JPH1149503A - Spherical carbon material and its production - Google Patents
Spherical carbon material and its productionInfo
- Publication number
- JPH1149503A JPH1149503A JP10018179A JP1817998A JPH1149503A JP H1149503 A JPH1149503 A JP H1149503A JP 10018179 A JP10018179 A JP 10018179A JP 1817998 A JP1817998 A JP 1817998A JP H1149503 A JPH1149503 A JP H1149503A
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- spherical
- pore diameter
- less
- pore
- 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.)
- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 239000011148 porous material Substances 0.000 claims abstract description 79
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000012856 packing Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 2
- 230000004580 weight loss Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 4
- 239000012808 vapor phase Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000000126 substance Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- 239000005011 phenolic resin Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910021642 ultra pure water Inorganic materials 0.000 description 18
- 239000012498 ultrapure water Substances 0.000 description 18
- 239000003463 adsorbent Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- 239000012535 impurity Substances 0.000 description 15
- 150000004045 organic chlorine compounds Chemical class 0.000 description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 229960001701 chloroform Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 239000012847 fine chemical Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 244000060011 Cocos nucifera Species 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 210000000056 organ Anatomy 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000013585 weight reducing agent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- GATVIKZLVQHOMN-UHFFFAOYSA-N Chlorodibromomethane Chemical compound ClC(Br)Br GATVIKZLVQHOMN-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- -1 purifiers Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- FMWLUWPQPKEARP-UHFFFAOYSA-N bromodichloromethane Chemical compound ClC(Cl)Br FMWLUWPQPKEARP-UHFFFAOYSA-N 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000011824 nuclear material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】液相系、及び気相系に於いて
存在する特定の物質に対し、吸着及びまたは触媒作用を
及ぼし、これら物質を除去または分解するのに適した、
浄水器、超純水製造装置、空気清浄機、悪臭・有機溶剤
等の分離・回収装置、特定物質の分離・精製装置、人工
臓器等に於いて、また医薬品等ファインケミカル分野に
於ける不純物除去、生体内の特定物質の除去等に於いて
好適に使用される吸着材、触媒、触媒担体として使用さ
れる炭素材及びその製造方法に関する。BACKGROUND OF THE INVENTION The present invention is suitable for removing and decomposing certain substances present in a liquid phase system and a gas phase system by adsorbing and / or catalyzing them.
Removal of impurities in water purifiers, ultrapure water production equipment, air purifiers, equipment for separating and recovering odors and organic solvents, separation and purification equipment for specific substances, artificial organs, etc., and fine chemicals such as pharmaceuticals. The present invention relates to a carbon material used as an adsorbent, a catalyst, and a catalyst carrier suitably used for removing a specific substance in a living body and a method for producing the same.
【０００２】[0002]
【従来の技術】従来から水中あるいは大気中に存在する
種々の有害物質、特に低分子化合物等を吸着または分解
除去する吸着材または触媒または触媒担体として炭素材
が注目されていた。しかし、例えば水道中の塩素化合物
は分子量が小さく、濃度が希薄である為に、充分にこれ
らを除去できる吸着性を有する炭素材を得ることができ
なかった。ところが最近になって、低賦活度で比較的比
表面積の小さい炭素材がこれら化合物に対し高い吸着性
を示すことが知られ、特開平６−１０６１６１にはヤシ
殻または木材の炭化物、及び石炭等を原料とした低賦活
度の炭素材は有機塩素化合物に対する吸着性が良好であ
ることが記載されている。2. Description of the Related Art Carbon materials have attracted attention as an adsorbent or a catalyst or a catalyst carrier for adsorbing or decomposing and removing various harmful substances existing in water or in the air, especially low-molecular compounds. However, for example, chlorine compounds in tap water have a small molecular weight and a low concentration, so that it was not possible to obtain an adsorbing carbon material capable of sufficiently removing these compounds. Recently, however, it has been known that a carbon material having a low activation degree and a relatively small specific surface area has a high adsorptivity to these compounds. Japanese Patent Application Laid-Open No. 6-106161 discloses coconut shell or wood carbide, coal and the like. It is described that a low-activation carbon material made of styrene has good adsorptivity to organic chlorine compounds.
【０００３】更に、特願平０７−２９６２５１、日本吸
着学会第９回研究発表会講演要旨集ｐ．４７〜４８に
は、本発明者らにより、フェノール樹脂粉末を主原料と
して開発した炭素材は、細孔直径０．６〜０．８ｎｍの
細孔が発達し、上水中の有機塩素化合物を効率的に除去
でき、優れた吸着特性を有することが示されている。Further, Japanese Patent Application No. 07-296251, Abstracts of the 9th Research Presentation Meeting of the Adsorption Society of Japan, p. 47-48, the carbon material developed by the present inventors using phenolic resin powder as a main raw material develops pores having a pore diameter of 0.6-0.8 nm and efficiently converts organic chlorine compounds in tap water. It has been shown to be able to be removed effectively and to have excellent adsorption properties.
【０００４】[0004]
【発明が解決しようとする課題】しかしこれらヤシ殻、
石炭、フェノール樹脂等を賦活して得た従来の炭素材
は、ペレット状、または大きな固まりを破砕して得た不
定形の破砕状であり、角が存在する形状である。これら
炭素材を浄水器、超純水製造装置、空気清浄器内等に充
填し低分子化合物除去用として用いると、浄水器、超純
水製造装置、空気清浄器等の長期間断続使用時の圧力変
化、塩素化合物、窒素酸化物、酸素等による酸化分解等
の影響を受け、炭素材の機械的強度の低下が生じ、徐々
に炭素材の角部分が劣化及び粉化し、これが炭素材の特
性を司る微細孔を潰したり、後段にあるフィルターの目
を閉塞すると言った問題があった。However, these coconut shells,
A conventional carbon material obtained by activating coal, a phenol resin, or the like is in the form of pellets or an irregular crushed shape obtained by crushing a large mass, and has a shape having corners. When these carbon materials are filled into water purifiers, ultrapure water production equipment, air purifiers, etc. and used for removing low molecular compounds, they can be used for long-term intermittent use of water purifiers, ultrapure water production equipment, air purifiers, etc. Under the influence of pressure change, oxidative decomposition by chlorine compounds, nitrogen oxides, oxygen, etc., the mechanical strength of the carbon material decreases, and the corners of the carbon material gradually deteriorate and powder, which is the characteristic of the carbon material. There is a problem that the micropores governing the filter are crushed or the eyes of the filter at the subsequent stage are closed.
【０００５】前記の長期間断続使用時の圧力変化とは、
例えば、浄水器、超純水製造装置等が上水道の蛇口の後
段に設置されるため、蛇口開栓時と閉栓時に３ｋｇ／ｃ
ｍ2以下程度の圧力変化が生じることを意味しており、
通常は炭素材使用中に数百回〜数千回この変化が生じ
る。この圧力変化が生じると、その度毎に装置内に充填
された炭素材はお互いの接触状態が変化し、僅かずつ劣
化していく。[0005] The pressure change during long-term intermittent use is as follows.
For example, since a water purifier, an ultrapure water production device, and the like are installed after the faucet of the water supply system, 3 kg / c is used when the faucet is opened and closed.
It means that a pressure change of about m 2 or less occurs,
Usually, this change occurs hundreds to thousands of times during the use of the carbon material. Whenever this pressure change occurs, the state of contact between the carbon materials filled in the apparatus changes each time, and the carbon materials gradually deteriorate.
【０００６】また、従来の炭素材には球状と称するもの
もあるが、その殆どがバインダー成分と核物質を転動造
粒法と呼ばれる方法で撹拌しつつ、核物質を団子状に２
次凝集させ賦活製造された物であり、造粒品の締まりが
弱く、破砕強度が低く、表面は滑沢ではなく凹凸を有す
るため、他の形状を有する炭素材と同様に前述の様な劣
化を受け易い。[0006] Some conventional carbon materials are called spherical, but most of them are agitated with a binder component and a nuclear material by a method called tumbling granulation method, and the nuclear material is collected in a ball shape.
It is a product that has been activated by agglomeration, and the granulated product has weak tightening, low crushing strength, and the surface has unevenness instead of lubrication. Easy to receive.
【０００７】また、従来の炭素材には、球状であり、表
面が滑沢であるものも存在するが、その粒子直径が１５
０μｍ以下であったり、または破砕強度、耐磨耗強度が
充分大きく無いため、浄水器、超純水製造装置、空気清
浄器等に利用した場合に、その炭素材を通過する水また
は空気等媒体の圧力損失の増加、各装置への充填時の取
り扱いの不便さ、前述と同様な炭素材使用中に於ける劣
化等の問題が生じ、これら用途においては不都合であっ
た。[0007] Some conventional carbon materials have a spherical shape and a smooth surface.
0μm or less, or the crushing strength and abrasion resistance are not sufficiently large. When used in water purifiers, ultrapure water production equipment, air purifiers, etc., water or air medium that passes through the carbon material However, problems such as an increase in pressure loss, inconvenience in handling at the time of filling each device, and deterioration during use of the carbon material similar to those described above occurred, which was inconvenient in these applications.
【０００８】粒子直径が１５０μｍ以下である球状炭素
材を用いた場合に於ける、炭素材を通過する水または空
気等の媒体による圧力損失の増加とは、炭素材を浄水
器、超純水製造装置、空気清浄器等に利用する際に、炭
素材を保持する編み目構造を有する不織布、メッシュ等
との関係で生じる。これは粒子直径が１５０μｍ以下の
炭素材を保持するためには、それ以下の目開き径の不織
布、メッシュ等を用いる必要があるため、上述の用途に
於いて水、空気等を通過させると、水、空気中の僅かな
微粒子の影響で目詰まりが生じるためである。When a spherical carbon material having a particle diameter of 150 μm or less is used, an increase in pressure loss due to a medium such as water or air passing through the carbon material means that the carbon material is purified by a water purifier, ultrapure water production. When it is used for an apparatus, an air purifier, or the like, it occurs in relation to a nonwoven fabric, a mesh, or the like having a stitch structure that holds a carbon material. This is because, in order to hold a carbon material having a particle diameter of 150 μm or less, it is necessary to use a nonwoven fabric with a mesh diameter of less than that, a mesh or the like. This is because clogging occurs due to the effect of slight particles in water and air.
【０００９】粒子直径が１５０μｍ以下である球状炭素
材を用いた場合に於ける、炭素材を各装置へ充填する際
の取り扱いの不便さとは、上述の各装置製造時に、粒子
直径が１５０μｍ以下である球状炭素材を容器から取り
出し、カラム等に充填する際に、その粒子が周囲へ舞い
上がり、飛散するため、取り扱い作業者、周囲環境への
悪影響が生じ易いこと等である。In the case where a spherical carbon material having a particle diameter of 150 μm or less is used, the inconvenience of handling when filling the carbon material into each device is as follows. When a certain spherical carbon material is taken out of a container and packed in a column or the like, the particles soar up and scatter around, which may easily affect the handling operator and the surrounding environment.
【００１０】また、従来より炭素材原料とし用いられる
ヤシ殻、石炭等の天然物は、その産出地によりアルカリ
金属類、アルカリ土類金属類、重金属類等の含有量が大
きく異る。このため、これら天然物を原料として製造し
た炭素材を浄水用吸着材、超純水製造用吸着材、医薬品
等ファインケミカル分野に於ける不純物除去用吸着材、
人工臓器用吸着材、生体内の特定物質除去用吸着剤、ま
たは特定物質の分離・精製用吸着材等として使用する際
には、それらの金属類の溶出に充分注意を払わねばせね
ばならないため、その炭素材の洗浄に大きな労力を要す
るという問題があった。また石油系ピッチ、石炭系ピッ
チを原料とする炭素材もあるが、原料ピッチ中にはベン
ツピレンを始めとして数々の芳香族系発ガン物質が存在
する可能性もあり、これらの溶出に対して注意を払わね
ばならないとの問題があった。[0010] Natural materials such as coconut shells and coal conventionally used as carbon material raw materials differ greatly in the content of alkali metals, alkaline earth metals, heavy metals and the like depending on the place of production. For this reason, carbon materials produced using these natural products as raw materials are adsorbents for water purification, adsorbents for ultrapure water production, adsorbents for impurity removal in the field of fine chemicals such as pharmaceuticals,
When used as an adsorbent for artificial organs, an adsorbent for removing specific substances in a living body, or an adsorbent for separating / purifying specific substances, it is necessary to pay sufficient attention to the elution of such metals. However, there is a problem that a large amount of labor is required for cleaning the carbon material. There are also carbon materials made from petroleum-based pitch and coal-based pitch, but there may be many aromatic carcinogens such as benzopyrene in the raw material pitch. Had to be paid.
【００１１】更に、浄水器、超純水製造用、空気清浄器
用、悪臭・有機溶剤等の分離・回収装置用の吸着材とし
て用いる際には、装置をよりコンパクトにするため、充
填密度の高い炭素材が望まれていた。Further, when used as an adsorbent for water purifiers, ultrapure water production, air purifiers, and separation / recovery devices for foul odors and organic solvents, the packing density is high to make the device more compact. Carbon materials were desired.
【００１２】本発明者らは上記の課題を解決すべく鋭意
研究した結果、本発明を完成したものであって、本発明
の目的は液相系、及び気相系に於いて存在する特定成分
に対し、吸着及びまたは触媒作用を及ぼし、浄水器、超
純水製造装置、空気清浄機、悪臭・有機溶剤等の分離・
回収装置、特定物質の分離・精製装置、人工臓器等に於
いて、また医薬品等ファインケミカル分野に於ける不純
物除去、生体内の特定物質の除去等に於いて好適に使用
される吸着材、触媒、触媒担体として使用される炭素
材、及びその製造方法を提供することにある。特に浄水
器用、超純水製造装置用、医薬品等ファインケミカル分
野に於ける不純物除去用等として用いた場合に、低沸点
有機塩素化合物、残留塩素等の除去性能に優れ、炭素材
自体からの不純物溶出が少なく、カラム等に充填して使
用する際の充填操作が容易で、かつ充填密度が高く、長
期間使用しても圧力損失の上昇、粉化が生じにくい炭素
材及びその製造方法を提供することにある。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. An object of the present invention is to provide specific components existing in a liquid phase system and a gas phase system. Exerts adsorption and / or catalytic action on water, purifiers, ultrapure water production equipment, air purifiers,
Adsorbents, catalysts, and the like that are preferably used in recovery devices, separation / purification devices for specific substances, artificial organs, etc., and in the removal of impurities in the field of fine chemicals such as pharmaceuticals, and the removal of specific substances in living bodies. An object of the present invention is to provide a carbon material used as a catalyst carrier and a method for producing the same. Particularly when used for water purifiers, ultrapure water production equipment, and for removing impurities in the field of fine chemicals such as pharmaceuticals, it excels in the performance of removing low-boiling organic chlorine compounds, residual chlorine, etc., and elutes impurities from the carbon material itself. The present invention provides a carbon material and a method for producing the same, which can be easily packed when used in a column or the like, and have a high packing density, and are less likely to cause an increase in pressure loss and powdering even when used for a long time. It is in.
【００１３】本発明の球状炭素材が吸着する特定成分、
又は触媒作用を及ぼす特定成分とは、残留塩素や、トリ
クロロメタン、ブロモジクロロメタン、ジブロモクロロ
メタン、トリブロモメタン等のトリハロメタン類、或は
トリクロロエタン、トリクロロエチレン、フロン、ジク
ロロメタン、四塩化炭素等のハロゲン化炭化水素類、或
はトルエン、ベンゼン、キシレン、ｎ−ヘキサン、シク
ロヘキサン等の炭化水素、或はアセトン、メチルエチル
ケトン等のケトン類、或はメタノール、エタノール等の
アルコール類や各種有機溶剤、或はメチルメルカプタ
ン、硫化水素、二酸化硫黄、酢酸、アセトアルデヒド、
ホルムアルデヒド、アンモニア、クレゾール等の悪臭原
因物質、或は二酸化窒素、一酸化窒素、オゾン等の有毒
ガス、或は蛋白質、糖類等、或は金、白金、コバルト、
イットリウム、ランタン等の金属錯体、又はコロイド等
であり、或は上記物質の複合混合物である。A specific component to which the spherical carbon material of the present invention adsorbs,
Or, the specific component having a catalytic action is residual chlorine, trihalomethanes such as trichloromethane, bromodichloromethane, dibromochloromethane, and tribromomethane, or halogenated carbon such as trichloroethane, trichloroethylene, freon, dichloromethane, and carbon tetrachloride. Hydrogens, hydrocarbons such as toluene, benzene, xylene, n-hexane, and cyclohexane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; and various organic solvents; and methyl mercaptan; Hydrogen sulfide, sulfur dioxide, acetic acid, acetaldehyde,
Odor-causing substances such as formaldehyde, ammonia and cresol; or toxic gases such as nitrogen dioxide, nitric oxide and ozone; or proteins and sugars; or gold, platinum and cobalt.
It is a metal complex such as yttrium or lanthanum, or a colloid, or a complex mixture of the above substances.
【００１４】これら特定成分は、水道水、家庭排水、工
業排水、河川、湖沼、海水、及び生体内体液の液相や、
大気、排気ガス等の気相に存在するものでもよい。These specific components include tap water, domestic effluent, industrial effluent, rivers, lakes and marshes, seawater, and the liquid phase of body fluids,
It may exist in the gas phase such as the atmosphere and exhaust gas.
【００１５】[0015]
【課題を解決するための手段】上述の目的は、比表面積
７００〜１６００ｍ2 ／ｇ、細孔直径０．０１〜１０μ
ｍの細孔容積が０．１５ｃｃ／ｇ以下、細孔直径１０ｎ
ｍ以下の細孔容積が０．２０〜１．２０ｃｃ／ｇであ
り、かつ細孔直径１０ｎｍ以下の細孔容積に占める細孔
直径１ｎｍ以下の細孔容積の割合が７８ｖｏｌ％以上で
あり、充填密度が０．５５〜０．８０ｇ／ｃｃ、破砕強
度が４０Ｋｇ／ｃｍ2 以上であり、灰分量が０．５％以
下の粒子直径１５０〜２０００μｍの球状炭素材により
達成される。The above-mentioned objects are to achieve a specific surface area of 700 to 1600 m 2 / g and a pore diameter of 0.01 to 10 μm.
m having a pore volume of 0.15 cc / g or less and a pore diameter of 10 n
m is 0.20 to 1.20 cc / g, and the ratio of the pore volume having a pore diameter of 1 nm or less to the pore volume having a pore diameter of 10 nm or less is 78 vol% or more. It is achieved by a spherical carbon material having a density of 0.55 to 0.80 g / cc, a crushing strength of 40 kg / cm 2 or more, and an ash content of 0.5% or less and a particle diameter of 150 to 2000 μm.
【００１６】また前述の目的は、粒子直径１５０〜２０
００μｍの球状樹脂、またはこの樹脂を非酸化性雰囲気
下５００℃以上で炭化して得た球状炭化物を、７００〜
１１００℃の温度範囲で、樹脂または炭化物を基準とす
る重量減少率が５〜７０％となる範囲で賦活することを
特徴とする球状炭素材の製造方法により達成される。The above-mentioned object is to achieve a particle diameter of 150 to 20.
A spherical resin obtained by carbonizing a 00 μm spherical resin or this resin at 500 ° C. or more in a non-oxidizing atmosphere,
It is achieved by a method for producing a spherical carbon material, wherein activation is performed in a temperature range of 1100 ° C. so that a weight reduction rate based on resin or carbide is 5 to 70%.
【００１７】ここで球状樹脂とは、例えばアルデヒド
類、フェノール類を主成分とする化学反応により製造
し、球状となったフェノール樹脂等であり、微粉砕した
樹脂の粉をバインダーと混合後、転動造粒法により機械
的に団子状に造粒成形した球状の成形樹脂とは異なる。Here, the spherical resin is, for example, a spherical phenol resin produced by a chemical reaction containing aldehydes and phenols as main components. It is different from a spherical molding resin mechanically granulated into a dumpling shape by the dynamic granulation method.
【００１８】[0018]
【発明の実施の形態】以下に本発明を詳細に記載する。
本発明の球状炭素材を得るには、フェノール樹脂、メラ
ミン樹脂、尿素樹脂、エポキシ樹脂等の熱硬化性樹脂を
利用し得るが、例えば以下の製造方法で得たフェノール
樹脂を出発原料とし得る。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
To obtain the spherical carbon material of the present invention, a thermosetting resin such as a phenol resin, a melamine resin, a urea resin, and an epoxy resin can be used. For example, a phenol resin obtained by the following production method can be used as a starting material.
【００１９】球状フェノ−ル樹脂の粒子直径が、１５０
〜２０００μｍ程度の粒子直径に適するものを製造する
方法としては、特開昭６３−４８３２０号公報記載の方
法により、フェノ−ル樹脂、ガラス粒子、ＳｉＣ、メソ
フェーズ、アルミナ、黒鉛、金雲母等を核物質として、
再度フェノール類、アルデヒド類を分散剤存在下で縮合
反応させ、縮合物が核物質の回りに凝集されて、粉粒体
を生成させた後脱水乾燥して得ることができる。When the particle diameter of the spherical phenol resin is 150
As a method for producing a material suitable for a particle diameter of about 2,000 μm, phenol resin, glass particles, SiC, mesophase, alumina, graphite, phlogopite, etc. are prepared by the method described in JP-A-63-48320. As a substance,
Phenols and aldehydes are again subjected to a condensation reaction in the presence of a dispersing agent, and the condensate is aggregated around a core substance to produce a powder and a granule, followed by dehydration and drying.
【００２０】本発明で使用する粒子直径１５０〜２００
０μｍの球状樹脂は、上述の様な方法で得た球状樹脂を
篩い分け、１５０μｍ以下及び２０００μｍ以上のもの
を除去して得ることができる。本発明の炭素材製造のた
めに用いる球状フェノール樹脂の粒子直径は通常１５０
〜２０００μｍが好適であるが、製造された炭素材の用
途により適する粒子直径は異なる。この時、製造工程中
の炭化処理、賦活処理により、粒子直径は最大３割程度
収縮することを考慮する必要がある。The particle diameter used in the present invention is 150 to 200.
The spherical resin of 0 μm can be obtained by sieving the spherical resin obtained by the above-mentioned method and removing those having a diameter of 150 μm or less and 2000 μm or more. The particle diameter of the spherical phenol resin used for producing the carbon material of the present invention is usually 150
２０００2000 μm is preferred, but the suitable particle diameter varies depending on the use of the produced carbon material. At this time, it is necessary to consider that the particle diameter shrinks by up to about 30% due to carbonization and activation during the manufacturing process.
【００２１】本発明の炭素材製造のために用いる出発原
料は、上記の様な製法で得るため、従来の炭素材原料で
あるヤシ殻、石炭等の天然物と比較して著しく純度が高
く、かつロット内、ロット間差が少なく安定したものを
得ることができる。Since the starting material used for producing the carbon material of the present invention is obtained by the above-mentioned production method, the purity is remarkably higher than that of the conventional carbon material raw materials such as coconut shell and coal. In addition, a stable product with little difference between lots and between lots can be obtained.
【００２２】本発明の炭素材は球状樹脂、またはこの樹
脂を非酸化性雰囲気下５００℃以上で熱処理した炭化物
を、７００〜１１００℃の温度範囲で炭化物を基準とし
た重量減少率が５〜７０％となる範囲で賦活処理を行う
ことにより目的の球状炭素材を得ることができる。この
球状炭素材は微粉化された炭素をバインダーと混合後、
転動造粒法で機械的に造粒成形した従来の球状炭素材と
呼ばれたものとは異なるものである。The carbon material of the present invention may be a spherical resin or a carbide obtained by heat-treating the resin at a temperature of 500 ° C. or more in a non-oxidizing atmosphere at a temperature range of 700 to 1100 ° C. with a weight reduction rate of 5 to 70 based on the carbide. %, The desired spherical carbon material can be obtained by performing the activation treatment. This spherical carbon material mixes finely divided carbon with a binder,
This is different from the conventional spherical carbon material mechanically granulated and formed by the tumbling granulation method.
【００２３】本発明の製造方法の賦活処理を行う前の炭
化は、電気炉、外熱式ガス炉などの熱処理装置を用いて
非酸化性雰囲気下５００〜９００℃で行われる。この場
合の非酸化性雰囲気とは、例えば、窒素、アルゴン、ヘ
リウム等の雰囲気である。また、この炭化温度は通常５
００〜９００℃であるが、好ましくは５５０〜８５０
℃、最も好ましくは６００〜８００℃である。炭化温度
が９００℃より高いと次の賦活処理工程での賦活速度が
遅くなり、賦活を効率的に進めることができなくなるの
で好ましくない。The carbonization before the activation treatment in the production method of the present invention is performed at 500 to 900 ° C. in a non-oxidizing atmosphere using a heat treatment apparatus such as an electric furnace or an externally heated gas furnace. The non-oxidizing atmosphere in this case is, for example, an atmosphere of nitrogen, argon, helium, or the like. The carbonization temperature is usually 5
00 to 900 ° C., preferably 550 to 850
° C, most preferably 600-800 ° C. If the carbonization temperature is higher than 900 ° C., the activation rate in the next activation treatment step becomes slow, and the activation cannot be efficiently advanced, which is not preferable.
【００２４】また炭化温度が５００℃以下の場合には温
度が低過ぎて炭化があまり進まず好ましくない。但し、
次の賦活時に、賦活処理する原料に対し、充分な熱容量
を有する炉に於いて、充分な雰囲気ガスの供給が可能で
あり、充分な排気ガスの処理能力を有する場合に於いて
は、この炭化行程を省略し、球状樹脂を直接賦活するこ
ともできる。When the carbonization temperature is 500 ° C. or lower, the temperature is too low and carbonization does not proceed very much, which is not preferable. However,
At the time of the next activation, in a furnace having a sufficient heat capacity with respect to the raw material to be activated, a sufficient atmosphere gas can be supplied, and in a case where the exhaust gas processing capacity is sufficient, the carbonization is performed. The step can be omitted, and the spherical resin can be directly activated.
【００２５】本発明の製造方法の賦活処理の温度領域は
７００〜１１００℃、好ましくは８００〜１０００℃、
最も好ましくは８５０〜９５０℃である。賦活処理の温
度が１１００℃より高い場合には、細孔直径１ｎｍ以上
の細孔が発達し、また炭素材表面が酸化し、低沸点有機
塩素化合物等の吸着容量及び、残留塩素の酸化還元反応
による分解の活性、または触媒的分解の活性が低下する
とともに、炭素材強度が低下するため好ましくない。The temperature range of the activation treatment in the production method of the present invention is 700 to 1100 ° C., preferably 800 to 1000 ° C.
Most preferably, it is 850-950 ° C. When the temperature of the activation treatment is higher than 1100 ° C., pores with a pore diameter of 1 nm or more develop, the surface of the carbon material is oxidized, the adsorption capacity of low-boiling organic chlorine compounds and the like, and the oxidation-reduction reaction of residual chlorine. This is not preferred because the decomposition activity or catalytic decomposition activity decreases and the carbon material strength decreases.
【００２６】また７００℃より低い場合には賦活が十分
に行われず、吸着能力が低く好ましくない。また、賦活
処理には、酸素、二酸化炭素、水蒸気もしくはこれらの
二種類以上の混合ガス、あるいはこれらのガスを含んだ
窒素、アルゴン、ヘリウム等の雰囲気ガス、メタン、プ
ロパン、ブタン等の燃焼排ガスなどを用いることがで
き、炭化物を基準とした重量減少率が５〜７０％となる
範囲で賦活を行う。On the other hand, when the temperature is lower than 700 ° C., the activation is not sufficiently performed, and the adsorption capacity is low, which is not preferable. In the activation treatment, oxygen, carbon dioxide, water vapor or a mixed gas of two or more of these, or an atmosphere gas containing these gases, such as nitrogen, argon, helium, or a combustion exhaust gas, such as methane, propane, butane, etc. Can be used, and the activation is performed in a range where the weight reduction rate based on the carbide is 5 to 70%.
【００２７】重量減少率が５％より小さい場合には細孔
の発達が不十分であり、細孔容積が小さすぎて十分な性
能を確保できず好ましくない。また、重量減少率が７０
％より大きい場合には低沸点有機塩素化合物等の吸着に
有効に働く細孔直径１ｎｍ以下の細孔の割合が小さくな
り、また粒子嵩密度が小さくなり、炭素材を充填した
際、有効に作用する吸着サイトの単位体積当たりの量が
減少し好ましくない。If the weight reduction ratio is less than 5%, the development of the pores is insufficient, and the pore volume is too small, so that sufficient performance cannot be secured, which is not preferable. In addition, the weight loss rate is 70
%, The proportion of pores having a pore diameter of 1 nm or less that effectively works for the adsorption of low-boiling organochlorine compounds and the like is reduced, and the particle bulk density is reduced. The amount of adsorption sites per unit volume decreases, which is not preferable.
【００２８】上記の如き本発明の製造方法により得られ
る、本発明の炭素材は、比表面積７００〜１６００ｍ2
／ｇ、細孔直径０．０１〜１０μｍの細孔容積が０．１
５ｃｃ／ｇ以下、細孔直径１０ｎｍ以下の細孔容積が
０．２０〜１．２０ｃｃ／ｇであり、かつ細孔直径１０
ｎｍ以下の細孔容積に占める細孔直径１ｎｍ以下の細孔
容積の割合が７８ｖｏｌ％以上、充填密度が０．５５〜
０．８０ｇ／ｃｃ、灰分量が０．５％以下、破砕強度が
４０ｋｇ／ｃｍ2 以上であることを特徴とする粒子直径
１５０〜２０００μｍの球状炭素材である。The carbon material of the present invention obtained by the production method of the present invention as described above has a specific surface area of 700 to 1600 m 2.
/ G, pore volume of pore diameter 0.01 to 10 μm is 0.1
A pore volume of 5 cc / g or less and a pore diameter of 10 nm or less is 0.20 to 1.20 cc / g, and a pore diameter of 10
The ratio of the pore volume having a pore diameter of 1 nm or less to the pore volume of not more than nm is 78 vol% or more, and the packing density is 0.55 to
A spherical carbon material having a particle diameter of 150 to 2000 μm, characterized by having a ash content of 0.80 g / cc, 0.5% or less, and a crushing strength of 40 kg / cm 2 or more.
【００２９】本発明の炭素材の比表面積は７００〜１６
００ｍ2 ／ｇ、好ましくは７５０〜１３００ｍ2 ／ｇ、
最も好ましくは８００〜１２００ｍ2 ／ｇである。比表
面積が７００ｍ2 ／ｇより小さい場合では、低沸点有機
塩素化合物等の吸着用サイトの量が少な過ぎて吸着容量
が低く好ましくない。さらに、比表面積が１６００ｍ2
／ｇ以上では低沸点有機塩素化合物等の吸着に有効に働
くと考えられる細孔直径１ｎｍ以下の細孔の割合が小さ
くなり好ましくない。The specific surface area of the carbon material of the present invention is 700 to 16
00 m 2 / g, preferably 750 to 1300 m 2 / g,
Most preferably, it is 800 to 1200 m 2 / g. If the specific surface area is less than 700 m 2 / g, the amount of adsorption sites for low-boiling organochlorine compounds and the like is too small, and the adsorption capacity is undesirably low. Furthermore, the specific surface area is 1600 m 2
/ G or more is not preferred because the ratio of pores having a pore diameter of 1 nm or less, which is considered to work effectively for the adsorption of low-boiling organic chlorine compounds and the like, becomes small.
【００３０】本発明の炭素材の細孔直径０．０１〜１０
μｍの細孔容積は０．１５ｃｃ／ｇ以下、好ましくは
０．１２ｃｃ／ｇ、最も好ましくは０．１ｃｃ／ｇ以下
である。細孔直径０．０１〜１０μｍの細孔容積が０．
１５ｃｃ／ｇより大きいと低沸点有機塩素化合物等以外
の、より分子量の大きい物質も吸着するため、系内に極
低濃度存在する低沸点有機塩素化合物等の吸着容量が低
下するとともに、カラム等に充填して用いる際の充填密
度及び粒子の機械的強度が小さくなり好ましくない。The carbon material of the present invention has a pore diameter of 0.01 to 10
The micrometer pore volume is 0.15 cc / g or less, preferably 0.12 cc / g, and most preferably 0.1 cc / g or less. The volume of pores having a pore diameter of 0.01 to 10 μm is 0.
If it is more than 15 cc / g, substances having a higher molecular weight other than the low-boiling-point organochlorine compounds and the like are also adsorbed. When used after filling, the packing density and the mechanical strength of the particles are undesirably reduced.
【００３１】本発明の炭素材の細孔直径１０ｎｍ以下の
細孔容積は０．２０〜１．２０ｃｃ／ｇ、好ましくは
０．４０〜１．１０ｃｃ／ｇ、最も好ましくは０．４０
〜１．００ｃｃ／ｇである。細孔直径１０ｎｍ以下の全
細孔容積が０．２０ｃｃ／ｇ以下だと、細孔直径１ｎｍ
以下の細孔容積も小さいため低沸点有機塩素化合物等の
吸着容量が低下するため好ましくない。細孔直径１０ｎ
ｍ以下の細孔容積が１．２０ｃｃ／ｇ以上であるとカラ
ム等に充填して用いる際の充填密度及び粒子の機械的強
度が小さくなり好ましくない。The pore volume of the carbon material of the present invention having a pore diameter of 10 nm or less is 0.20 to 1.20 cc / g, preferably 0.40 to 1.10 cc / g, and most preferably 0.40 cc / g.
~ 1.00 cc / g. If the total pore volume of pores having a pore diameter of 10 nm or less is 0.20 cc / g or less, the pore diameter is 1 nm.
Since the following pore volumes are also small, the adsorption capacity of low-boiling organic chlorine compounds and the like decreases, which is not preferable. Pore diameter 10n
When the pore volume of m or less is 1.20 cc / g or more, the packing density and the mechanical strength of the particles when packed into a column or the like are undesirably reduced.
【００３２】本発明の炭素材の細孔直径１０ｎｍ以下の
細孔容積に占める細孔直径１ｎｍ以下の細孔容積の割合
は７８Ｖｏｌ％以上、好ましくは８５ｖｏｌ％以上、最
も好ましくは９０ｖｏｌ％以上である。低沸点有機塩素
化合物等の低分子量物質の吸着に於いて、特に有効に作
用するのは細孔直径１ｎｍ以下の細孔と考えられるの
で、この細孔容積が細孔直径１０ｎｍ以下の細孔容積の
７８Ｖｏｌ％より小さいと低沸点有機塩素化合物等の吸
着容量が低下し、分子量のより大きい物質に対する吸着
量が増加し、これらの吸着による炭素材の破過が進行し
好ましくない。The ratio of the pore volume having a pore diameter of 1 nm or less to the pore volume having a pore diameter of 10 nm or less in the carbon material of the present invention is 78 vol% or more, preferably 85 vol% or more, and most preferably 90 vol% or more. . In the adsorption of low-molecular-weight substances such as low-boiling-point organochlorine compounds, it is considered that pores having a pore diameter of 1 nm or less are particularly effective. If it is less than 78% by volume, the adsorption capacity of low-boiling-point organochlorine compounds and the like decreases, the amount of adsorption to substances having a higher molecular weight increases, and breakage of the carbon material due to the adsorption proceeds undesirably.
【００３３】本発明の炭素材をカラム等の容器に充填し
て用いた際の充填密度は０．５５〜０．８０ｇ／ｃｃ、
好ましくは０．６０〜０．７５ｇ／ｃｃ、最も好ましく
は０．６２〜 ０．７２ｇ／ｃｃである。充填密度が小
さすぎると、単位容積当たりの吸着容量が低下し好まし
くない。また、大きすぎると炭素材の細孔容積が低下し
吸着能力の低下を来すので好ましくない。When the carbon material of the present invention is packed in a container such as a column and used, the packing density is 0.55 to 0.80 g / cc.
Preferably it is 0.60 to 0.75 g / cc, most preferably 0.62 to 0.72 g / cc. If the packing density is too low, the adsorption capacity per unit volume decreases, which is not preferable. On the other hand, if it is too large, the pore volume of the carbon material is reduced and the adsorption capacity is lowered, which is not preferable.
【００３４】本発明の炭素材の灰分量は０．５％以下、
好ましくは０．３０％、最も好しくは０．２％以下が良
い。灰分量が０．２％以下であると炭素材からの不純物
溶出量を低く抑えることができ、超純水製造装置、医薬
品等ファインケミカル分野に於ける不純物除去装置用吸
着材、人工臓器用吸着材、生体内の特定物質除去用吸着
剤等に好適に用いることができる。 灰分量が高いと、不
純物溶出濃度が高値を示すことが多く、使用前の炭素材
洗浄に要する労力が非常に大きくなってしまい好ましく
ない。The ash content of the carbon material of the present invention is 0.5% or less,
Preferably it is 0.30%, most preferably 0.2% or less. When the ash content is 0.2% or less, the amount of impurities eluted from the carbon material can be suppressed to a low level, and the adsorbent for the impurity removing device and the adsorbent for artificial organs in the ultrapure water production device, the fine chemical field such as pharmaceuticals, etc. It can be suitably used as an adsorbent for removing a specific substance in a living body. If the ash content is high, the impurity elution concentration often shows a high value, and the labor required for cleaning the carbon material before use is undesirably increased.
【００３５】核物質としてＳｉＣ、アルミナ等を用いて
製造した球状フェノール樹脂を原料として炭素材を得た
際には、炭素材中にこれら物質が残留するので、用途に
応じた核物質の選択が必要である。When a carbon material is obtained from a spherical phenol resin produced using SiC, alumina, or the like as a core material, these materials remain in the carbon material. is necessary.
【００３６】本発明の炭素材の強度は、４０ｋｇ／ｃｍ
2 以上、好ましくは４５ｋｇ／ｃｍ2 以上、最も好しく
は５０ｋｇ／ｃｍ2 以上が良い。強度が低いと、長期間
浄水器、超純水製造器用、空気清浄器用等に用いた場
合、炭素材の粉化が生じ炭素材自身の細孔の詰まり、後
段のフィルターの詰まり等が生じ好ましくない。The strength of the carbon material of the present invention is 40 kg / cm
2 or more, preferably 45 kg / cm 2 or more, and most preferably 50 kg / cm 2 or more. If the strength is low, when used for a long term for water purifiers, ultrapure water production equipment, air purifiers, etc., powdering of the carbon material occurs and clogging of the pores of the carbon material itself, clogging of the subsequent filter, etc. are preferable. Absent.
【００３７】本発明の炭素材の粒子直径は１５０〜２０
００μｍ、好ましくは、水系で使用する際には２００〜
８００μｍ、気相系で使用する際には５００〜２０００
μｍである。粒子直径が１５０μｍ以下であると、これ
をカラム等に充填して使用する際の充填時の操作性が低
下するとともに、これを保持するために、目開きの細か
い不織布、メッシュ等を使用するため水、空気等を通過
させて用いる際に微粒子の詰まり等が生じ圧力損失の上
昇を招きやすい。The carbon material of the present invention has a particle diameter of 150 to 20.
00 μm, preferably 200 to 200 μm when used in an aqueous system.
800 μm, 500-2000 when used in a gas phase system
μm. When the particle diameter is 150 μm or less, the operability at the time of packing when used in a column or the like is reduced, and in order to use the same, a nonwoven fabric with a fine opening, a mesh, or the like is used. When used by passing through water, air, or the like, clogging of fine particles or the like occurs, which tends to cause an increase in pressure loss.
【００３８】粒子直径が２０００μｍ以上であると、炭
素材が吸着及びまたは触媒作用を及ぼす特定成分との接
触サイトが減少するため、吸着及びまたは触媒作用の効
率が低下し好ましくない。If the particle diameter is 2000 μm or more, the number of sites at which the carbon material comes into contact with a specific component which exerts adsorption and / or catalysis is reduced, and the efficiency of adsorption and / or catalysis is undesirably reduced.
【００３９】[0039]
【発明の効果】本発明の方法で製造される、本発明の球
状炭素材は上記の如き物性上の特徴を有し、液相系及び
気相系に於いて存在する特定の物質に対し、吸着及びま
たは触媒作用を及ぼし、これら物質を効率よく除去また
は分解できると同時に、長期間浄水器、超純水製造装
置、空気清浄器、悪臭・有機溶剤等の分離・回収装置、
医薬品等ファインケミカル分野に於ける不純物除去用装
置等の吸着材または触媒または触媒担体として用いて
も、粉化による炭素材自身の細孔の詰まり、後段のフィ
ルターの詰まり等が生じにくい。さらに炭素材自身から
の不純物溶出も極めて少ないため、不純物溶出を極端に
避けねばならない超純水製造装置、人工臓器、医薬品等
ファインケミカル分野に於ける不純物除去用装置または
特定物質の分離・精製用装置、生体内の特定物質除去用
吸着剤等には好適に用いることができるものであるから
工業上極めて有用なものである。さらに、本発明の炭素
材は水中の残留塩素、オゾン、大気中の一酸化窒素等に
対し、触媒的に作用するが、白金、金、銀、チタン等の
金属及びまたは金属化合物を担時させる担体としての利
用にも適する。The spherical carbon material of the present invention produced by the method of the present invention has the above-mentioned physical characteristics, and is suitable for a specific substance existing in a liquid phase system and a gas phase system. It exerts adsorption and / or catalysis and can remove or decompose these substances efficiently, and at the same time, has a long-term water purifier, ultrapure water production equipment, air purifier, separation and recovery equipment for odor and organic solvents, etc.
Even when used as an adsorbent, a catalyst or a catalyst carrier for an impurity removing device in the field of fine chemicals such as pharmaceuticals, clogging of pores of the carbon material itself due to pulverization, clogging of a subsequent filter, and the like hardly occur. Furthermore, since the elution of impurities from the carbon material itself is extremely small, the elution of impurities must be extremely avoided.Ultra pure water production equipment, equipment for removing impurities or equipment for separating and purifying specific substances in the field of fine chemicals such as artificial organs and pharmaceuticals Since it can be suitably used as an adsorbent for removing a specific substance in a living body, it is industrially extremely useful. Further, the carbon material of the present invention acts catalytically on residual chlorine in water, ozone, nitric oxide in the atmosphere, etc., but causes metals such as platinum, gold, silver and titanium and / or metal compounds to be supported. Also suitable for use as a carrier.
【００４０】本発明の方法で製造される、本発明の球状
炭素材は前述の如き物性上の特徴を有し、例えば、水道
水中及び工場排水中の低濃度から高濃度に至るまでの低
分子量有機物除去用吸着材、残留塩素分解除去用触媒等
として用いることができる。特に、水道水中に極微量含
まれるトリハロメタン類を除去する浄水器、超純水製造
装置内に充填して用いることにより、大きな効果を発揮
することができる。The spherical carbon material of the present invention produced by the method of the present invention has the above-mentioned physical characteristics, for example, low molecular weight from low concentration to high concentration in tap water and industrial wastewater. It can be used as an adsorbent for removing organic substances, a catalyst for removing and removing residual chlorine, and the like. In particular, a great effect can be exhibited by filling and using a water purifier that removes a trace amount of trihalomethanes contained in tap water and an ultrapure water production device.
【００４１】本発明の球状炭素材が吸着する特定成分、
又は触媒作用を及ぼす特定成分は、残留塩素や、トリク
ロロメタン、ブロモジクロロメタン、ジブロモクロロメ
タン、トリブロモメタン等のトリハロメタン類、或はト
リクロロエタン、トリクロロエチレン、フロン、ジクロ
ロメタン、四塩化炭素等のハロゲン化炭化水素類、或は
トルエン、ベンゼン、キシレン、ｎ−ヘキサン、シクロ
ヘキサン等の炭化水素、或はアセトン、メチルエチルケ
トン等のケトン類、或はメタノール、エタノール等のア
ルコール類や各種有機溶剤、或はメチルメルカプタン、
硫化水素、二酸化硫黄、酢酸、アセトアルデヒド、ホル
ムアルデヒド、アンモニア、クレゾール等の悪臭原因物
質、或は二酸化窒素、一酸化窒素、オゾン等の有毒ガ
ス、或は蛋白質、糖類等、或は金、白金、コバルト、イ
ットリウム、ランタン等の金属錯体、又はコロイド等で
あり、或は上記物質の複合混合物である。A specific component to which the spherical carbon material of the present invention adsorbs,
Alternatively, the specific component that exerts a catalytic effect is residual chlorine, trichloromethane such as trichloromethane, bromodichloromethane, dibromochloromethane, or tribromomethane, or halogenated hydrocarbon such as trichloroethane, trichloroethylene, freon, dichloromethane, or carbon tetrachloride. Or hydrocarbons such as toluene, benzene, xylene, n-hexane, and cyclohexane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; and various organic solvents; and methyl mercaptan;
Odor-causing substances such as hydrogen sulfide, sulfur dioxide, acetic acid, acetaldehyde, formaldehyde, ammonia, and cresol; or toxic gases such as nitrogen dioxide, nitric oxide, and ozone; or proteins and sugars; or gold, platinum, and cobalt , Yttrium, lanthanum, or other metal complexes, or colloids, or a complex mixture of the above substances.
【００４２】これら特定成分は、水道水、家庭排水、工
業排水、河川、湖沼、海水、及び生体内体液の液相や、
大気、排気ガス等の気相に存在するものでもよい。These specific components include tap water, domestic wastewater, industrial wastewater, rivers, lakes and marshes, seawater, and the liquid phase of body fluids,
It may exist in the gas phase such as the atmosphere and exhaust gas.
【００４３】（測定評価法）次に、本発明に用いた測定
評価方法について以下に示す。(Measurement Evaluation Method) Next, the measurement evaluation method used in the present invention will be described below.
【００４４】（１）炭素材の比表面積の測定法 被測定炭素材０．１ｇ程度を正確に秤量した後、高精度
全自動ガス吸着装置ＢＥＬＳＯＲＰ２８（日本ベル株式
会社製）の専用セルに入れ、該装置を用いて窒素を吸着
させＢ．Ｅ．Ｔ法により求めた。(1) Method for measuring specific surface area of carbon material After accurately measuring about 0.1 g of the carbon material to be measured, it is placed in a dedicated cell of a high-precision fully automatic gas adsorption apparatus BELSORP28 (manufactured by Nippon Bell Co., Ltd.). Nitrogen was adsorbed using the apparatus and B. E. FIG. It was determined by the T method.
【００４５】（２） 細孔容積の測定法 本発明の吸着材の細孔容積の測定は、細孔直径０．０１
〜１０μｍ の範囲についてはポロシメ−タ−による水
銀圧入法（島津製作所製、ポアサイザ−９３１０）によ
り測定し、細孔直径１０ｎｍ以下の細孔容積は全自動ガ
ス吸着測定装置（日本ベル株式会社製、ベルソ−プ２
８）で窒素吸着測定を行った。具体的には、細孔直径２
〜１０ｎｍの範囲の細孔容積は７７Ｋに於ける窒素ガス
の吸着等温線をＤ−Ｈ解析することにより求め、細孔直
径２ｎｍ以下の細孔容積は７７Ｋに於ける窒素ガスの吸
着等温線のｔ−ｐｌｏｔからＭＰ法を用いて解析するこ
とにより求めた。(2) Method of Measuring Pore Volume The pore volume of the adsorbent of the present invention was measured using a pore diameter of 0.01.
The range of 10 μm to 10 μm is measured by a mercury intrusion method using a porosimeter (Poresizer-9310, manufactured by Shimadzu Corporation). Bell soap 2
The nitrogen adsorption measurement was performed in 8). Specifically, the pore diameter 2
The pore volume in the range of 10 nm to 10 nm was obtained by DH analysis of the adsorption isotherm of nitrogen gas at 77K, and the pore volume of pores having a diameter of 2 nm or less was determined by the adsorption isotherm of nitrogen gas at 77K. It was determined by analyzing from t-plot using the MP method.
【００４６】（３）灰分量 １０５℃で２時間乾燥した試料約１ｇｒを白金坩堝に精
秤し、７００℃、２時間灰化し、再度精秤して灰分量を
求めた。但し、金属担持触媒とするために金属及びまた
は金属化合物等を担持した場合、及び球状フェノール樹
脂を製造する際に添加した核物質のうち、前述の灰化に
より残留する成分を含む場合には、これらに由来する灰
分量を炭素材の灰分量の測定値から差し引いた値を、炭
素材の灰分量とした。(3) Ash Content About 1 gr of a sample dried at 105 ° C. for 2 hours was precisely weighed in a platinum crucible, incinerated at 700 ° C. for 2 hours, and again accurately weighed to determine the ash content. However, in the case of supporting a metal and / or a metal compound or the like to form a metal-supported catalyst, and in the case of including a component remaining due to the above-mentioned incineration among core materials added when manufacturing a spherical phenol resin, The value obtained by subtracting the ash content derived from these from the measured value of the ash content of the carbon material was defined as the ash content of the carbon material.
【００４７】（４）不純物含有濃度 １０５℃で２時間乾燥した試料約１ｇｒを白金坩堝に精
秤し、７００℃、２時間灰化したものに、フッ化水素酸
約１〜２ｍｌ添加してホットプレート上で加熱する。乾
固する手前で硝酸を加えて超純水で７〜８倍に希釈す
る。液量が１／３程度になったら再度超純水を加え、硝
酸を約１ｍｌ加え１時間加熱後、超純水を加え５０ｍｌ
に定量する。同様の操作でブランクを作製して、各試料
の測定結果を補正する。不純物の定量は、蛍光Ｘ線定性
分析で検出を確認した元素について、日立製作所（株）
製デュアルモノクロＩＣＰ発光分析装置Ｐ−５２００型
を用いたＩＣＰ発光分析により行った。(4) Concentration of impurity content About 1 gr of a sample dried at 105 ° C. for 2 hours was precisely weighed in a platinum crucible, and about 1 to 2 ml of hydrofluoric acid was added to the incinerated substance at 700 ° C. for 2 hours. Heat on plate. Before drying, add nitric acid and dilute 7-8 times with ultrapure water. When the liquid volume becomes about 1/3, add ultrapure water again, add about 1 ml of nitric acid, heat for 1 hour, add ultrapure water and add 50 ml
To be determined. A blank is prepared by the same operation, and the measurement result of each sample is corrected. Quantitative determination of impurities was performed for elements whose detection was confirmed by X-ray fluorescence qualitative analysis, using Hitachi, Ltd.
Was performed by ICP emission analysis using a dual monochrome ICP emission spectrometer Model P-5200 manufactured by Toshiba Corporation.
【００４８】（５） 破砕強度測定法 強度測定はＫＡＴＯ ＴＥＣＨ ＣＯ．ＬＴＤ社製圧縮
試験器（ＫＥＳ−ＦＢ３）にて測定した。強度測定で評
価する破砕強度は、炭素材の破砕時の荷重値と炭素材の
直径より、次式で計算した。 引張強度：σ［ｋｇ／ｃｍ2 ］＝ ２Ｐ／πｄ２ Ｐ： 荷重［ｋｇ］ ｄ：ペレット直径［ｃｍ］(5) Crushing strength measuring method The strength was measured by KATO TECH CO. It was measured with a compression tester (KES-FB3) manufactured by LTD. The crushing strength evaluated by the strength measurement was calculated from the load value at the time of crushing the carbon material and the diameter of the carbon material by the following formula. Tensile strength: σ [kg / cm 2 ] = 2P / πd2 P: load [kg] d: pellet diameter [cm]
【００４９】（６）低沸点有機塩素化合物吸着速度測定
法 トリハロメタン類の１つであるクロロホルムの４０００
ｐｐｂ水溶液４０ｍｌに、１００ｍｇの炭素材を添加
し、２５℃で振とうを行い、炭素材添加後１時間経過時
における溶液中のクロロホルム濃度をＥＣＤガスクロを
用いたヘッドスペース法で求め、１時間経過時のクロロ
ホルム除去量より各炭素材のクロロホルム吸着速度を求
め、炭素材１ｇ当たりに換算し、これを低沸点有機塩素
化合物の吸着速度とした。(6) Method for measuring adsorption rate of low-boiling organochlorine compounds Chloroform, which is one of trihalomethanes, is 4000
100 mg of a carbon material was added to 40 ml of an aqueous ppb solution, and the mixture was shaken at 25 ° C., and the concentration of chloroform in the solution at 1 hour after the addition of the carbon material was determined by a headspace method using an ECD gas chromatograph. The chloroform adsorption rate of each carbon material was determined from the amount of chloroform removed at the time, and converted to per 1 g of the carbon material, which was defined as the adsorption rate of the low boiling organic chlorine compound.
【００５０】（７）残留塩素分解速度測定法 ８ｐｐｍの次亜塩素酸水溶液４０ｍｌに炭素材１００ｍ
ｇを添加し、２５℃で振とうを行い、炭素材添加後１時
間経過時に該次亜塩素酸水溶液の一部を採水し、ＤＰＤ
試薬を加え発色させ、５５１ｎｍの吸光度を測定し、予
め求めた検量線より次亜塩素酸水溶液の濃度を求め、１
時間経過時の残留塩素分解量を各炭素材毎に求め、炭素
材１ｇ当たりに換算し、これを各炭素材の残留塩素分解
速度とした。(7) Residual chlorine decomposition rate measuring method A carbon material of 100 m was added to 40 ml of an 8 ppm aqueous solution of hypochlorous acid.
g, and shaken at 25 ° C., and one hour after the addition of the carbon material, a part of the aqueous hypochlorous acid solution was sampled.
The reagent was added to develop color, the absorbance at 551 nm was measured, and the concentration of the aqueous solution of hypochlorous acid was determined from a previously determined calibration curve.
The amount of residual chlorine decomposed over time was determined for each carbon material, converted to per gram of carbon material, and used as the residual chlorine decomposition rate of each carbon material.
【００５１】（８）耐磨耗強度 予め１００メッシュの篩で粉を除去した炭素材約７ｇを
精秤し、長さ１５ｃｍの試験管に入れ、孤動振とう器
（株式会社ヤヨイ社製ＹＳ−８Ｄ）のホルダーに試験管
を取り付け、振とう幅８ｃｍで３００ｒｐｍ、１時間振
とうする。振とう後、試験管内の試料を取り出し、再び
１００メッシュの篩を通し、発生した粉の量を精秤し、
炭素材の粉化率を求め耐磨耗強度とした。(8) Abrasion resistance About 7 g of carbon material from which powder was previously removed with a 100-mesh sieve was precisely weighed, placed in a test tube having a length of 15 cm, and placed on a rocking shaker (YS manufactured by Yayoi Co., Ltd.). Attach the test tube to the holder of (−8D) and shake at 300 rpm for 1 hour with a shaking width of 8 cm. After shaking, the sample in the test tube was taken out, passed through a 100-mesh sieve again, and the amount of generated powder was precisely weighed.
The powdering rate of the carbon material was determined and defined as abrasion resistance.
【００５２】（９）通水による圧力損失経時変化テスト 内径１ｃｍ、長さ５ｃｍのアクリル製の円筒に各炭素材
を充填し、両端を炭素材が漏れ出さない限りに於いて最
大限目開きの大きいポリエステル製不織布で抑え、その
周囲をアクリル円筒にしっかり固定し、炭素材充填カラ
ムを作製した。このカラムの通水口側の直前に圧力ゲー
ジを設け、流速１（Ｌ／分）での通水時に於ける、カラ
ムに発生する通水圧力を測定し、通水開始後１０時間後
の圧力を通水開始直後の圧力で除した値を１００倍して
パーセント表示し、圧力損失上昇率とした。(9) Time-dependent change test of pressure loss due to water flow An acrylic cylinder having an inner diameter of 1 cm and a length of 5 cm is filled with each carbon material, and the both ends are maximally opened as long as the carbon material does not leak. A large polyester nonwoven fabric was used, and the periphery was firmly fixed to an acrylic cylinder to produce a carbon material-filled column. A pressure gauge was provided immediately before the water flow port side of this column to measure the water flow pressure generated in the column at the time of flow at a flow rate of 1 (L / min), and the pressure 10 hours after the start of water flow was measured. The value divided by the pressure immediately after the start of water flow was multiplied by 100 and expressed as a percentage, and the resulting value was defined as the rate of increase in pressure loss.
【００５３】（１０）炭素材充填時の作業性評価試験 各炭素材２０ｇを空気清浄器用の炭素材保持用ポリエス
テル不織布２枚の間隙に、サンドイッチ状に充填する作
業を繰り返し、各炭素材充填不織布２０セットをそれぞ
れ準備するのに要する時間及び、作業終了後の周囲の汚
れの状態を観察し、炭素材充填時の作業性評価試験とし
た。(10) Workability evaluation test at the time of filling the carbon material The operation of filling 20 g of each carbon material in a gap between two pieces of the polyester nonwoven fabric for holding the carbon material for the air purifier in a sandwich manner was repeated, and each carbon material nonwoven fabric was filled. The time required to prepare each of the 20 sets and the state of dirt around the work after the completion of the work were observed, and the workability evaluation test at the time of filling the carbon material was performed.
【００５４】次に本発明を実施例によりさらに具体的に
説明するが、本発明は実施例により限定されるものでは
ない。Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.
【００５５】[0055]
実施例１ 〔球状炭素材の製造方法〕４０Ｌの反応溶液に、１８重
量％の塩酸と、９重量％のホルムアルデヒドからなる混
合水溶液を３０ｋｇ入れ、そのフラスコに、２８℃で撹
拌しながらフェノール／水＝９０／１０の水溶液１ｋｇ
を添加した。その後も暫く撹拌を継続すると、急激に白
濁した。白濁と同時に撹拌を停止しそのまま放置した。Example 1 [Production Method of Spherical Carbon Material] 30 kg of a mixed aqueous solution composed of 18% by weight of hydrochloric acid and 9% by weight of formaldehyde was placed in a 40 L reaction solution, and phenol / water was stirred in the flask at 28 ° C. = 1 kg of 90/10 aqueous solution
Was added. When stirring was continued for a while after that, it became cloudy rapidly. The stirring was stopped at the same time as the cloudiness, and the mixture was left as it was.
【００５６】内温が徐々に上昇し、ピンク色のスラリー
状の生成が認められた。次いで更に撹拌を続けながら８
０℃まで昇温し約２０分間撹拌を継続した。さらに内容
物を水洗後、０．２重量％のアンモニア水溶液中、６０
℃の温度で６０分間処理し、水洗後、２００℃の温度で
２時間乾燥し、０．１〜１５０μｍの球状フェノール樹
脂を得た。The internal temperature gradually increased, and formation of a pink slurry was observed. Then, with further stirring, 8
The temperature was raised to 0 ° C., and stirring was continued for about 20 minutes. Further, the contents were washed with water.
After treating at a temperature of 60 ° C. for 60 minutes, washing with water, and drying at a temperature of 200 ° C. for 2 hours, a spherical phenol resin of 0.1 to 150 μm was obtained.
【００５７】更にこの樹脂とフェノール及びアルデヒド
等を下記の比率で混合・撹拌した。球状フェノール樹脂
／フェノール／９２％ホルムアルデヒド／ヘキサメチレ
ンテトラミン／アラビアゴム／水＝５／１００／４０／
１０／１／１００。撹拌を継続しながら、約６０分で８
５℃まで昇温し、そのまま６０分反応を行い、希釈水を
投入し、内温が下がるまで冷却後、これを濾別した後、
乾燥し、含水率が２％以下になるまで乾燥を行い更に、
篩により１５０μｍ以下及び２０００μｍ以上の粒径の
樹脂を除去し、粒子直径１５０〜２０００μｍの真球状
フェノール樹脂を得た。Further, the resin, phenol, aldehyde and the like were mixed and stirred at the following ratio. Spherical phenolic resin / phenol / 92% formaldehyde / hexamethylenetetramine / gum arabic / water = 5/100/40 /
10/1/100. While stirring, 8 minutes in about 60 minutes.
The temperature was raised to 5 ° C., the reaction was carried out for 60 minutes, and dilution water was added. After cooling until the internal temperature was lowered, this was separated by filtration.
Dry and dry until the water content is 2% or less.
The resin having a particle diameter of 150 μm or less and 2000 μm or more was removed by a sieve to obtain a spherical phenol resin having a particle diameter of 150 to 2000 μm.
【００５８】更に、この樹脂を６００℃で３時間、窒素
気流中で炭化し、その炭化物を、８５０℃、９００℃及
び９５０℃で６時間、水蒸気を飽和した窒素気流中で賦
活し、賦活程度を示す重量減少率がそれぞれ２３％、３
０％、４４％の真球状炭素材試料１、試料２、試料３を
得た。Further, this resin is carbonized at 600 ° C. for 3 hours in a nitrogen gas stream, and the carbide is activated at 850 ° C., 900 ° C. and 950 ° C. for 6 hours in a nitrogen gas stream saturated with water vapor. Are 23% and 3%, respectively.
0% and 44% spherical carbon material samples 1, 2, and 3 were obtained.
【００５９】比較例１ 比較例として、従来より行われている球状炭素材の製造
方法である転動造粒法により、球状炭素材を作製した。
その方法は、熱硬化性フェノール樹脂／熱溶融性フェノ
ール樹脂／結晶性セルロース／１０％ポリビニルアルコ
ール水溶液＝４／３／２／１の割合で混合した組成物１
０ｋｇを公転１５ＲＰＭ、自転３０ＲＰＭで１０ｍｉｎ
混練（品川式万能撹拌器（株）ダルトン社製）後、深江
工業株式会社製ハイスピードミキサーＦＳ−ＧＳ−１０
Ｊでアジテーター回転数３００ｒｐｍ、チョッパー回転
数３６００ｒｐｍで１０分間転動造粒して粒子直径１５
０〜２０００μｍの球状フェノール樹脂を得た後、この
球状樹脂を６００℃で３時間、窒素気流中で炭化し、そ
の炭化物を、９５０℃で水蒸気を飽和した窒素気流中で
６時間賦活することにより行った。賦活時の重量減少率
は５４％の炭素材試料４を得、比較例とした。また、同
程度の粒子直径を有する市販浄水用ヤシ殻破砕状炭素材
を試料５、および試料６とした（表１参照）。Comparative Example 1 As a comparative example, a spherical carbon material was produced by a rolling granulation method which is a conventional method for producing a spherical carbon material.
The method is as follows: composition 1 in which thermosetting phenolic resin / hot-melting phenolic resin / crystalline cellulose / 10% aqueous polyvinyl alcohol solution is mixed at a ratio of 4/3/2/1.
0kg 10 min at 15 RPM and 30 RPM
After kneading (Shinagawa Universal Stirrer Co., Ltd. Dalton Co., Ltd.), high speed mixer FS-GS-10 manufactured by Fukae Kogyo Co., Ltd.
Rolling granulation for 10 minutes at an agitator rotation speed of 300 rpm and a chopper rotation speed of 3600 rpm at J
After obtaining a spherical phenol resin of 0 to 2000 μm, the spherical resin is carbonized at 600 ° C. for 3 hours in a nitrogen stream, and the carbide is activated for 6 hours in a nitrogen stream saturated with steam at 950 ° C. went. A carbon material sample 4 having a weight reduction rate of 54% at the time of activation was obtained and used as a comparative example. In addition, commercially available crushed coconut shell carbonaceous materials for water purification having the same particle diameter were used as Sample 5 and Sample 6 (see Table 1).
【００６０】熱硬化性フェノール樹脂は鐘紡株式会社製
ベルパールＲ８００、熱溶融性フェノール樹脂は鐘紡株
式会社製ベルパールＳ８９０、結晶性セルロースは旭化
成社製ＴＧ−１０１を用いた。The thermosetting phenolic resin used was Bellpearl R800 manufactured by Kanebo Co., Ltd., the thermofusible phenolic resin used was Bellpearl S890 manufactured by Kanebo Co., Ltd., and the crystalline cellulose was TG-101 manufactured by Asahi Kasei Corporation.
【００６１】製造例で得られた炭素材の特性値と市販の
浄水用炭素材の特性値を表１に示す。試料１〜３はいず
れの特性値も本発明の規定する範囲内となっている。転
動造粒で製造した試料４の球状炭素材及び、市販の浄水
用炭素材である試料５及び６は、何れも７００ｍ2 ／ｇ
以上の比表面積を有しているが、細孔直径０．０１〜１
０μｍの細孔容積（ｃｃ／ｇ）または細孔直径１０ｎｍ
以下の細孔容積（ｃｃ／ｇ）または細孔直径１０ｎｍ以
下の細孔容積と細孔直径１ｎｍ以下の細孔容積の割合等
に於いて本発明に規定する範囲を満たしていない点があ
る。Table 1 shows the characteristic values of the carbon material obtained in the production examples and the characteristic values of the commercially available carbon material for water purification. Samples 1 to 3 all have characteristic values within the range specified by the present invention. The spherical carbon material of Sample 4 manufactured by tumbling granulation and Samples 5 and 6, which are commercially available carbon materials for water purification, each had 700 m 2 / g.
Although having the above specific surface area, the pore diameter is 0.01 to 1
0 μm pore volume (cc / g) or pore diameter 10 nm
The following pore volume (cc / g) or the ratio of the pore volume with a pore diameter of 10 nm or less to the pore volume with a pore diameter of 1 nm or less does not satisfy the range specified in the present invention.
【００６２】[0062]
【表１】 [Table 1]
【００６３】実施例２ 実施例１で使用したと同様の試料１〜６について、不純
物含有量の測定を行った。その結果を表２に示すが、試
料１〜３の灰分量は本発明の規定する範囲内であり、測
定した金属類の含有量も、バイダーを添加して製造した
試料４及びヤシ殻を原料とした市販の浄水用炭素材であ
る試料５及び６に比較して低値である。Example 2 The same sample 1 to 6 as used in Example 1 was subjected to measurement of the impurity content. The results are shown in Table 2. The ash content of Samples 1 to 3 was within the range specified in the present invention, and the measured metal content was the same as that of Sample 4 and coconut shell produced by adding a binder. The values are lower than those of samples 5 and 6, which are commercially available carbon materials for water purification.
【００６４】[0064]
【表２】 [Table 2]
【００６５】[0065]
【実施例３】実施例１で使用したと同様の試料１〜６に
ついて低沸点有機塩素化合物吸着速度の評価を行った。
その結果を表３に示すが、本発明の試料１〜３はいずれ
も比較例の試料４〜６に比べ低沸点有機塩素化合物吸着
速度が高値を示すが、その中でも特に試料３は低沸点有
機塩素化合物吸着速度が特に大きくなっている。Example 3 Samples 1 to 6 similar to those used in Example 1 were evaluated for the adsorption rate of low-boiling organochlorine compounds.
The results are shown in Table 3. Samples 1 to 3 of the present invention exhibit higher adsorption rates of low-boiling organochlorine compounds than Samples 4 to 6 of Comparative Examples. The chlorine compound adsorption rate is particularly large.
【００６６】[0066]
【表３】 [Table 3]
【００６７】[0067]
【実施例４】実施例１で使用したと同様の試料１〜６に
ついて、残留塩素分解速度の測定を行った。その結果を
表３に示すが、炭素材の特性が本発明に規定する範囲内
である試料１〜３は、残留塩素分解速度が、試料４〜６
に比較して高値である。Example 4 For the same samples 1 to 6 used in Example 1, the residual chlorine decomposition rate was measured. The results are shown in Table 3. Samples 1 to 3 in which the properties of the carbon material are within the range specified in the present invention have residual chlorine decomposition rates of Samples 4 to 6
Is higher than that of.
【００６８】[0068]
【表４】 [Table 4]
【００６９】[0069]
【実施例５】実施例１で使用したと同様の本発明の試料
１〜３及び比較例の試料４に加え、さらに市販のピッチ
系で粒子径５００〜６００μｍの球状炭素材である試料
７について、破砕強度及び耐磨耗性の評価を行った。そ
の結果を表５に示すが、試料１〜３の破砕強度は本発明
の規定する範囲内であり転動造粒品、ピッチ系球状品に
比較して高値を示す。更に耐磨耗性も試料１〜３は比較
例に比較して高値を示す。Example 5 In addition to Samples 1 to 3 of the present invention similar to that used in Example 1 and Sample 4 of Comparative Example, a sample 7 which is a commercially available pitch-based spherical carbon material having a particle diameter of 500 to 600 μm was prepared. , Crushing strength and abrasion resistance were evaluated. The results are shown in Table 5, and the crushing strength of Samples 1 to 3 is within the range specified by the present invention, and shows a higher value than rolling granules and pitch-based spherical products. Further, the abrasion resistance of Samples 1 to 3 is higher than that of Comparative Example.
【００７０】[0070]
【表５】 [Table 5]
【００７１】[0071]
【実施例６】比較例として、実施例１で核物質として使
用するために製造した、粒子直径０．１〜１５０μｍの
球状フェノール樹脂を６００℃で３時間、窒素気流中で
炭化し、その炭化物を、９５０℃で水蒸気を飽和した窒
素気流中で６時間賦活することにより重量減少率５０％
で、粒子直径０．１〜１５０μｍの球状炭素材を得た。
この球状炭素材の比表面積は１５５０ｍ2 ／ｇであり、
これを試料８とした。Example 6 As a comparative example, a spherical phenolic resin having a particle diameter of 0.1 to 150 μm produced for use as a core material in Example 1 was carbonized at 600 ° C. for 3 hours in a nitrogen stream, and the carbonized product was obtained. Is activated in a nitrogen stream saturated with steam at 950 ° C. for 6 hours to reduce the weight by 50%.
Thus, a spherical carbon material having a particle diameter of 0.1 to 150 μm was obtained.
The specific surface area of this spherical carbon material is 1550 m 2 / g,
This was designated as Sample 8.
【００７２】実施例１で使用したと同様の試料１〜３及
び試料８を用いて、通水による圧力損失経時変化テスト
を行った。その結果を表６に示すが、本発明の球状炭素
材である試料１〜３は１０時間経過後も圧力損失の上昇
は低値であったが、試料８は著しく圧力損失の上昇が認
められた。Using the same samples 1 to 3 and sample 8 as used in Example 1, a time-dependent change test of pressure loss due to passing water was performed. The results are shown in Table 6. As is apparent from Table 6, the increase in pressure loss was low even after 10 hours in Samples 1 to 3, which are the spherical carbon materials of the present invention, but in Sample 8, a significant increase in pressure loss was observed. Was.
【００７３】[0073]
【表６】 [Table 6]
【００７４】[0074]
【実施例７】実施例６で使用したと同様の試料１〜３及
び８について、炭素材充填時の作業性評価試験を行っ
た。その結果を表７に示すが、本発明の球状炭素材であ
る試料１〜３は周囲に飛散することもなく、短時間に充
填を行えたが試料８は充填により長時間を要したにも関
わらず、その炭素材が広範囲の床面に飛散し、周囲環境
への汚染が認められた。Example 7 Samples 1 to 3 and 8 similar to those used in Example 6 were subjected to a workability evaluation test at the time of filling a carbon material. The results are shown in Table 7. Samples 1 to 3, which are spherical carbon materials of the present invention, could be filled in a short time without being scattered around, but Sample 8 required a long time for filling. Regardless, the carbon material scattered over a wide range of floors, and contamination of the surrounding environment was observed.
【００７５】[0075]
【表７】 [Table 7]
Claims (5)
直径０．０１〜１０μｍの細孔容積が０．１５ｃｃ／ｇ
以下、細孔直径１０ｎｍ以下の細孔容積が０．２０〜
１．２０ｃｃ／ｇであり、かつ細孔直径１０ｎｍ以下の
細孔容積に占める細孔直径１ｎｍ以下の細孔容積の割合
が７８ｖｏｌ％以上であり、充填密度が０．５５〜０．
８０ｇ／ｃｃ、破砕強度が４０ｋｇ／ｃｍ2 以上である
粒子直径１５０〜２０００μｍの球状炭素材。1. A pore having a specific surface area of 700 to 1600 m 2 / g and a pore diameter of 0.01 to 10 μm having a pore volume of 0.15 cc / g.
Hereinafter, the pore volume of pore diameter 10 nm or less is 0.20 to 0.20.
1. The proportion of the pore volume having a pore diameter of 1 nm or less to the pore volume having a pore diameter of 10 nm or less is 78 vol% or more, and the packing density is 0.55 to 0.
A spherical carbon material having a particle diameter of 150 to 2000 μm and a crushing strength of 80 g / cc and a crushing strength of 40 kg / cm 2 or more.
囲第１項記載の球状炭素材。2. The spherical carbon material according to claim 1, wherein the ash content is 0.5% or less.
脂、またはこの樹脂を非酸化性雰囲気下５００℃以上で
炭化して得た球状炭化物を、７００〜１１００℃の温度
範囲で、樹脂または炭化物を基準とする重量減少率が５
〜７０％となる範囲で賦活することを特徴とする特許請
求の範囲第１項または第２項項記載の球状炭素材の製造
方法。3. A spherical resin having a particle diameter of 150 to 2000 μm or a spherical carbide obtained by carbonizing the resin at a temperature of 500 ° C. or higher in a non-oxidizing atmosphere at a temperature of 700 to 1100 ° C., based on the resin or carbide. Weight loss rate is 5
3. The method for producing a spherical carbon material according to claim 1, wherein the activation is performed within a range of about 70%.
ことができる特許請求の範囲第１項または第２項記載の
球状炭素材4. The spherical carbon material according to claim 1 or 2, which is capable of adsorbing a specific component in a gas phase or a liquid phase.
作用を及ぼす特許請求の範囲第１項または第２項記載の
球状炭素材5. The spherical carbon material according to claim 1, which has a catalytic action on a specific component in a gas phase or a liquid phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01817998A JP3390649B2 (en) | 1997-06-02 | 1998-01-12 | Spherical carbon material and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-160566 | 1997-06-02 | ||
| JP16056697 | 1997-06-02 | ||
| JP01817998A JP3390649B2 (en) | 1997-06-02 | 1998-01-12 | Spherical carbon material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1149503A true JPH1149503A (en) | 1999-02-23 |
| JP3390649B2 JP3390649B2 (en) | 2003-03-24 |
Family
ID=26354825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01817998A Expired - Fee Related JP3390649B2 (en) | 1997-06-02 | 1998-01-12 | Spherical carbon material and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3390649B2 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006247527A (en) * | 2005-03-10 | 2006-09-21 | Kansai Coke & Chem Co Ltd | Adsorbent |
| JP2007039289A (en) * | 2005-08-04 | 2007-02-15 | Toda Kogyo Corp | Spherical porous carbon particle powder and method for producing the same |
| JP2007223877A (en) * | 2006-02-27 | 2007-09-06 | Showa Denko Kk | Method for producing high-purity titanium tetrachloride and high-purity titanium tetrachloride obtainable thereby |
| JP2008100883A (en) * | 2006-10-20 | 2008-05-01 | Sumitomo Chemical Co Ltd | Amorphous carbon powder and its production method |
| JP2008535754A (en) * | 2005-03-29 | 2008-09-04 | ブリティッシュ アメリカン タバコ （インヴェストメンツ） リミテッド | Porous carbon material and smoking article and smoke filter containing the material |
| WO2010008072A1 (en) * | 2008-07-18 | 2010-01-21 | 株式会社クレハ | Treating agent for oxidizing agent-containing waste water, method for treating oxidizing agent-containing waste water, apparatus for treating oxidizing agent-containing waste water, purifying agent for organic solvent, method for purifying organic solvent, and apparatus for purifying organic solvent |
| US7651974B2 (en) | 2002-11-01 | 2010-01-26 | Kureha Chemical Industry Co., Ltd. | Adsorbent for oral administration |
| JP2010195641A (en) * | 2009-02-26 | 2010-09-09 | Teijin Chem Ltd | Method for producing carbonyl chloride and method for producing polycarbonate resin using the same as raw material |
| US20100248041A1 (en) * | 2007-10-30 | 2010-09-30 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery, electrode and carbonaceous material |
| JP2010269225A (en) * | 2009-05-20 | 2010-12-02 | Kuraray Chem Corp | Anion adsorbent molding and water purifier using the same |
| JP2011084454A (en) * | 2009-10-15 | 2011-04-28 | Chan Sieh Enterprises Co Ltd | Spherical activated carbon and method for producing the same |
| US8357366B2 (en) | 2004-04-02 | 2013-01-22 | Kureha Corporation | Adsorbent for an oral administration, and agent for treating or preventing renal or liver disease |
| US8440228B2 (en) | 2004-04-02 | 2013-05-14 | Kureha Corporation | Adsorbent for an oral administration, and agent for treating or preventing renal or liver disease |
| WO2014175098A1 (en) * | 2013-04-25 | 2014-10-30 | 日産自動車株式会社 | Catalyst, electrode catalyst layer using said catalyst, membrane electrode assembly, and fuel cell |
| US8920796B2 (en) | 2003-10-22 | 2014-12-30 | Kureha Corporation | Adsorbent for oral administration, and agent for treating or preventing renal or liver disease |
| KR20180054614A (en) * | 2015-09-16 | 2018-05-24 | 나노메이커스 | Method for producing a polymer-based material |
| WO2019244905A1 (en) * | 2018-06-19 | 2019-12-26 | 株式会社アドール | Activated carbon |
| JP6683968B1 (en) * | 2018-06-19 | 2020-04-22 | 株式会社アドール | Activated carbon |
| CN111511466A (en) * | 2017-12-28 | 2020-08-07 | 株式会社可乐丽 | Adsorption filter |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6757705B2 (en) * | 2016-09-14 | 2020-09-23 | 関西熱化学株式会社 | Spherical phenolic resin activated carbon for methane storage, its production method, methane storage material using the activated carbon, and methane storage method using the activated carbon. |
-
1998
- 1998-01-12 JP JP01817998A patent/JP3390649B2/en not_active Expired - Fee Related
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7651974B2 (en) | 2002-11-01 | 2010-01-26 | Kureha Chemical Industry Co., Ltd. | Adsorbent for oral administration |
| US8309130B2 (en) | 2002-11-01 | 2012-11-13 | Kureha Corporation | Adsorbent for oral administration |
| US8920796B2 (en) | 2003-10-22 | 2014-12-30 | Kureha Corporation | Adsorbent for oral administration, and agent for treating or preventing renal or liver disease |
| US8357366B2 (en) | 2004-04-02 | 2013-01-22 | Kureha Corporation | Adsorbent for an oral administration, and agent for treating or preventing renal or liver disease |
| US8518447B2 (en) | 2004-04-02 | 2013-08-27 | Kureha Corporation | Method for treating or preventing renal or liver disease |
| US8865161B2 (en) | 2004-04-02 | 2014-10-21 | Kureha Corporation | Adsorbent for an oral administration, and agent for treating or preventing renal or liver disease |
| US8440228B2 (en) | 2004-04-02 | 2013-05-14 | Kureha Corporation | Adsorbent for an oral administration, and agent for treating or preventing renal or liver disease |
| JP2006247527A (en) * | 2005-03-10 | 2006-09-21 | Kansai Coke & Chem Co Ltd | Adsorbent |
| JP2008535754A (en) * | 2005-03-29 | 2008-09-04 | ブリティッシュ アメリカン タバコ （インヴェストメンツ） リミテッド | Porous carbon material and smoking article and smoke filter containing the material |
| JP2007039289A (en) * | 2005-08-04 | 2007-02-15 | Toda Kogyo Corp | Spherical porous carbon particle powder and method for producing the same |
| JP2007223877A (en) * | 2006-02-27 | 2007-09-06 | Showa Denko Kk | Method for producing high-purity titanium tetrachloride and high-purity titanium tetrachloride obtainable thereby |
| JP2008100883A (en) * | 2006-10-20 | 2008-05-01 | Sumitomo Chemical Co Ltd | Amorphous carbon powder and its production method |
| US20100248041A1 (en) * | 2007-10-30 | 2010-09-30 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery, electrode and carbonaceous material |
| WO2010008072A1 (en) * | 2008-07-18 | 2010-01-21 | 株式会社クレハ | Treating agent for oxidizing agent-containing waste water, method for treating oxidizing agent-containing waste water, apparatus for treating oxidizing agent-containing waste water, purifying agent for organic solvent, method for purifying organic solvent, and apparatus for purifying organic solvent |
| JP5629578B2 (en) * | 2008-07-18 | 2014-11-19 | 株式会社クレハ | Oxidant-containing wastewater treatment agent, oxidant-containing wastewater treatment method, oxidant-containing wastewater treatment device, organic solvent purification agent, organic solvent purification method, and organic solvent purification device |
| JP2010195641A (en) * | 2009-02-26 | 2010-09-09 | Teijin Chem Ltd | Method for producing carbonyl chloride and method for producing polycarbonate resin using the same as raw material |
| JP2010269225A (en) * | 2009-05-20 | 2010-12-02 | Kuraray Chem Corp | Anion adsorbent molding and water purifier using the same |
| JP2011084454A (en) * | 2009-10-15 | 2011-04-28 | Chan Sieh Enterprises Co Ltd | Spherical activated carbon and method for producing the same |
| WO2014175098A1 (en) * | 2013-04-25 | 2014-10-30 | 日産自動車株式会社 | Catalyst, electrode catalyst layer using said catalyst, membrane electrode assembly, and fuel cell |
| JPWO2014175098A1 (en) * | 2013-04-25 | 2017-02-23 | 日産自動車株式会社 | ELECTRODE CATALYST FOR FUEL CELL AND ELECTRODE CATALYST LAYER, MEMBRANE ELECTRODE ASSEMBLY AND FUEL CELL |
| KR20180054614A (en) * | 2015-09-16 | 2018-05-24 | 나노메이커스 | Method for producing a polymer-based material |
| CN111511466A (en) * | 2017-12-28 | 2020-08-07 | 株式会社可乐丽 | Adsorption filter |
| CN111511466B (en) * | 2017-12-28 | 2022-06-24 | 株式会社可乐丽 | Adsorption filter |
| WO2019244905A1 (en) * | 2018-06-19 | 2019-12-26 | 株式会社アドール | Activated carbon |
| JP6683968B1 (en) * | 2018-06-19 | 2020-04-22 | 株式会社アドール | Activated carbon |
| JPWO2019244905A1 (en) * | 2018-06-19 | 2020-06-25 | 株式会社アドール | Activated carbon |
| JP2020110801A (en) * | 2018-06-19 | 2020-07-27 | 株式会社アドール | Activated carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3390649B2 (en) | 2003-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3390649B2 (en) | Spherical carbon material and method for producing the same | |
| Martini et al. | Methyl orange and tartrazine yellow adsorption on activated carbon prepared from boiler residue: Kinetics, isotherms, thermodynamics studies and material characterization | |
| Zhang et al. | CuFe2O4/activated carbon composite: a novel magnetic adsorbent for the removal of acid orange II and catalytic regeneration | |
| Alhamed | Adsorption kinetics and performance of packed bed adsorber for phenol removal using activated carbon from dates’ stones | |
| EP0794240B1 (en) | Mercury adsorbent | |
| US7241430B2 (en) | Activated carbon for odor control and method for making same | |
| Mittal et al. | Batch and bulk adsorptive removal of anionic dye using metal/halide-free ordered mesoporous carbon as adsorbent | |
| Pradhan | Production and characterization of activated carbon produced from a suitable industrial sludge | |
| JPH03213144A (en) | Novel product and method for removing mercury from liquid hydrocarbon and use thereof | |
| CN105164766A (en) | Carbon bodies and ferromagnetic carbon bodies | |
| Barman et al. | Biochar from waste Sterculia foetida and its application as adsorbent for the treatment of PAH compounds: Batch and optimization | |
| JP2015529560A (en) | Filter media containing nitrogen and sulfur | |
| Chaghaganooj et al. | Ce and Mn/bio-waste-based activated carbon composite: Characterization, phenol adsorption and regeneration | |
| Hashemian | MnFe2O4/bentonite nano composite as a novel magnetic material for adsorption of acid red 138 | |
| Darweesh et al. | A unique, inexpensive, and abundantly available adsorbent: Composite of synthesized silver nanoparticles (AgNPs) and banana leaves powder (BLP) | |
| Kouotou et al. | Removal of metallic trace elements (Pb 2+, Cd 2+, Cu 2+, and Ni 2+) from aqueous solution by adsorption onto cerium oxide modified activated carbon | |
| Li et al. | Removal of heavy metals from aqueous solution by carbon nanotubes: adsorption equilibrium and kinetics | |
| Singh et al. | Fly ash and TiO2 modified fly ash as adsorbing materials for removal of Cd (II) and Pb (II) from aqueous solutions | |
| Piania et al. | Trihalomethanes (THMs) removal from aqueous solutions using environmental friendly and effective adsorbent onto Mespilus germanica modified by Fe | |
| Suresh et al. | Adsorption of arsenic in aqueous solution onto iron impregnated bagasse fly ash | |
| Inayat et al. | Review of recent progress in wastewater treatment using carbon nanotubes | |
| Chang et al. | Investigations of solvent-regenerable carbon-sulfur surface compounds for phenol removal in a packed column | |
| Khan et al. | Synthesis of monolith silica anchored graphene oxide composite with enhanced adsorption capacities for carbofuran and imidacloprid | |
| Shafiq et al. | Lead and copper scavenging from aqueous solutions using Eucalyptus camaldulensis derived activated carbon: Equilibrium, kinetics and sorption mechanism | |
| JP3578259B2 (en) | Decomposition and removal of formaldehyde in air |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090117 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090117 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100117 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110117 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110117 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120117 Year of fee payment: 9 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120117 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120117 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130117 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130117 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140117 Year of fee payment: 11 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |