JP2016104464A - Adsorptive removal filter and adsorptive removal method - Google Patents
Adsorptive removal filter and adsorptive removal method Download PDFInfo
- Publication number
- JP2016104464A JP2016104464A JP2014242715A JP2014242715A JP2016104464A JP 2016104464 A JP2016104464 A JP 2016104464A JP 2014242715 A JP2014242715 A JP 2014242715A JP 2014242715 A JP2014242715 A JP 2014242715A JP 2016104464 A JP2016104464 A JP 2016104464A
- Authority
- JP
- Japan
- Prior art keywords
- adsorption
- filter
- aqueous solution
- fullerene
- aromatic hydrocarbons
- 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
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000000274 adsorptive effect Effects 0.000 title abstract 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 171
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 73
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 48
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 239000012528 membrane Substances 0.000 abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 75
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 52
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 46
- 239000005711 Benzoic acid Substances 0.000 description 28
- 235000010233 benzoic acid Nutrition 0.000 description 28
- 238000002474 experimental method Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 11
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052903 pyrophyllite Inorganic materials 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 4
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 2
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
- -1 C60 saturated toluene Chemical class 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- DHKVCYCWBUNNQH-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,5,7-tetrahydropyrazolo[3,4-c]pyridin-6-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)C=NN2 DHKVCYCWBUNNQH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000026350 Inborn Genetic disease Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- SQISUZWPWJHTEP-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1.NC1=CC=CC=C1 SQISUZWPWJHTEP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 208000016361 genetic disease Diseases 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
本発明は、吸着除去フィルター及び吸着除去方法に関する。 The present invention relates to an adsorption removal filter and an adsorption removal method.
芳香族炭化水素や多環式芳香族炭化水素は、有機物の不完全燃焼によって容易く作られる。芳香族炭化水素や多環式芳香族炭化水素は一般に嫌水性であるが、少量であれば水に溶ける。芳香族炭化水素や多環式芳香族炭化水素が河川水や飲料水に溶解した場合、人間が摂取し、体内に取り込むおそれが生じる。体内に取り込まれると、遺伝的疾患を引き起こすおそれが生じる。芳香族炭化水素や多環式芳香族炭化水素は人体にとって有害な物質である。 Aromatic hydrocarbons and polycyclic aromatic hydrocarbons are easily produced by incomplete combustion of organic matter. Aromatic hydrocarbons and polycyclic aromatic hydrocarbons are generally hydrophilic, but are soluble in water in small amounts. When aromatic hydrocarbons or polycyclic aromatic hydrocarbons are dissolved in river water or drinking water, humans may ingest them and take them into the body. When taken into the body, it can cause genetic disorders. Aromatic hydrocarbons and polycyclic aromatic hydrocarbons are harmful to the human body.
現在の河川水や飲料水の濾過プラントは、沈殿濾過法なので、陽イオン性の有機物で沈殿する物もあるが、芳香族炭化水素や多環式芳香族炭化水素の多くは通り抜け、芳香族炭化水素や多環式芳香族炭化水素を完全に取り除くことはできていない。一部の地域では、オゾン処理や紫外線処理のシステムで有機物を分解しているが、このようなシステムを今まである浄水場に付加するのは高価になるという課題がある。低価で導入でき、水中の芳香族炭化水素を容易に吸着除去する方法及び装置が求められている。 Current river water and drinking water filtration plants are precipitation filtration methods, and some of them are precipitated with cationic organic matter. Hydrogen and polycyclic aromatic hydrocarbons cannot be completely removed. In some areas, organic matter is decomposed by ozone treatment or ultraviolet treatment systems, but adding such a system to a conventional water treatment plant is expensive. There is a need for a method and apparatus that can be introduced at a low price and can easily adsorb and remove aromatic hydrocarbons in water.
非特許文献１は、“Ａｄｓｏｒｐｔｉｏｎ ｏｆ ｓｏｍｅ ａｒｏｍａｔｉｃ ｃｏｍｐｏｕｎｄｓ ｂｙ ａ ｓｙｎｔｈｅｔｉｃ ｍｅｓｏｐｏｒｏｕｓ ｓｉｌｉｃａｔｅ”に関する。ＦＳＭ−１６を用いたベンゼンやトルエン、フェノール、安息香酸の吸着実験が開示されている。 Non-Patent Document 1 relates to “Adsorption of some aromatic compounds by a synthetic mesoporous silicate”. An adsorption experiment of benzene, toluene, phenol and benzoic acid using FSM-16 is disclosed.
非特許文献２は、“Ｒｅｍｏｖａｌ ｏｆ ｓｏｍｅ ａｒｏｍａｔｉｃ ｈｙｄｒｏｃａｒｂｏｎｓ ｆｒｏｍ ｗａｔｅｒ ｂｙ ｐｙｒｏｐｈｙｌｌｉｔｅ”に関する。パイロフィライトの芳香族炭化水素の吸着除去剤としての利用を研究した論文である。 Non-Patent Document 2 relates to “Removal of some aromatic hydrocarbons from water by pyrophyllite”. This paper studies the use of pyrophyllite as an adsorbent and removal agent for aromatic hydrocarbons.
本発明は、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去可能な吸着除去フィルター及び吸着除去方法を提供することを課題とする。 An object of the present invention is to provide an adsorption removal filter and an adsorption removal method that can easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water.
本発明者は、上記事情を鑑みて、まず、フラーレンがπ表面からなる活性面を有するため、前記活性面で様々な有機物を吸着可能であると考察し、吸着除去剤の可能性を検討した。しかし、ベンゼンの吸着除去は可能であるが、アニリンや安息香酸のような電荷を有する有機物の吸着除去はできなかった。
本発明者は、更に試行錯誤を続け、フラーレンは球状なので、π活性面が小さく、電荷を有する置換基を安定に保持することができないのではないかと考え、フラーレンより合成され、一般に、直径が数ｎｍで長さ数百μｍの柱状の物質であるフラーレンナノウィスカーを用いれば、π活性面が長く、かつ、広いので、電荷を有する置換基を安定に保持でき、電荷を有する置換基を有する芳香族炭化水素や多環式芳香族炭化水素でも吸着可能であるのではないかと考察するに至った。
そこで、フラーレンナノウィスカーを吸着除去剤として疎水性の有害有機物の吸着除去の実験を行い、フラーレンナノウィスカーがベンゼン、アニリン及び安息香酸を非常に良く吸着し、有害有機物を容易に除去できることを見出して、本発明を完成した。
本発明は、以下の構成を有する。
In view of the above circumstances, the present inventor first considered that fullerenes have an active surface composed of a π surface, and therefore considered that various organic substances can be adsorbed on the active surface, and examined the possibility of an adsorption removing agent. . However, benzene can be adsorbed and removed, but organic substances having electric charges such as aniline and benzoic acid cannot be adsorbed and removed.
The present inventor continued further trial and error, and because fullerene is spherical, the π active surface is small, and it may not be possible to stably hold a charged substituent. If fullerene nanowhiskers, which are columnar substances of several nanometers and several hundreds of micrometers in length, are used, the π-active surface is long and wide, so that a substituent having a charge can be stably held and a substituent having a charge is included. We came to consider that even aromatic hydrocarbons and polycyclic aromatic hydrocarbons could be adsorbed.
Therefore, we conducted experiments on adsorption and removal of hydrophobic harmful organic substances using fullerene nanowhiskers as an adsorption remover, and found that fullerene nanowhiskers adsorb benzene, aniline and benzoic acid very well and can easily remove harmful organic substances. The present invention has been completed.
The present invention has the following configuration.
（１） 厚さが１μｍ以上であり、孔径０．２ｎｍ以下の孔を有する支持フィルターと、前記支持フィルターの一面に形成された吸着除去膜と、を有し、前記吸着除去膜がフラーレンナノウィスカーからなり、膜厚が１００ｎｍ以上であることを特徴とする吸着除去フィルター。
（２） 前記フラーレンナノウィスカーが、長さ４．２３μｍ以上１０．３９μｍ以下であり、径０．３６３μｍ上０．６６９μｍ以下であることを特徴とする（１）に記載の吸着除去フィルター。
(1) A support filter having a thickness of 1 μm or more and having a pore diameter of 0.2 nm or less, and an adsorption removal film formed on one surface of the support filter, wherein the adsorption removal film is a fullerene nanowhisker An adsorption removal filter comprising a film thickness of 100 nm or more.
(2) The adsorption removal filter according to (1), wherein the fullerene nanowhisker has a length of 4.23 μm to 10.39 μm and a diameter of 0.363 μm to 0.669 μm.
（３） （１）又は（２）に記載の吸着除去フィルターを用いて、吸着除去目的物たる芳香族炭化水素や多環式芳香族炭化水素が溶解された水溶液を通過させる工程と、有することを特徴とする吸着除去方法。
（４） 前記工程の後に、吸着除去フィルターを通過させた水溶液を、遠心分離及びフィルター分離処理して、固定層から上澄み液を分離する工程と、を有することを特徴とする（３）に記載の吸着除去方法。
(3) Using the adsorption / removal filter according to (1) or (2), a process of passing an aqueous solution in which an aromatic hydrocarbon or a polycyclic aromatic hydrocarbon, which is an adsorption / removal target, is dissolved, and Adsorption removal method characterized by this.
(4) After the said process, it has the process of carrying out the centrifugation and the filter separation process of the aqueous solution which passed the adsorption removal filter, and isolate | separating a supernatant liquid from a fixed layer, (3) characterized by the above-mentioned. Adsorption removal method.
（５） 吸着除去目的物たる芳香族炭化水素や多環式芳香族炭化水素が溶解された水溶液に、所定量以上のフラーレンナノウィスカー粉末を分散させる工程と、室温±１０℃の温度範囲内で、２時間以上攪拌する工程と、を有することを特徴とする吸着除去方法。
（６） 前記攪拌工程の後に、撹拌した水溶液を、遠心分離及びフィルター分離処理して、前記水溶液からフラーレンナノウィスカー粉末を分離する工程と、を有することを特徴とする（５）に記載の吸着除去方法。
(5) A step of dispersing a fullerene nanowhisker powder in a predetermined amount or more in an aqueous solution in which an aromatic hydrocarbon or polycyclic aromatic hydrocarbon as an adsorption removal target is dissolved, and within a temperature range of room temperature ± 10 ° C. And a step of stirring for 2 hours or more.
(6) After the stirring step, the step of separating the fullerene nanowhisker powder from the aqueous solution by subjecting the stirred aqueous solution to centrifugal separation and filter separation treatment, and adsorbing according to (5) Removal method.
本発明の吸着除去フィルターは、厚さが１μｍ以上であり、孔径０．２ｎｍ以下の孔を有する支持フィルターと、前記支持フィルターの一面に形成された吸着除去膜と、を有し、前記吸着除去膜がフラーレンナノウィスカーからなり、膜厚が１００ｎｍ以上である構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。また、本発明の吸着除去フィルターは、濾過プラントにおいて容易に取り付けることができ、有用である。 The adsorption removal filter of the present invention has a support filter having a thickness of 1 μm or more and a pore diameter of 0.2 nm or less, and an adsorption removal film formed on one surface of the support filter, and the adsorption removal Since the film is composed of fullerene nanowhiskers and has a film thickness of 100 nm or more, it is possible to easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water. Moreover, the adsorption removal filter of this invention can be easily attached in a filtration plant, and is useful.
本発明の吸着除去方法は、先に記載の吸着除去フィルターを用いて、吸着除去目的物たる芳香族炭化水素が溶解された水溶液を通過させる工程と、を有する構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。 The adsorption / removal method of the present invention has a step of passing an aqueous solution in which an aromatic hydrocarbon as an adsorption / removal target is dissolved using the adsorption / removal filter described above, so that the aromatic hydrocarbon in water And polycyclic aromatic hydrocarbons can be easily adsorbed and removed.
本発明の吸着除去方法は、吸着除去目的物たる芳香族炭化水素が溶解された水溶液に、所定量以上のフラーレンナノウィスカー粉末を分散させる工程と、室温±１０℃の温度範囲内で、２時間以上攪拌する工程と、を有する構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。 The adsorption / removal method of the present invention comprises a step of dispersing a predetermined amount or more of fullerene nanowhisker powder in an aqueous solution in which an aromatic hydrocarbon as an adsorption / removal target is dissolved, and a temperature range of room temperature ± 10 ° C. for 2 hours. Therefore, it is possible to easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water.
（本発明の実施形態）
（吸着除去フィルター）
まず、本発明の実施形態である吸着除去フィルターについて説明する。
図１は、本発明の実施形態である吸着除去フィルターの一例を示す模式図であって、平面図（ａ）及び（ａ）のＡ−Ａ’線における断面図（ｂ）である。
図１（ａ）に示すように、本発明の実施形態である吸着除去フィルター１は、平面視略円形状とされている。しかし、これに限られるものではない。
(Embodiment of the present invention)
(Adsorption removal filter)
First, an adsorption removal filter according to an embodiment of the present invention will be described.
FIG. 1 is a schematic diagram illustrating an example of an adsorption removal filter according to an embodiment of the present invention, and is a cross-sectional view (b) taken along the line AA ′ in plan views (a) and (a).
As shown to Fig.1 (a), the adsorption removal filter 1 which is embodiment of this invention is made into the substantially circular shape in planar view. However, it is not limited to this.
図１（ｂ）に示すように、吸着除去フィルター１は、支持フィルター２１と、吸着除去膜１１と、を有している。
支持フィルター２１には、２以上の孔２１ｃが設けられている。孔２１ｃは、一面側からから他面側に連通している。支持フィルター２１の厚さは１μｍ以上とされている。孔径０．２ｎｍ以下とされている。支持フィルター２１としては、市販の濾過フィルターを用いることができる。
As illustrated in FIG. 1B, the adsorption removal filter 1 includes a support filter 21 and an adsorption removal film 11.
The support filter 21 is provided with two or more holes 21c. The hole 21c communicates from one surface side to the other surface side. The thickness of the support filter 21 is 1 μm or more. The pore diameter is set to 0.2 nm or less. A commercially available filter can be used as the support filter 21.
＜吸着除去膜＞
吸着除去膜１１は、支持フィルター２１の一面に形成されている。
吸着除去膜１１の膜厚ｔは１００ｎｍ以上とされている。１００ｎｍ未満では、十分吸着除去できない。
<Adsorption removal film>
The adsorption removal film 11 is formed on one surface of the support filter 21.
The film thickness t of the adsorption removal film 11 is 100 nm or more. If it is less than 100 nm, it cannot be sufficiently removed by adsorption.
図２は、図１（ｂ）のＢ部拡大図である。
吸着除去膜１１は、フラーレンナノウィスカー３１が凝集されてなる。
フラーレンナノウィスカー３１の隙間３１ｃを介して、一面側から他面側に水を通過させることができる。
FIG. 2 is an enlarged view of a portion B in FIG.
The adsorption removal film 11 is formed by aggregating fullerene nanowhiskers 31.
Water can be passed from one surface side to the other surface side through the gap 31 c of the fullerene nanowhisker 31.
＜フラーレンナノウィスカー＞
図３は、フラーレンナノウィスカーの一例を示す斜視図である。
また、図４は、フラーレンナノウィスカーの一例を示す側面図である。
フラーレンナノウィスカー３１は、六方晶形状の繊維状の物質である。フラーレン３２が凝集されて合成された柱状の物質である。最初は、チタン酸ジルコン酸鉛のコロイド内にフラーレンを入れて製造された。フラーレンナノウィスカーは、Ｃ６０の分子結晶の二倍以上のヤング率を持ち、曲げて変形できる。
<Fullerene nano whisker>
FIG. 3 is a perspective view showing an example of fullerene nanowhiskers.
FIG. 4 is a side view showing an example of fullerene nanowhiskers.
The fullerene nanowhiskers 31 are hexagonal fibrous materials. It is a columnar substance in which fullerenes 32 are aggregated and synthesized. Initially, fullerene was produced in a colloid of lead zirconate titanate. Fullerene nanowhiskers have a Young's modulus more than twice that of C60 molecular crystals, and can be bent and deformed.
フラーレンナノウィスカー３１は、長さｌが４．２３μｍ以上１０．３９μｍ以下が好ましい。また、径ｄは、０．３６３μｍ上０．６６９μｍ以下であることが好ましい。これらにより、効率よく、吸着除去できる。 The fullerene nanowhiskers 31 preferably have a length l of 4.23 μm or more and 10.39 μm or less. The diameter d is preferably 0.363 μm and 0.669 μm or less. By these, adsorption removal can be carried out efficiently.
＜フラーレンナノウィスカーの合成方法＞
フラーレンナノウィスカー３１は液・液界面折出法で合成する。
まず、Ｃ６０飽和トルエン溶液にイソプロピルアルコールを加える。
次に、２１℃以下で所定時間、保存する。これにより、底に綿状成長物が形成される。この形成時に光を遮断すると綿状成長物（Ｃ６０ナノウィスカー）が成長しないこと、Ｃ６０ナノウィスカーの成長速度は光の波長に依存することに留意する。
<Synthesis method of fullerene nanowhisker>
The fullerene nanowhisker 31 is synthesized by a liquid / liquid interface folding method.
First, isopropyl alcohol is added to a C60 saturated toluene solution.
Next, it is stored at 21 ° C. or lower for a predetermined time. As a result, a cotton-like growth is formed at the bottom. It should be noted that if the light is blocked during the formation, the cotton-like growth (C60 nanowhiskers) does not grow, and the growth rate of the C60 nanowhiskers depends on the wavelength of the light.
＜フラーレン＞
フラーレン３２は、炭素原子が閉じ、分子内には大きな隙間があるカゴ状の分子である。フラーレンにはサッカーボール状のＣ６０（カーボン６０）とラグビーボール状のＣ７０（カーボン７０）などがある。フラーレン分子は炭素の二重結合と一重結合とでできている。Ｃ６０は、表面に活性面を有し、高体積弾性率、低摩擦係数、超伝導発現、高い電子受容性、水素化物の形成、光・電子線照射、高温・高圧作用によるポリマー化、様々な誘導体形成、抗菌作用（活性酸素発生）などの特性を示す。
<Fullerene>
The fullerene 32 is a cage molecule in which carbon atoms are closed and there are large gaps in the molecule. Fullerenes include soccer ball-like C60 (carbon 60) and rugby ball-like C70 (carbon 70). Fullerene molecules are composed of carbon double and single bonds. C60 has an active surface on the surface, high volume modulus, low friction coefficient, superconductivity, high electron acceptability, hydride formation, light / electron beam irradiation, polymerization by high temperature / high pressure action, various Derivative formation, antibacterial action (active oxygen generation) and other characteristics.
＜芳香族炭化水素＞
吸着除去したい芳香族炭化水素としては、例えば、ベンゼンのような、電荷のない芳香族炭化水素だけでなく、アニリンのような、ベンゼン環にアミノ基が１つ結合し、水中で＋電荷を有する置換基を備える芳香族炭化水素や、安息香酸のような、ベンゼン環にカルボキシル基が１つ結合し、水中で−電荷を有する置換基を備える芳香族炭化水素を挙げることができる。
また、ベンゼン環が多数反応した高分子である多環式芳香族炭化水素であってもよい。
<Aromatic hydrocarbon>
As an aromatic hydrocarbon to be adsorbed and removed, for example, not only an aromatic hydrocarbon such as benzene but also an aniline such as aniline, an amino group is bonded to the benzene ring and has a positive charge in water. Examples thereof include aromatic hydrocarbons having a substituent and aromatic hydrocarbons having a substituent having a negative charge in water, such as benzoic acid, having one carboxyl group bonded to a benzene ring.
Further, it may be a polycyclic aromatic hydrocarbon which is a polymer in which a large number of benzene rings are reacted.
＜吸着機構＞
図５は、フラーレンナノウィスカーの吸着機構の一例を示す説明図である。
フラーレンナノウィスカーにベンゼンが近づくと、π活性面同士が連結し、吸着される。
水中で＋電荷を帯びたアニリンや、−電荷を帯びた安息香酸が近づいた場合も、複数のフラーレンが連結し、π活性面を長く、かつ、広く形成するので、安定して吸着保持できる。
<Adsorption mechanism>
FIG. 5 is an explanatory view showing an example of an adsorption mechanism of fullerene nanowhiskers.
When benzene approaches the fullerene nanowhisker, the π-active surfaces are connected and adsorbed.
Even when + charged aniline or -charged benzoic acid approaches in water, a plurality of fullerenes are connected to form a long and wide π-active surface, and can be stably adsorbed and retained.
図６は、フラーレンの吸着機構の一例を示す説明図である。
フラーレンにベンゼンが近づくと、π活性面同士が連結し、吸着される。
一方、水中で＋電荷を帯びたアニリンや、−電荷を帯びた安息香酸が近づいた場合は、電荷を帯びた置換基が結合を不安定化し、安定して吸着保持できない。
FIG. 6 is an explanatory view showing an example of a fullerene adsorption mechanism.
When benzene approaches fullerene, the π-active surfaces are connected and adsorbed.
On the other hand, when an aniline having a positive charge or a benzoic acid having a negative charge approaches in water, the charged substituent destabilizes the bond and cannot be stably adsorbed and retained.
＜芳香族炭化水素や多環式芳香族炭化水素の吸着除去方法１＞
本発明の実施形態である芳香族炭化水素や多環式芳香族炭化水素の吸着除去方法は、吸着除去フィルター１を用いて、吸着除去目的物たる芳香族炭化水素や多環式芳香族炭化水素が溶解された水溶液を通過させる工程と、を有する。吸着除去フィルター１内のフラーレンナノウィスカー３１の隙間を水が通過するときに、フラーレンナノウィスカー３１の表面に芳香族炭化水素や多環式芳香族炭化水素が吸着する。これにより、フィルターを通過させた水に溶解された芳香族炭化水素や多環式芳香族炭化水素の量を少なくすることができる。
<Method 1 for adsorption and removal of aromatic hydrocarbons and polycyclic aromatic hydrocarbons>
The method for adsorbing and removing aromatic hydrocarbons and polycyclic aromatic hydrocarbons, which is an embodiment of the present invention, uses an adsorption removal filter 1 to adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons as objects of adsorption. Passing an aqueous solution in which is dissolved. When water passes through the gap between the fullerene nanowhiskers 31 in the adsorption removal filter 1, aromatic hydrocarbons and polycyclic aromatic hydrocarbons are adsorbed on the surface of the fullerene nanowhiskers 31. Thereby, the quantity of the aromatic hydrocarbon and polycyclic aromatic hydrocarbon which were dissolved in the water which passed the filter can be decreased.
前記工程の後に、吸着除去フィルターを通過させた水溶液を、遠心分離及びフィルター分離処理して、固定層から上澄み液を分離する工程と、を有することが好ましい。これにより、水中の芳香族炭化水素や多環式芳香族炭化水素をより多く除去できる。 After the step, it is preferable to have a step of separating the supernatant from the fixed layer by subjecting the aqueous solution passed through the adsorption removal filter to centrifugation and filter separation. Thereby, more aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water can be removed.
＜芳香族炭化水素や多環式芳香族炭化水素の吸着除去方法２＞
本発明の実施形態である芳香族炭化水素や多環式芳香族炭化水素の吸着除去方法は、吸着除去目的物たる芳香族炭化水素や多環式芳香族炭化水素が溶解された水溶液に、所定量以上のフラーレンナノウィスカー粉末を分散させる工程と、室温±１０℃の温度範囲内で、２時間以上攪拌する工程と、を有する。攪拌時、フラーレンナノウィスカー３１の表面に芳香族炭化水素や多環式芳香族炭化水素が吸着する。これにより、フィルターを通過させた水に溶解された芳香族炭化水素や多環式芳香族炭化水素の量を少なくすることができる。
<Adsorption and removal method 2 of aromatic hydrocarbons and polycyclic aromatic hydrocarbons>
The method for adsorbing and removing aromatic hydrocarbons and polycyclic aromatic hydrocarbons, which is an embodiment of the present invention, is carried out in an aqueous solution in which aromatic hydrocarbons and polycyclic aromatic hydrocarbons, which are adsorption removal objects, are dissolved. There are a step of dispersing fullerene nanowhisker powder of a fixed amount or more and a step of stirring for 2 hours or more within a temperature range of room temperature ± 10 ° C. At the time of stirring, aromatic hydrocarbons and polycyclic aromatic hydrocarbons are adsorbed on the surface of the fullerene nanowhiskers 31. Thereby, the quantity of the aromatic hydrocarbon and polycyclic aromatic hydrocarbon which were dissolved in the water which passed the filter can be decreased.
前記攪拌工程の後に、撹拌した水溶液を、遠心分離及びフィルター分離処理して、前記水溶液からフラーレンナノウィスカー粉末を分離する工程と、を有することが好ましい。これにより、水中の芳香族炭化水素や多環式芳香族炭化水素をより容易に、かつ、より多く除去できる。 Preferably, after the stirring step, the stirred aqueous solution is subjected to centrifugal separation and filter separation to separate fullerene nanowhisker powder from the aqueous solution. Thereby, more aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water can be removed more easily.
本発明の実施形態である吸着除去フィルター１は、厚さが１μｍ以上であり、孔径０．２ｎｍ以下の孔を有する支持フィルター２１と、支持フィルター２１の一面に形成された吸着除去膜１１と、を有し、吸着除去膜１１がフラーレンナノウィスカー３１からなり、膜厚ｔが１００ｎｍ以上である構成なので、水中の芳香族炭化水素を容易に吸着除去できる。 An adsorption removal filter 1 according to an embodiment of the present invention has a support filter 21 having a thickness of 1 μm or more and a pore diameter of 0.2 nm or less, an adsorption removal film 11 formed on one surface of the support filter 21, The adsorption removal film 11 is composed of fullerene nanowhiskers 31 and has a thickness t of 100 nm or more, so that it is possible to easily adsorb and remove aromatic hydrocarbons in water.
本発明の実施形態である吸着除去フィルター１は、フラーレンナノウィスカー３１が、長さ４．２３μｍ以上１０．３９μｍ以下であり、径０．３６３μｍ上０．６６９μｍ以下である構成なので、水中の芳香族炭化水素を容易に吸着除去できる。 The adsorption / removal filter 1 according to the embodiment of the present invention has a configuration in which the fullerene nanowhiskers 31 have a length of 4.23 μm or more and 10.39 μm or less and a diameter of 0.363 μm and 0.669 μm or less. Hydrocarbons can be easily adsorbed and removed.
本発明の実施形態である吸着除去方法は、吸着除去フィルター１を用いて、吸着除去目的物たる芳香族炭化水素や多環式芳香族炭化水素が溶解された水溶液を通過させる工程と、を有する構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。 The adsorption / removal method according to the embodiment of the present invention includes a step of passing an aqueous solution in which an aromatic hydrocarbon or a polycyclic aromatic hydrocarbon, which is an adsorption / removal target, is dissolved, using the adsorption / removal filter 1. Since it is configured, it is possible to easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water.
本発明の実施形態である吸着除去方法は、前記工程の後に、吸着除去フィルターを通過させた水溶液を、遠心分離及びフィルター分離処理して、固定層から上澄み液を分離する工程と、を有する構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。 The adsorption / removal method according to an embodiment of the present invention includes a step of, after the above-mentioned step, separating the supernatant liquid from the fixed layer by centrifuging and filtering the aqueous solution that has passed through the adsorption / removal filter. Therefore, it is possible to easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water.
本発明の実施形態である吸着除去方法は、吸着除去目的物たる芳香族炭化水素や多環式芳香族炭化水素が溶解された水溶液に、所定量以上のフラーレンナノウィスカー粉末を分散させる工程と、室温±１０℃の温度範囲内で、２時間以上攪拌する工程と、を有する構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。 The adsorption removal method according to an embodiment of the present invention includes a step of dispersing a predetermined amount or more of fullerene nanowhisker powder in an aqueous solution in which an aromatic hydrocarbon or a polycyclic aromatic hydrocarbon as an adsorption removal object is dissolved, and Therefore, the aromatic hydrocarbon and polycyclic aromatic hydrocarbon in water can be easily adsorbed and removed.
本発明の実施形態である吸着除去方法は、前記攪拌工程の後に、撹拌した水溶液を、遠心分離及びフィルター分離処理して、前記水溶液からフラーレンナノウィスカー粉末を分離する工程と、を有する構成なので、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去できる。 The adsorption removal method according to an embodiment of the present invention has a step of, after the stirring step, a step of separating the fullerene nanowhisker powder from the aqueous solution by subjecting the stirred aqueous solution to centrifugation and filter separation treatment, It can easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water.
本発明の実施形態である吸着除去フィルター及び吸着除去方法は、上記実施形態に限定されるものではなく、本発明の技術的思想の範囲内で、種々変更して実施することができる。本実施形態の具体例を以下の実施例で示す。しかし、本発明はこれらの実施例に限定されるものではない。 The adsorption removal filter and the adsorption removal method according to the embodiment of the present invention are not limited to the above embodiment, and can be implemented with various modifications within the scope of the technical idea of the present invention. Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.
（実施例１−１）
＜水溶液（ベンゼン水溶液）の調整＞
まず、ベンゼン（ｂｅｎｚｅｎｅ：Ｂｚ）１００ｍｌと脱イオン水（超純水）１００ｍｌを三角フラスコに注ぎ、密封した。
次に、１２時間攪拌した。
次に、一晩静置した。
ベンゼンと分離して得られた、ベンゼンを溶解した水溶液を第１の水溶液とした。
(Example 1-1)
<Preparation of aqueous solution (benzene aqueous solution)>
First, 100 ml of benzene (Bz) and 100 ml of deionized water (ultra pure water) were poured into an Erlenmeyer flask and sealed.
Next, it stirred for 12 hours.
Next, it was left overnight.
An aqueous solution obtained by separating benzene and dissolving benzene was used as a first aqueous solution.
次に、超純水を用いて、前記第１の水溶液を希釈して、第２の水溶液（初期溶液）を調製した。平衡濃度を１ｍｍｏｌ・ｄｍ−３とした。 Next, the first aqueous solution was diluted with ultrapure water to prepare a second aqueous solution (initial solution). The equilibrium concentration was 1 mmol · dm −3 .
＜水溶液における被吸着物質の吸着前の濃度測定＞
第２の水溶液（初期溶液）における被吸着物質の吸着前の濃度を、全有機炭素計（ｔｏｔａｌ ｏｒｇａｎｉｃ ｃａｒｂｏｎ ａｎａｌｙｚｅｒ）で測定した。全有機炭素計は、水溶液中の有機物の濃度を測定する装置である。
<Measurement of concentration of adsorbed substance in aqueous solution before adsorption>
The density | concentration before adsorption | suction of the to-be-adsorbed substance in 2nd aqueous solution (initial solution) was measured with the total organic carbon analyzer (total organic carbon analyzer). The total organic carbon meter is a device that measures the concentration of organic substances in an aqueous solution.
＜吸着実験＞
まず、非特許文献３に記載の方法で、フラーレンナノウィスカー（Ｃ６０ ｆｕｌｌｅｒｅｎｅ ｎａｎｏｗｈｉｓｋｅｒ：ＦＮＷ）を合成した。
次に、顕微鏡観察を行い、フラーレンナノウィスカーの直径や長さを調べた。
次に、ほぼ同じ長さと直径のフラーレンナノウィスカーを採取した。
次に、第２の被水溶液（初期溶液）６ｃｍ３を試料ビン（密封容器：ストッパー付きガラスボトル）内に注入し、ＦＮＷを２０ｍｇ添加した。
次に、所定時間（２時間又は３時間）、攪拌した。
次に、０．２μｍフィルター（ディスポーザブル・フィルター）で濾過した。
<Adsorption experiment>
First, fullerene nanowhiskers (FNW) were synthesized by the method described in Non-Patent Document 3.
Next, microscopic observation was performed to examine the diameter and length of fullerene nanowhiskers.
Next, fullerene nanowhiskers having almost the same length and diameter were collected.
Next, 6 cm 3 of the second aqueous solution (initial solution) was poured into a sample bottle (sealed container: glass bottle with stopper), and 20 mg of FNW was added.
Next, the mixture was stirred for a predetermined time (2 hours or 3 hours).
Next, it filtered with the 0.2 micrometer filter (disposable filter).
＜水溶液における被吸着物質の吸着後の濃度測定＞
第２の水溶液（初期溶液）における被吸着物質の吸着後の濃度を、全有機炭素計で測定した。
式（１）に従い、ベンゼンの吸着量Ａを算出した。ここで、Ｖは容積であり、Ｃ０は吸着前の溶液の濃度であり、Ｃは吸着後の溶液の濃度であり、Ｗは吸着剤の重さである。
平衡濃度は、吸着処理が平衡に達したときの溶液の濃度であり、吸着等温線は、一定の温度下で平衡濃度の変化による吸着量を示したグラフである。
<Measurement of concentration of adsorbed substance in aqueous solution after adsorption>
The density | concentration after adsorption | suction of the to-be-adsorbed substance in 2nd aqueous solution (initial solution) was measured with the total organic carbon meter.
The adsorption amount A of benzene was calculated according to the formula (1). Here, V is the volume, C0 is the concentration of the solution before adsorption, C is the concentration of the solution after adsorption, and W is the weight of the adsorbent.
The equilibrium concentration is the concentration of the solution when the adsorption treatment reaches equilibrium, and the adsorption isotherm is a graph showing the amount of adsorption due to the change in the equilibrium concentration at a constant temperature.
図７は、水溶液の調整から吸着量の算出までの工程を示す説明図である。 FIG. 7 is an explanatory diagram showing steps from adjustment of the aqueous solution to calculation of the adsorption amount.
（実施例１−２〜実施例１−１６）
平衡濃度を１ｍｍｏｌ・ｄｍ−３〜９ｍｍｏｌ・ｄｍ−３とした他は実施例１−１と同様にして、それぞれベンゼンの吸着実験を行った。
(Example 1-2 to Example 1-16)
Except that the equilibrium concentration of 1mmol · dm -3 ~9mmol · dm -3 in the same manner as in Example 1-1, each received adsorption experiment benzene.
（比較例１−１）
ＦＮＷの代わりに、市販のフラーレン（Ｃ６０：Ｆｌ）を用い、平衡濃度を１ｍｍｏｌ・ｄｍ−３とした他は実施例１−１と同様にして、ベンゼンの吸着実験を行った。
(Comparative Example 1-1)
A benzene adsorption experiment was conducted in the same manner as in Example 1-1 except that a commercially available fullerene (C60: Fl) was used instead of FNW, and the equilibrium concentration was 1 mmol · dm −3 .
（比較例１−２〜比較例１−１４）
平衡濃度を１．１ｍｍｏｌ・ｄｍ−３〜９．１ｍｍｏｌ・ｄｍ−３とした他は比較例１−１と同様にして、ベンゼンの吸着実験を行った。
(Comparative Example 1-2 to Comparative Example 1-14)
A benzene adsorption experiment was conducted in the same manner as Comparative Example 1-1 except that the equilibrium concentration was 1.1 mmol · dm −3 to 9.1 mmol · dm −3 .
図８は、実施例１−１〜実施例１−１６及び比較例１−１〜比較例１−１４に基づいて、得られた吸着量と平衡濃度の関係を示すグラフ（吸着等温線：Ａｄｓｏｒｐｔｉｏｎ ｉｓｏｔｈｅｒｍｓ）である。
図８の黒丸が、（式１）により求めた吸着量に基づく、フラーレンナノウィスカーによるベンゼンの吸着除去についての吸着等温線である。フラーレンナノウィスカーは非常に多くのベンゼンを吸着した。
また、図８の白四角は、フラーレンを用いたベンゼンの吸着除去の吸着等温線である。フラーレンナノウィスカーとほぼ同じ程度の吸着量を示した。
つまり、Ｆ１とＦＮＷでＢｚ吸着特性に違いは見られなかった。これは、フラーレンとフラーレンナノウィスカーの比表面積がほぼ同じ値であるためと考えられる。
FIG. 8 is a graph (adsorption isotherm: Adsorption) showing the relationship between the amount of adsorption and the equilibrium concentration obtained based on Example 1-1 to Example 1-16 and Comparative Example 1-1 to Comparative Example 1-14. isotherms).
The black circles in FIG. 8 are adsorption isotherms for adsorption removal of benzene by fullerene nanowhiskers based on the adsorption amount obtained by (Equation 1). Fullerene nanowhiskers adsorbed a great deal of benzene.
Also, the white squares in FIG. 8 are adsorption isotherms for the adsorption removal of benzene using fullerene. The adsorption amount was almost the same as that of fullerene nanowhiskers.
That is, there was no difference in Bz adsorption characteristics between F1 and FNW. This is presumably because fullerenes and fullerene nanowhiskers have substantially the same specific surface area.
＜水溶液（アニリン水溶液）の調整＞
まず、超純水を用いて、１０ｍｍｏｌ・ｄｍ−３のアニリン（ａｎｉｌｉｎｅ：Ａｎ）溶液を調製した。
<Preparation of aqueous solution (aniline aqueous solution)>
First, a 10 mmol · dm −3 aniline (Aniline) solution was prepared using ultrapure water.
アニリンはベンゼン環にアミノ基がついたもので、芳香族炭化水素としては、親水的である。酸性側ではアニリンは正電荷を持つが、ｐＨが７の中性付近では僅かに正電荷を帯びるだけであり、電荷を持たない。 Aniline has a benzene ring with an amino group and is hydrophilic as an aromatic hydrocarbon. On the acidic side, aniline has a positive charge, but at a neutral pH of 7, it is only slightly charged and has no charge.
次に、前記第１の水溶液を希釈したものに、アニリン溶液を加入して第３の水溶液（初期溶液）を調製した。平衡濃度を１ｍｍｏｌ・ｄｍ−３とした。 Next, an aniline solution was added to the diluted first aqueous solution to prepare a third aqueous solution (initial solution). The equilibrium concentration was 1 mmol · dm −3 .
＜吸着実験＞
まず、非特許文献３に記載の方法で、ＦＮＷを合成した。
次に、第３の水溶液（初期溶液）を試料ビン（密封容器）内に注入し、ＦＮＷを２０ｍｇ添加した。
次に、所定時間、攪拌した。
次に、０．２μｍフィルターで濾過した。
<Adsorption experiment>
First, FNW was synthesized by the method described in Non-Patent Document 3.
Next, the third aqueous solution (initial solution) was poured into a sample bottle (sealed container), and 20 mg of FNW was added.
Next, the mixture was stirred for a predetermined time.
Next, it filtered with the 0.2 micrometer filter.
濾過の前後の水溶液について全有機炭素計で濃度を測定した。
これにより、アニリンの吸着量を算出した。
The concentration of the aqueous solution before and after filtration was measured with a total organic carbon meter.
Thereby, the adsorption amount of aniline was calculated.
（実施例２−２〜実施例２−１１）
平衡濃度を１．５ｍｍｏｌ・ｄｍ−３〜１１ｍｍｏｌ・ｄｍ−３とした他は実施例２−１と同様にして、それぞれアニリンの吸着実験を行った。
(Example 2-2 to Example 2-11)
Except that the equilibrium concentration of 1.5mmol · dm -3 ~11mmol · dm -3 in the same manner as in Example 2-1, each received adsorption experiment aniline.
（比較例２−１）
ＦＮＷの代わりに、市販のフラーレン（Ｃ６０：Ｆｌ）を用い、平衡濃度を１ｍｍｏｌ・ｄｍ−３とした他は実施例１−１と同様にして、アニリンの吸着実験を行った。
(Comparative Example 2-1)
An aniline adsorption experiment was conducted in the same manner as in Example 1-1 except that a commercially available fullerene (C60: Fl) was used instead of FNW and the equilibrium concentration was 1 mmol · dm −3 .
（比較例２−２〜比較例２−１１）
平衡濃度を２．３ｍｍｏｌ・ｄｍ−３〜１２ｍｍｏｌ・ｄｍ−３とした他は比較例２−１と同様にして、アニリンの吸着実験を行った。
(Comparative Example 2-2 to Comparative Example 2-11)
An aniline adsorption experiment was performed in the same manner as in Comparative Example 2-1, except that the equilibrium concentration was 2.3 mmol · dm −3 to 12 mmol · dm −3 .
図９は、実施例２−１〜実施例２−１１及び比較例２−１〜比較例２−１１に基づいて、得られた吸着量と平衡濃度の関係を示すグラフ（吸着等温線：Ａｄｓｏｒｐｔｉｏｎ ｉｓｏｔｈｅｒｍｓ）である。
Ｆ１とＦＮＷでＡｎ吸着特性に違いは見られた。
ＦＮＷは、Ａｎをよく吸着したが、Ｆ１はほとんど吸着しなかった。
FIG. 9 is a graph (adsorption isotherm: Adsorption) showing the relationship between the amount of adsorption and the equilibrium concentration obtained based on Example 2-1 to Example 2-11 and Comparative Example 2-1 to Comparative Example 2-11. isotherms).
There was a difference in An adsorption characteristics between F1 and FNW.
FNW adsorbed An well, but F1 hardly adsorbed.
（実施例３−１）
＜被水溶液（安息香酸水溶液）の調整＞
まず、超純水を用いて、１０ｍｍｏｌ・ｄｍ−３の安息香酸溶液を調製した。
(Example 3-1)
<Preparation of aqueous solution (benzoic acid aqueous solution)>
First, a 10 mmol · dm −3 benzoic acid solution was prepared using ultrapure water.
安息香酸はベンゼン環にカルボキシル基を持つもので、芳香族炭化水素としては親水的である。安息香酸は酸性側では負電荷を持ち、アルカリ側では電気的に中性である。アニリンと電気的には逆の性質を持つ芳香族炭化水素である。 Benzoic acid has a carboxyl group on the benzene ring and is hydrophilic as an aromatic hydrocarbon. Benzoic acid has a negative charge on the acidic side and is electrically neutral on the alkaline side. It is an aromatic hydrocarbon that is electrically opposite to aniline.
次に、前記第１の水溶液を希釈したものに、安息香酸溶液を加入して第４の被水溶液（初期溶液）を調製した。平衡濃度を１ｍｍｏｌ・ｄｍ−３とした。 Next, a benzoic acid solution was added to the diluted first aqueous solution to prepare a fourth aqueous solution (initial solution). The equilibrium concentration was 1 mmol · dm −3 .
＜吸着実験＞
まず、非特許文献３に記載の方法で、ＦＮＷを合成した。
次に、第４の水溶液（初期溶液）を試料ビン（密封容器）内に注入し、ＦＮＷを２０ｍｇ添加した。
次に、所定時間、攪拌した。
次に、０．２μｍフィルターで濾過した。
<Adsorption experiment>
First, FNW was synthesized by the method described in Non-Patent Document 3.
Next, the fourth aqueous solution (initial solution) was poured into a sample bottle (sealed container), and 20 mg of FNW was added.
Next, the mixture was stirred for a predetermined time.
Next, it filtered with the 0.2 micrometer filter.
濾過の前後の水溶液について全有機炭素計で濃度を測定した。
これにより、安息香酸の吸着量を算出した。
The concentration of the aqueous solution before and after filtration was measured with a total organic carbon meter.
Thereby, the adsorption amount of benzoic acid was calculated.
（実施例３−２〜実施例３−９）
平衡濃度を２ｍｍｏｌ・ｄｍ−３〜９ｍｍｏｌ・ｄｍ−３とした他は実施例３−１と同様にして、それぞれ安息香酸の吸着実験を行った。
(Example 3-2 to Example 3-9)
Except that the equilibrium concentration of 2mmol · dm -3 ~9mmol · dm -3 in the same manner as in Example 3-1, each received adsorption experiment benzoic acid.
（比較例３−１）
ＦＮＷの代わりに、市販のフラーレン（Ｃ６０：Ｆｌ）を用い、平衡濃度を１ｍｍｏｌ・ｄｍ−３とした他は実施例３−１と同様にして、安息香酸の吸着実験を行った。
(Comparative Example 3-1)
A benzoic acid adsorption experiment was conducted in the same manner as in Example 3-1, except that a commercially available fullerene (C60: Fl) was used instead of FNW and the equilibrium concentration was 1 mmol · dm −3 .
（比較例３−２〜比較例３−１１）
平衡濃度を２ｍｍｏｌ・ｄｍ−３〜９．５ｍｍｏｌ・ｄｍ−３とした他は比較例３−１と同様にして、安息香酸の吸着実験を行った。
(Comparative Example 3-2 to Comparative Example 3-11)
Except that the equilibrium concentration of 2mmol · dm -3 ~9.5mmol · dm -3 in the same manner as in Comparative Example 3-1, was adsorption experiment benzoic acid.
図１０は、実施例３−１〜実施例３−９及び比較例３−１〜比較例３−１１に基づいて、得られた吸着量と平衡濃度の関係を示すグラフ（吸着等温線：Ａｄｓｏｒｐｔｉｏｎ ｉｓｏｔｈｅｒｍｓ）である。
Ｆ１とＦＮＷで安息香酸の吸着特性に違いは見られた。
ＦＮＷは、安息香酸をよく吸着したが、Ｆ１はほとんど吸着しなかった。
FIG. 10 is a graph (adsorption isotherm: Adsorption) showing the relationship between the obtained adsorption amount and the equilibrium concentration based on Example 3-1 to Example 3-9 and Comparative Example 3-1 to Comparative Example 3-11. isotherms).
Differences were observed in the adsorption characteristics of benzoic acid between F1 and FNW.
FNW adsorbed benzoic acid well, but F1 hardly adsorbed.
（比較例４−１）
ＦＮＷの代わりに、メソポア材（ＦＳＭ−１６）を用い、平衡濃度を０．１ｍｍｏｌ・ｄｍ−３とした他は実施例１−１の同様にして、安息香酸の吸着実験を行った。
ＦＳＭ−１６は、珪酸塩多孔体に一種でカネマイトという粘土鉱物（層状ケイ酸塩）と界面活性剤から合成される材料であり、直径数ｎｍのメソ孔がある。カネマイトに界面活性剤をインターカレーションしたのちに、５５０℃で焼成して、直径４ｎｍのメソポア孔を形成して合成したものである。
(Comparative Example 4-1)
A benzoic acid adsorption experiment was conducted in the same manner as in Example 1-1 except that mesopore material (FSM-16) was used instead of FNW and the equilibrium concentration was 0.1 mmol · dm −3 .
FSM-16 is a material synthesized from a clay mineral (layered silicate) called kanemite and a surfactant in a silicate porous body, and has mesopores with a diameter of several nm. After intercalating a surfactant with kanemite, it was baked at 550 ° C. to form a mesopore with a diameter of 4 nm and synthesized.
（比較例４−２〜比較例４−１４）
平衡濃度を０．２ｍｍｏｌ・ｄｍ−３〜１．５ｍｍｏｌ・ｄｍ−３とした他は比較例４−１と同様にして、それぞれ安息香酸の吸着実験を行った。
(Comparative Example 4-2 to Comparative Example 4-14)
Except that the equilibrium concentration of 0.2mmol · dm -3 ~1.5mmol · dm -3 in the same manner as in Comparative Example 4-1, each received adsorption experiment benzoic acid.
（比較例５−１）
ＦＮＷの代わりに、メソポア材（ＦＳＭ−１６）を用い、平衡濃度を０．１ｍｍｏｌ・ｄｍ−３とした他は実施例３−１と同様にして、ベンゼンの吸着実験を行った。
(Comparative Example 5-1)
A benzene adsorption experiment was conducted in the same manner as in Example 3-1, except that mesopore material (FSM-16) was used instead of FNW and the equilibrium concentration was 0.1 mmol · dm −3 .
（比較例５−２〜比較例５−３４）
平衡濃度を０．２ｍｍｏｌ・ｄｍ−３〜１．５ｍｍｏｌ・ｄｍ−３とした他は比較例５−１と同様にして、それぞれ安息香酸の吸着実験を行った。
(Comparative Example 5-2 to Comparative Example 5-34)
Except that the equilibrium concentration of 0.2mmol · dm -3 ~1.5mmol · dm -3 in the same manner as in Comparative Example 5-1, each received adsorption experiment benzoic acid.
図１１は、比較例４−１〜比較例５−３４に基づいて、得られた吸着量と平衡濃度の関係を示すグラフ（吸着等温線：Ａｄｓｏｒｐｔｉｏｎ ｉｓｏｔｈｅｒｍｓ）である。
図１１の白丸は、比表面積の大きいＦＳＭ−１６を用いたベンゼンの吸着例である。Ｆ１とＦＮＷに対して、メソポワ剤ＦＳＭ−１６のＢｚ吸着特性は非常に低かった。
メソポワ剤ＦＳＭ−１６の安息香酸の吸着特性も非常に低かった。
FIG. 11 is a graph (Adsorption isotherms) showing the relationship between the amount of adsorption and the equilibrium concentration obtained based on Comparative Example 4-1 to Comparative Example 5-34.
The white circles in FIG. 11 are examples of benzene adsorption using FSM-16 having a large specific surface area. For F1 and FNW, the Bz adsorption characteristics of the mesopore agent FSM-16 were very low.
The adsorption characteristics of benzoic acid of Mesopowa agent FSM-16 were also very low.
（比較例６−１）
ＦＮＷの代わりに、市販のパイロフィライトを用い、平衡濃度を３ｍｍｏｌ・ｄｍ−３とした他は実施例１２−１と同様にして、アニリンの吸着実験を行った。
パイロフィライトは、粘土鉱物の一種である。
(Comparative Example 6-1)
An aniline adsorption experiment was conducted in the same manner as in Example 12-1, except that a commercially available pyrophyllite was used instead of FNW and the equilibrium concentration was 3 mmol · dm −3 .
Pyrophyllite is a kind of clay mineral.
（比較例６−２〜比較例６−１２）
平衡濃度を３．３ｍｍｏｌ・ｄｍ−３〜１４．５ｍｍｏｌ・ｄｍ−３とした他は比較例６−１と同様にして、それぞれアニリンの吸着実験を行った。
(Comparative Example 6-2 to Comparative Example 6-12)
Except that the equilibrium concentration of 3.3mmol · dm -3 ~14.5mmol · dm -3 in the same manner as in Comparative Example 6-1, each received adsorption experiment aniline.
（比較例７−１）
ＦＮＷの代わりに、市販のモンモリロナイトを用い、平衡濃度を１ｍｍｏｌ・ｄｍ−３とした他は実施例２−１と同様にして、アニリンの吸着実験を行った。
モンモリロナイトは、粘土鉱物の一種である。
(Comparative Example 7-1)
An aniline adsorption experiment was conducted in the same manner as in Example 2-1, except that a commercially available montmorillonite was used instead of FNW, and the equilibrium concentration was 1 mmol · dm −3 .
Montmorillonite is a kind of clay mineral.
（比較例７−２〜比較例７−２６）
平衡濃度を１．５ｍｍｏｌ・ｄｍ−３〜１７ｍｍｏｌ・ｄｍ−３とした他は比較例７−１と同様にして、それぞれアニリンの吸着実験を行った。
(Comparative Example 7-2 to Comparative Example 7-26)
Except that the equilibrium concentration of 1.5mmol · dm -3 ~17mmol · dm -3 in the same manner as in Comparative Example 7-1, each received adsorption experiment aniline.
（比較例８−１）
ＦＮＷの代わりに、市販のパイロフィライトを用い、平衡濃度を１．３ｍｍｏｌ・ｄｍ−３とした他は実施例３−１と同様にして、安息香酸の吸着実験を行った。
(Comparative Example 8-1)
A benzoic acid adsorption experiment was conducted in the same manner as in Example 3-1, except that a commercially available pyrophyllite was used instead of FNW and the equilibrium concentration was 1.3 mmol · dm −3 .
（比較例８−２〜比較例８−１３）
平衡濃度を１．５ｍｍｏｌ・ｄｍ−３〜１１ｍｍｏｌ・ｄｍ−３とした他は比較例８−１と同様にして、それぞれ安息香酸の吸着実験を行った。
(Comparative Example 8-2 to Comparative Example 8-13)
Except that the equilibrium concentration of 1.5mmol · dm -3 ~11mmol · dm -3 in the same manner as in Comparative Example 8-1, each received adsorption experiment benzoic acid.
図１２は、比較例６−１〜比較例８−１３に基づいて、得られた吸着量と平衡濃度の関係を示すグラフ（吸着等温線：Ａｄｓｏｒｐｔｉｏｎ ｉｓｏｔｈｅｒｍｓ）である。
ＦＮＷに対して、パイオフィライトのＡｎ吸着特性は非常に低く、Ｆ１よりも低かった。
ＦＮＷに対して、モンモリライトのＡｎ吸着特性はＦ１と同程度に低かった。
パイロフィライトの安息香酸の吸着特性も非常に低かった。
FIG. 12 is a graph (Adsorption isotherms) showing the relationship between the amount of adsorption and the equilibrium concentration obtained based on Comparative Example 6-1 to Comparative Example 8-13.
With respect to FNW, the anion adsorption property of pyophyllite was very low and lower than that of F1.
Compared with FNW, the An adsorption property of montmorillonite was as low as F1.
The adsorption properties of pyrophyllite with benzoic acid were also very low.
図８〜１２の評価結果は次のとおりである。
フラーレンナノウィスカーに関して：
ベンゼン：傾き、０．０５８８ Ｒ２＝０．６９８６７
アニリン：傾き、０．０２１７ Ｒ２＝０．３７８６８
安息香酸：傾き、０．０１８４ Ｒ２＝０．８２１８３
フラーレンン関して：
ベンゼン：傾き、０．０５７８ Ｒ２＝０．８９４５９
アニリン：傾き、０．００４７ Ｒ２＝０．２３４２９
安息香酸：傾き、０．００６４ Ｒ２＝０．４２９４２
ＦＳＭ−１６に関して：
ベンゼン：傾き、０．０１５９ Ｒ２＝論文に記載なし
安息香酸：傾き、０．００９１８ Ｒ２＝論文に記載なし
モンモリロナイトに関して：
アニリン：傾き、０．００６９ Ｒ２＝０．７０２３８
パイロフィライトに関して：
アニリン：傾き、０．００２０ Ｒ２＝０．５３２３０７
安息香酸：傾き、０．００１９ Ｒ２＝０．３６５２４
The evaluation results of FIGS. 8 to 12 are as follows.
About fullerene nanowhiskers:
Benzene: slope, 0.0588 R 2 = 0.69867
Aniline: Tilt, 0.0217 R 2 = 0.37868
Benzoic acid: slope, 0.0184 R 2 = 0.82183
About Fulleren:
Benzene: slope, 0.0578 R 2 = 0.89459
Aniline: Tilt, 0.0047 R 2 = 0.23429
Benzoic acid: slope, 0.0064 R 2 = 0.42942
Regarding FSM-16:
Benzene: slope, 0.0159 R 2 = not stated in the paper
Benzoic acid: slope, 0.00918 R 2 = not described in paper
About Montmorillonite:
Aniline: Tilt, 0.0069 R 2 = 0.70238
Regarding pyrophyllite:
Aniline: Tilt, 0.0020 R 2 = 0.532307
Benzoic acid: slope, 0.0019 R 2 = 0.36524
（実施例４）
（吸着除去フィルターの作製）
図１３は、吸着除去フィルターの作製工程を示す説明図である。
まず、膜厚０．１ｍｍ、孔径０．６５μｍの支持フィルターを用意した。
次に、吸引ろ過装置にセットした注入容器に支持フィルターをセットした。
次に、注入容器にフラーレンナノウィスカー（０．０２２２ｇ）を均一に分散した水溶液を注入した。
Example 4
(Production of adsorption removal filter)
FIG. 13 is an explanatory view showing a production process of the adsorption removal filter.
First, a support filter having a film thickness of 0.1 mm and a hole diameter of 0.65 μm was prepared.
Next, the support filter was set in the injection container set in the suction filtration device.
Next, an aqueous solution in which fullerene nanowhiskers (0.0222 g) were uniformly dispersed was injected into an injection container.
次に、吸引ろ過装置を起動し、脱気して、前記水溶液をろ過した。これにより、支持フィルター上にフラーレンナノウィスカーの膜を形成した。 Next, the suction filtration apparatus was started, deaerated, and the aqueous solution was filtered. Thus, a fullerene nanowhisker film was formed on the support filter.
次に、フラーレンナノウィスカー膜の上に支持フィルターを載せた。
次に、超純水を注入してから、吸引ろ過装置を起動し、脱気して、前記超純水をろ過した。これにより、フラーレンナノウィスカー膜を均一の厚さ約０．０２ｍｍにした。
次に、フラーレンナノウィスカー膜を十分乾燥した。
以上により、吸着除去フィルターを作製した。
Next, a support filter was placed on the fullerene nanowhisker membrane.
Next, after injecting ultrapure water, the suction filtration device was started, degassed, and the ultrapure water was filtered. As a result, the fullerene nanowhisker film had a uniform thickness of about 0.02 mm.
Next, the fullerene nanowhisker film was sufficiently dried.
The adsorption removal filter was produced by the above.
図１４は、作製した吸着除去フィルターのフラーレンナノウィスカー膜表面の一部のＳＥＭ像である。 FIG. 14 is an SEM image of a part of the fullerene nanowhisker film surface of the produced adsorption removal filter.
（吸着除去フィルターの吸着試験：濾過性能評価）
図１５は、吸着除去フィルターの吸着試験を示す説明図である。
ベンゼン水溶液を吸引ろ過した。
ろ過後の水溶液濃度と、ろ過前の水溶液の濃度を比較した。
９．８５４ｍｍｏｌ・ｄｍ−３のベンゼン水溶液をこのフィルターに通した水溶液の濃度は４．９３４ｍｍｏｌ・ｄｍ−３であった。これにより、ベンゼンの吸着量は２．２１６ｍｍｏｌ／ｇであった。
(Adsorption test of adsorption removal filter: Filtration performance evaluation)
FIG. 15 is an explanatory diagram showing an adsorption test of the adsorption removal filter.
The aqueous benzene solution was filtered with suction.
The aqueous solution concentration after filtration was compared with the concentration of the aqueous solution before filtration.
The concentration of the aqueous solution obtained by passing a 9.854 mmol · dm −3 aqueous solution of benzene through this filter was 4.934 mmol · dm −3 . Thereby, the adsorption amount of benzene was 2.216 mmol / g.
本発明の吸着除去フィルター及び吸着除去方法は、水中の芳香族炭化水素や多環式芳香族炭化水素を容易に吸着除去可能な吸着除去フィルター及び吸着除去方法を提供することができ、吸着除去フィルター産業、水中の芳香族炭化水素や多環式芳香族炭化水素の除去産業等において利用可能性がある。 The adsorption removal filter and the adsorption removal method of the present invention can provide an adsorption removal filter and an adsorption removal method that can easily adsorb and remove aromatic hydrocarbons and polycyclic aromatic hydrocarbons in water. It can be used in industry, removal of aromatic hydrocarbons in water and polycyclic aromatic hydrocarbons, and the like.
１…吸着除去フィルター、１１…フラーレンナノウィスカー膜、２１…支持フィルター、２１ｃ…孔、３１…フラーレンナノウィスカー、３１ｃ…隙間、３２…フラーレン。
DESCRIPTION OF SYMBOLS 1 ... Adsorption removal filter, 11 ... Fullerene nano whisker membrane, 21 ... Support filter, 21c ... Hole, 31 ... Fullerene nano whisker, 31c ... Gap, 32 ... Fullerene.
Claims (6)
前記吸着除去膜がフラーレンナノウィスカーからなり、膜厚が１００ｎｍ以上であることを特徴とする吸着除去フィルター。 A support filter having a thickness of 1 μm or more and having pores having a pore diameter of 0.2 nm or less, and an adsorption removal film formed on one surface of the support filter;
The adsorption removal filter, wherein the adsorption removal film is made of fullerene nanowhiskers and has a thickness of 100 nm or more.
室温±１０℃の温度範囲内で、２時間以上攪拌する工程と、を有することを特徴とする吸着除去方法。 A step of dispersing a predetermined amount or more of fullerene nanowhisker powder in an aqueous solution in which an aromatic hydrocarbon or polycyclic aromatic hydrocarbon which is an adsorption removal target is dissolved;
And a step of stirring for 2 hours or more within a temperature range of room temperature ± 10 ° C.
6. The adsorption removal method according to claim 5, further comprising a step of separating the fullerene nanowhisker powder from the aqueous solution by subjecting the stirred aqueous solution to centrifugation and filter separation after the stirring step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014242715A JP6422156B2 (en) | 2014-12-01 | 2014-12-01 | Adsorption removal filter and adsorption removal method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014242715A JP6422156B2 (en) | 2014-12-01 | 2014-12-01 | Adsorption removal filter and adsorption removal method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016104464A true JP2016104464A (en) | 2016-06-09 |
| JP6422156B2 JP6422156B2 (en) | 2018-11-14 |
Family
ID=56102227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014242715A Active JP6422156B2 (en) | 2014-12-01 | 2014-12-01 | Adsorption removal filter and adsorption removal method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6422156B2 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0768252A (en) * | 1993-05-03 | 1995-03-14 | Rohm & Haas Co | Method of isolating toxic hydrophobic organic substance during settling |
| JPH07185327A (en) * | 1993-12-28 | 1995-07-25 | Nec Corp | Adsorbent and filter media and utilization of the same |
| JPH0947759A (en) * | 1995-08-04 | 1997-02-18 | Daicel Chem Ind Ltd | Waste water treatment |
| JP2005254393A (en) * | 2004-03-11 | 2005-09-22 | National Institute For Materials Science | Continuous fiber fullerene thin line and manufacturing method thereof |
| JP2006124266A (en) * | 2004-10-01 | 2006-05-18 | National Institute For Materials Science | C60 fullerene tube and its manufacturing method |
| JP2006131460A (en) * | 2004-11-08 | 2006-05-25 | National Institute For Materials Science | Very short fullerene nanowhisker and its manufacturing method |
| JP2009051708A (en) * | 2007-08-29 | 2009-03-12 | National Institute For Materials Science | Substrate with thin fullerene wire and method for producing the same |
-
2014
- 2014-12-01 JP JP2014242715A patent/JP6422156B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0768252A (en) * | 1993-05-03 | 1995-03-14 | Rohm & Haas Co | Method of isolating toxic hydrophobic organic substance during settling |
| JPH07185327A (en) * | 1993-12-28 | 1995-07-25 | Nec Corp | Adsorbent and filter media and utilization of the same |
| JPH0947759A (en) * | 1995-08-04 | 1997-02-18 | Daicel Chem Ind Ltd | Waste water treatment |
| JP2005254393A (en) * | 2004-03-11 | 2005-09-22 | National Institute For Materials Science | Continuous fiber fullerene thin line and manufacturing method thereof |
| JP2006124266A (en) * | 2004-10-01 | 2006-05-18 | National Institute For Materials Science | C60 fullerene tube and its manufacturing method |
| JP2006131460A (en) * | 2004-11-08 | 2006-05-25 | National Institute For Materials Science | Very short fullerene nanowhisker and its manufacturing method |
| JP2009051708A (en) * | 2007-08-29 | 2009-03-12 | National Institute For Materials Science | Substrate with thin fullerene wire and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6422156B2 (en) | 2018-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Far et al. | PPI-dendrimer-functionalized magnetic metal–organic framework (Fe3O4@ MOF@ PPI) with high adsorption capacity for sustainable wastewater treatment | |
| An et al. | Separation performance of graphene oxide membrane in aqueous solution | |
| Alizadehgiashi et al. | Nanocolloidal hydrogel for heavy metal scavenging | |
| Ang et al. | Polycationic polymer-regulated assembling of 2D MOF nanosheets for high-performance nanofiltration | |
| Li et al. | Aggregation kinetics and self-assembly mechanisms of graphene quantum dots in aqueous solutions: cooperative effects of pH and electrolytes | |
| Zhu et al. | Improved interfacial affinity and CO2 separation performance of asymmetric mixed matrix membranes by incorporating postmodified MIL-53 (Al) | |
| Zhang et al. | Adsorption of p-nitrophenol from aqueous solutions using nanographite oxide | |
| Zhang et al. | Polyethersulfone enwrapped graphene oxide porous particles for water treatment | |
| Zhan et al. | Highly efficient removal of pathogenic bacteria with magnetic graphene composite | |
| Liu et al. | Three-dimensional graphene oxide nanostructure for fast and efficient water-soluble dye removal | |
| Han et al. | Synthesis of CNT@ MIL-68 (Al) composites with improved adsorption capacity for phenol in aqueous solution | |
| Jung et al. | A facile methodology for the production of in situ inorganic nanowire hydrogels/aerogels | |
| White et al. | Functional hollow carbon nanospheres by latex templating | |
| US10266634B2 (en) | Chemically stable hollow spherical COF and synthesis thereof | |
| Plisko et al. | Fabrication and characterization of polyamide-fullerenol thin film nanocomposite hollow fiber membranes with enhanced antifouling performance | |
| Cheng et al. | Solvated graphenes: an emerging class of functional soft materials | |
| Gu et al. | Hydrophilic mesoporous carbon nanoparticles as carriers for sustained release of hydrophobic anti-cancer drugs | |
| Barrejón et al. | Cross-linked carbon nanotube adsorbents for water treatment: tuning the sorption capacity through chemical functionalization | |
| Rashid et al. | Synthesis, properties, water and solute permeability of MWNT buckypapers | |
| Lin et al. | Nano-WS2 embedded PES membrane with improved fouling and permselectivity | |
| Manimegalai et al. | Carbon-based nanomaterial intervention and efficient removal of various contaminants from effluents–A review | |
| Martín et al. | Enhanced ultrafiltration PES membranes doped with mesostructured functionalized silica particles | |
| CN107405539A (en) | Urea release compositions and method | |
| Sahu et al. | Advanced polymeric nanocomposite membranes for water and wastewater treatment: a comprehensive review | |
| CN104507552A (en) | Membrane for filtrating water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170920 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180425 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180501 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180703 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180712 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181002 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181012 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6422156 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |