度の下限は、好ましくは0.030g/cm3以上であり、より好ましくは0.035g/cm3以上であり、更に好ましくは0.040g/cm3以上である。
本発明の活性炭素繊維シートのシート密度の上限は、好ましくは0.200g/cm3以下であり、より好ましくは0.190g/cm3以下であり、更に好ましくは0.180又は0.170g/cm3以下である。
シート密度を上記のような範囲とすることによって、キャニスタ内に収納できる吸着材の容量の範囲内において、キャニスタ用に要求される体積当たりの吸脱着性能についてより優れたシートとすることができる。
本発明の活性炭素繊維シートの引張強度(MD)の下限は、好ましくは0.05kN/m以上であり、より好ましくは0.06kN/m以上である。
本発明の活性炭素繊維シートの引張強度(MD)の上限は、特に制限はなく任意でありうるが、好ましくは2.50kN/m以下であり、より好ましくは2.40kN/m以下であり、さらに好ましくは2.30、2.20、2.10又は2.00kN/m以下である。
引張強度(MD)を上記のような範囲とすることによって、フレキシブル性を有するシートとすることができる。そのため、加工性に優れ、破損しにくく、キャニスタへの収納作業などにおける取扱いが容易な吸収材とすることができる。
本発明の活性炭素繊維シートの引張強度(CD)の下限は、好ましくは0.05kN/m以上であり、より好ましくは0.06kN/m以上であり、更に好ましくは0.07kN/m以上である。
本発明の活性炭素繊維シートの引張強度(CD)の上限は、特に制限はなく任意でありうるが、好ましくは2.50kN/m以下、より好ましくは2.40kN/m以下、さらに好ましくは2.30、2.20、2.10又は2.00kN/m以下でありうる。
引張強度(CD)を上記のような範囲とすることによって、フレキシブル性を有するシートとすることができる。そのため、加工性に優れ、破損しにくく、キャニスタへの収納作業などにおける取扱いが容易な吸収材とすることができる。
本発明の活性炭素繊維シートは、所定の水分含有量を有するものが好適である。例えば、23℃、相対湿度50%の条件下における水分含有量の下限は、好ましくは1%以上、より好ましくは2%以上であり、更に好ましくは3%以上である。
また23℃、相対湿度50%の条件下における水分含有量の上限は、好ましくは25%以下、より好ましくは22%以下、更に好ましくは15又は10%以下である。
上記の条件下における水分含有量を上記のような範囲とすることによって、自動車キャニスタ用の吸着材としてより優れたシートとすることができる。
本発明の活性炭素繊維シートは、吸着材として、所定のメチレンブルー吸着性能を有することが好ましい。メチレンブルー吸収性能は、活性炭素繊維シート重量当たりのメチレンブルー吸着量として示すことができる。本発明の活性炭素繊維シートが有するメチレンブルー吸着性能は、好ましくは60ml/g以上であり、より好ましくは70ml/g以上であり、更に好ましくは80、90又は100ml/g以上である。
本発明の活性炭素繊維シートは、吸着材として、所定のヨウ素吸着性能を有することが好ましい。ヨウ素吸収性能は、活性炭素繊維シート重量当たりのヨウ素吸着量として示すことができる。本発明の活性炭素繊維シートが有するヨウ素吸着性能は、好ましくは800mg/g以上であり、より好ましくは900mg/g以上であり、更に好ましくは1000、1100又は1200mg/g以上である。
本発明の活性炭素繊維シートは、吸着材として、所定のn―ブタン吸脱着性能を有することが好ましい。n-ブタン吸脱着性能は、蒸散ガスの吸脱着性能の指標となるため、n-ブタンの吸脱着性能が優れるものは、自動車キャニスタ用途に好適である。n-ブタン吸脱着性能は、n-ブタンを十分に吸収破過させた後、所定の脱着条件下に置いたときに吸着材から脱離させた後、吸着を繰り返す際の吸着量を、活性炭素繊維シート重量当たりのn-ブタンの有効吸着量として示すことができる。
また、本発明の活性炭素繊維シートの好ましい形態としては、下記実施例において示した測定方法に従って求められるn-ブタンの有効吸脱着率が、好ましくは29.0%以上であり、より好ましくは31.0%以上であり、更に好ましくは32.0又は34.0%でありうる。
本発明の活性炭素繊維シートは、上記の物性又は性能に係る項目のうち、少なくとも1つ又は任意の2つ以上の組合せからなる条件を満たすものであるが、好ましい組合せの例を以下に示す。なお、本発明の活性炭素繊維シートは下記の組合せの例に限定されるものではない。
以下の(1)~(3)の要件を満たす自動車キャニスタ用活性炭素繊維シート。
(1)比表面積が1400~2200m2/gである。
(2)細孔径が0.7nmより大きく2.0nm以下である細孔の細孔容積が、0.20~1.20cm3/gである。
(3)シート密度が0.030~0.200g/cm3である。
また、自動車キャニスタには大きさの制限があるため、活性炭素繊維シートを用いて吸着可能な量を担保する観点から、更に上記(3)のシート密度要件を満たすことが好ましい。活性炭素繊維シートは、原料の繊維シートを炭化して形成されることもあり、一般に、やや嵩高く、密度が低い傾向がある。上記(3)の要件を満たすために、活性炭素繊維シートは、製造過程において加圧処理等が行われ、圧密化されたものが好ましい。
このように、実施形態1のシートは、自動車キャニスタに求められる吸着性能および吸着容量の観点から好適な形態となっている。
実施形態1の(1)~(3)の要件に加え更に、下記(4)の要件を満たす自動車キャニスタ用活性炭素繊維シート。
(4)全細孔容積が0.50~1.20cm3/gである。
本発明の活性炭素繊維シートは、自動車キャニスタに収納される吸着材として好適である。すなわち、本発明は、他の一実施形態として、自動車キャニスタも提供することができる。
筐体内において吸着材を収納する吸着材室と、
吸着材室とエンジンとの間でガスを吸入または送出可能に連通するための第1の送出入口と、
吸着材室と燃料タンクとの間でガスを吸入または送出可能に連通するための第2の送出入口と、
吸着材室または外気から所定の圧力が負荷されたときに開口し、吸着材室と外気との間でガスを吸入または排出可能に連通するための第3の送出入口と、
を備えるキャニスタ。
また、本発明の活性炭素繊維シートを外気口寄りの吸着材室に用いる場合、本発明の活性炭素繊維シートはパージによる有効吸脱着量が高いため、自動車を長時間停車した場合の蒸散燃料ガスのリーク量を低減することができるという点でも自動車キャニスタに用いる吸着材として好適である。
吸着材室を2つ又はそれ以上有する自動車用キャニスタであって、
最も蒸散燃料ガス送出入口寄りに設けられた第1の吸着材室よりも外気口寄りに設けられた第2又はそれ以降の吸着材室に、本発明の活性炭素繊維シートが収納されている自動車用キャニスタ。
また、好ましい活性炭素炭素繊維シートの一形態としては、例えば、上記のように2つ又はそれ以上の吸着材室を有する自動車キャニスタにおいて、第2又はそれ以降の吸着材室用の活性炭素繊維シートとすることも好適である。
上記の形態において、吸着材室は2つでもよいし、それ以上の数であってもよい。また、吸着材室が3つ以上ある場合には、本発明の活性炭素繊維シートは、第2の吸着材室以後の少なくとも1つの吸着材室に収納されていればよい。
上記本発明の活性炭素繊維シートは、上記に示したような所定の項目のうちから選ばれる要件を満たすように製造する。本発明の活性炭素繊維シートは、例えば、以下のようにして作製することができる。
リン酸系触媒若しくは有機スルホン酸系触媒のいずれか一方または双方を保持させた原料シートを炭化及び賦活化すること、並びに
当該活性炭素繊維シートの密度が0.030~0.200g/cm3となるように加圧処理すること、
を含む製法を挙げられる(以下、製法実施形態1という)。
<繊維の種類>
原料シートを構成する繊維としては、例えば、セルロース系繊維、ピッチ系繊維、PAN系繊維、フェノール樹脂系繊維などが挙げられ、好ましくはセルロース系繊維が挙げられる。
セルロース系繊維とは、セルロース及び/又はその誘導体を主成分として構成される繊維である。セルロース、セルロース誘導体は、化学合成品、植物由来、再生セルロース、バクテリアが産生したセルロースなど、その由来はいずれであってもよい。セルロース系繊維として好ましくは、例えば、樹木などから得られる植物系セルロース物質で形成された繊維、および、植物系セルロース物質(綿、パルプなど)に化学処理を施して溶解させて得られる長い繊維状の再生セルロース系物質から構成された繊維などを用いうる。また、この繊維には、リグニンやヘミセルロースなどの成分が含まれていても構わない。
繊維シートは、多数の繊維を薄く広いシート状に加工したもののことをいい、織物、編み物、および不織布などが含まれる。
製法実施形態1では、上記のようにして用意された原料シートに、触媒を保持させる。原料シートに触媒を保持させて炭化処理を行い、さらに水蒸気や二酸化炭素、空気ガス等を用いて賦活化し、多孔質の活性炭素繊維シートを得ることができる。触媒としては、例えば、リン酸系触媒、有機スルホン酸系触媒などを用いうる。
リン酸系触媒としては、例えば、リン酸、メタリン酸、ピロリン酸、亜リン酸、ホスホン酸、亜ホスホン酸、ホスフィン酸等のリンのオキシ酸、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸三アンモニウム、ジメチルホスホノプロパンアミド、ポリリン酸アンモニウム、ポリホスホニトリルクロライド、およびリン酸、テトラキス(ヒドロキシメチル)ホスホニウム塩またはトリス(1-アジリジニル)ホスフィンオキサイドと尿素、チオ尿素、メラミン、グアニン、シアナミツド、ヒドラジン、ジシアンジアミドまたはこれらのメチロール誘導体との縮合物などが挙げられ、好ましくはリン酸水素二アンモニウムが挙げられる。リン酸系触媒は、1種を単独で用いてもよく、2種以上を併用してもよい。リン酸系触媒を水溶液として用いる場合、その濃度は、好ましくは0.05~2.0mol/Lであり、より好ましくは0.1~1.0mol/Lである。
有機スルホン酸としては、1又は複数のスルホ基を有する有機化合物を用いることができ、例えば脂肪族系、芳香族系など種々の炭素骨格にスルホ基が結合した化合物が利用可能である。有機スルホン酸系触媒としては、取扱いの観点から、低分子量のものが好ましい。
上記、リン酸系触媒および有機スルホン酸系触媒は、混合して、混合触媒として用いてもよい。混合比は適宜調整してよい。
原料シートに対し触媒を保持させる。ここで「保持」とは、触媒が原料シートに接触した状態を保つことを意味し、付着、吸着、含浸などの諸形態でありうる。触媒を、保持させる方法には特に制限はないが、例えば、触媒を含む水溶液に浸漬する方法、触媒を含む水溶液を原料シートに対して振りかける方法、気化した触媒蒸気に接触させる方法、触媒を含む水溶液に原料シートの繊維を混ぜて抄紙する方法などが挙げられる。
触媒を保持させた原料シートを用意した後、それを炭化処理を行う。活性炭素繊維シートを得るための炭化処理は、一般的な活性炭の炭化方法に沿って行うことができるが、好ましい実施形態として、以下のようにして行うことができる。
加熱温度の上限は、好ましくは1400℃以下であり、より好ましくは1300℃以下であり、さらに好ましくは1200℃以下又は1000℃以下である。
このような加熱温度設定とすることにより、繊維形態が維持された炭素繊維シートを得ることができる。加熱温度が上記の下限以下であると、炭素繊維の炭素含有量が80%以下で炭化が不十分となりやすい。
加熱処理時間の上限は任意でありうるが、好ましくは180分以下であり、より好ましくは160分であり、さらに好ましくは140分以下である。
原料シートに十分に触媒を含浸させ、上記の好適な加熱温度に設定し、加熱処理時間を調整することにより、細孔形成の進行程度を調整することができ、比表面積、各種細孔の容積、平均細孔直径などの多孔体としての物性を調整することができる。
加熱処理時間が上記の下限より少ないと、炭化が不十分となりやすい。
本発明における賦活化処理としては、例えば上記加熱処理後に連続して、水蒸気を供給し適切な賦活温度で所定時間保持することで行うことができ、活性炭素繊維シートを得ることができる。
他方、賦活温度の上限は、好ましくは1400℃以下であり、より好ましくは1300℃以下であり、さらに好ましくは1200又は1000℃以下である。
なお、加熱処理後に連続して賦活処理を行う場合、加熱処理温度と同等程度に調整することが望ましい。
賦活時間の上限は任意でありうるが、好ましくは180分以下であり、より好ましくは160分以下であり、さらに好ましくは140分以下、100分以下、50分以下、30分以下である。
本発明の活性炭素繊維シートは、シート密度が調整されたものであることが好ましい。シート密度を調整するためには、製造工程のいずれかの段階において、圧密化処理することが好ましい。圧密化処理は、例えば、シートを加圧処理し、高密度化することにより行いうる。
(1)原料シートに樹脂などのバインダーを含有させ加温加圧処理を施し、高密度化した原料シートを調製し、炭化処理する。
(2)炭化処理を行う工程において、炭化処理を行いつつ、シートを加圧処理する。
(3)炭化処理を施した後、樹脂などのバインダーを含有させ活性炭素繊維シートを加温加圧処理する。
(4)活性炭素繊維シートを解繊し、パルプ等と混抄する。
活性炭素繊維シートを約30mg採取し、200℃で20時間真空乾燥して秤量し、高精度ガス/蒸気吸着量測定装置BELSORP-maxII(マイクロトラック・ベル社)を使用して測定した。液体窒素の沸点(77K)における窒素ガスの吸着量を相対圧が10-8オーダー~0.990の範囲で測定し、試料の吸着等温線を作成した。この吸着等温線を、解析相対圧範囲を吸着等温線I型(ISO9277)の条件で自動的に決定したBET法により解析し、重量当たりのBET比表面積(単位:m2/g)を求め、これを比表面積(単位:m2/g)とした。
上記比表面積の項で得られた等温吸着線の、相対圧0.990での結果より1点法での全細孔容積(単位:cm3/g)を算出した。
次式3により算出した。
平均細孔直径(単位:nm)=4×全細孔容積×103÷比表面積 ・・・式3
上記比表面積の項で得られた等温吸着線を、高精度ガス/蒸気吸着量測定装置BELSORP-maxII(マイクロトラック・ベル社)付属の解析ソフトBELMasterを用いて、解析設定を「スムージング(細孔分布の解析全点で前後1点を使用した移動平均処理)」、「分布関数:No-assumption」、「細孔径の定義:Solid and Fluid Def. Pore Size」、「Kernel:Slit-C-Adsorption」としたGCMC法によって解析し、得られた吸着時の細孔分布曲線の結果から、0.7nmの積算細孔容積を読み取り、ウルトラマイクロ孔容積(単位:cm3/g)とした。
上記比表面積の項で得られた等温吸着線を、高精度ガス/蒸気吸着量測定装置BELSORP-maxII(マイクロトラック・ベル社)付属の解析ソフトBELMasterを用いて、解析設定を「スムージング(細孔分布の解析全点で前後1点を使用した移動平均処理)」、「分布関数:No-assumption」、「細孔径の定義:Solid and Fluid Def. Pore Size」、「Kernel:Slit-C-Adsorption」としたGCMC法によって解析し、得られた吸着時の細孔分布曲線の結果から、2.0nmの積算細孔容積を読み取り、マイクロ孔容積(単位:cm3/g)とした。
活性炭素繊維シートを、温度23±2℃、相対湿度50±5%の環境下で12時間以上静置し、重量と縦横の寸法からシート坪量(単位:g/m2)を求めた。
活性炭素繊維シートを、温度23±2℃、相対湿度50±5%の環境下で12時間以上静置し、デジタル小型側厚器FS-60DS(大栄科学精器製作所社)を用いて、0.3KPaの荷重をかけた際のシート厚さ(単位:mm)を測定した。
次式4により算出した。
シート密度(単位:g/cm3)=シート坪量÷シート厚み÷103 ・・・式4
活性炭素繊維シートを、温度23±2℃、相対湿度50±5%の環境下で12時間以上静置し、Machine Direction(MD)方向及びこれと直行するCross Direction(CD)方向から、それぞれ試験片(幅15mm、長さ50~60mm)を各方向が長さとなるように切り取り、テンシロン万能試験機RTG-1210(エー・アンド・デイ社)を用いて、つかみ間隔40mm、引っ張り速度100mm/分で引っ張り、次式5および6により引張強度および伸び率をそれぞれ算出した。
引張強度(単位:kN/m)=試験中に加わった最大荷重(単位:N)÷15mm
伸び率(単位:%)=最大荷重時の伸長量(単位:mm)÷40mm
活性炭素繊維シートを、温度23±2℃、相対湿度50±5%の環境下で12時間以上静置後、試料を0.5~1.0g採取し、乾燥機で115±5℃3時間以上乾燥させた際の重量変化から、水分(単位:%)を求めた。
日本水道協会規格水道用粉末活性炭(JWWA K113)のメチレンブルー脱色力(単位:ml/g)に従って測定した結果を、メチレンブルー吸着性能(単位:ml/g)とした。
日本水道協会規格水道用粉末活性炭(JWWA K113)のヨウ素吸着性能(単位:mg/g)に従って測定した。
活性炭素繊維シートを0.114cm3採取し、触媒分析装置BELCATII(マイクロトラック・ベル社)を使用して測定した。試験温度25℃で、窒素ガスで0.2%濃度に希釈したノルマルブタンガス50cm3/分を試料に流しn-ブタンを吸着破過させ、その後、活性炭素繊維シート体積の2000倍になるよう窒素ガス23cm3/分を約600秒間試料に流しn-ブタンを脱着させる事を3回繰り返した。2回目吸着量、2回目脱着量、3回目吸着量、3回目脱着量の平均を有効吸脱着量(mmol/g)、有効吸脱着量を1回目の吸着量で除した割合を有効吸脱着率(%)とした。
レーヨン繊維(1.7dtex、繊維長40mm)からなる坪量300g/m2のニードルパンチ不織布に5~8%リン酸水素二アンモニウム水溶液を含浸し、絞液後、乾燥して、8~10重量%付着させた。得られた前処理不織布を加圧しながら窒素雰囲気中、900℃まで50分で昇温し、この温度で4分保持した。引き続きその温度で露点60℃の水蒸気を含有する窒素気流中で10分間賦活処理を行った。
レーヨン繊維(3.3dtex、繊維長76mm)からなる坪量300g/m2のニードルパンチ不織布に5~8%リン酸水素二アンモニウム水溶液を含浸し、絞液後、乾燥して、8~10重量%付着させた。得られた前処理不織布を窒素雰囲気中、900℃まで50分で昇温し、この温度で12分保持した。引き続きその温度で露点60℃の水蒸気を含有する窒素気流中で10分間賦活処理を行った。
実施例2における900℃までの昇温時間を25分に、900℃保持時間を2分に、賦活処理時間を6分に変更した以外は、実施例2と同じ方法で、比較例1の活性炭素繊維シートを作製した。
市販のキャニスタに充填された粒状活性炭を取り出し、比較例2の吸着材として用いた。市販のキャニスタとして、品番:77740-48220(トヨタ部品山口共販株式会社)のキャニスタを用いた。
Claims (5)
- 比表面積が1400~2200m2/gであり、
細孔径が0.7nmより大きく2.0nm以下である細孔の細孔容積が、0.20~1.20cm3/gであり、且つ
シート密度が0.030~0.200g/cm3である、
自動車キャニスタ用活性炭素繊維シート。 - 全細孔容積が0.50~1.20cm3/gである、請求項1に記載の自動車キャニスタ用活性炭素繊維シート。
- 該活性炭素繊維シートは、セルロース系繊維の炭化処理物である、請求項1または2に記載の自動車キャニスタ用活性炭素繊維シート。
- 請求項1~3のいずれか一項に記載の自動車キャニスタ用活性炭素繊維シートを備えた自動車キャニスタ。
- 自動車キャニスタ用活性炭素繊維シートの製造方法であって、
リン酸系触媒若しくは有機スルホン酸系触媒のいずれか一方または双方を保持させた原料シートを、炭化及び賦活化すること、並びに
当該活性炭素繊維シートの密度が0.030~0.200g/cm3となるように圧密化処理することを含む、製造方法。
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JP7229788B2 (ja) * | 2019-01-22 | 2023-02-28 | 日本製紙株式会社 | 活性炭素繊維材料 |
WO2022181616A1 (ja) | 2021-02-24 | 2022-09-01 | 日本製紙株式会社 | キャニスタ用成形吸着体 |
KR20230148422A (ko) | 2021-02-24 | 2023-10-24 | 닛뽄세이시가부시끼가이샤 | 캐니스터용 성형 흡착체 |
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CA3098440A1 (en) | 2019-12-26 |
CN112154264B (zh) | 2022-05-03 |
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TWI695733B (zh) | 2020-06-11 |
CA3098440C (en) | 2023-01-24 |
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US20210198111A1 (en) | 2021-07-01 |
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