JP4943516B2 - 銀−酸化チタン−ゼオライト吸着分解素材 - Google Patents
銀−酸化チタン−ゼオライト吸着分解素材 Download PDFInfo
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- JP4943516B2 JP4943516B2 JP2009551616A JP2009551616A JP4943516B2 JP 4943516 B2 JP4943516 B2 JP 4943516B2 JP 2009551616 A JP2009551616 A JP 2009551616A JP 2009551616 A JP2009551616 A JP 2009551616A JP 4943516 B2 JP4943516 B2 JP 4943516B2
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- titanium oxide
- zeolite
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- toluene
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- 229910021536 Zeolite Inorganic materials 0.000 title claims description 124
- 239000010457 zeolite Substances 0.000 title claims description 124
- 238000000354 decomposition reaction Methods 0.000 title claims description 37
- 230000000274 adsorptive effect Effects 0.000 title claims description 18
- 239000000463 material Substances 0.000 title claims description 14
- MZFIXCCGFYSQSS-UHFFFAOYSA-N silver titanium Chemical compound [Ti].[Ag] MZFIXCCGFYSQSS-UHFFFAOYSA-N 0.000 title 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 123
- 239000010936 titanium Substances 0.000 claims description 87
- 229910052719 titanium Inorganic materials 0.000 claims description 87
- 239000002131 composite material Substances 0.000 claims description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 40
- 229910052709 silver Inorganic materials 0.000 claims description 32
- 239000004332 silver Substances 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 16
- -1 silver ions Chemical class 0.000 claims description 15
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 27
- 239000010802 sludge Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 150000003608 titanium Chemical class 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/50—Silver
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
(A)酸化チタン、並びにゼオライトを構成する組成に調製されたアルミニウム成分及び珪素成分を含む混合物をアルカリで処理して光触媒活性を有する酸化チタン−ゼオライト複合体を製造する工程、及び
(B)前記工程(A)で得られた酸化チタン−ゼオライト複合体を、銀イオンを含む溶液に浸漬してイオン交換により酸化チタン−ゼオライト複合体中のアルカリ金属イオンを銀イオンで置換する工程。
実施例1として、純粋試薬を用いてAg−酸化チタン−ゼオライト複合体を合成した製造方法を説明する。
製造方法の実施例2として製紙スラッジ(PS:Paper Sludge)をゼオライト原料としてAg−酸化チタン−ゼオライト複合体を製造する方法を説明する。
焼成カオリン(2SiO2−Al203) …… 50.6重量%、
アナターゼ型酸化チタン(TiO2) …… 21.5重量%、
タルク(4Si02−3MgO) …… 15.6重量%、
非晶質酸化アルミニウム(Al203) …… 12.2重量%。
製紙スラッジ焼却灰 …… 5.0g、
水ガラス …… 5.9g、
NaOH …… 6.3g、
水 ……55 g。
参考例としてAg−酸化チタン−ゼオライト混合物を作成した。
実施例1として記載した酸化チタン−ゼオライト複合体の製造工程で製造した金属置換前の酸化チタン−ゼオライト複合体を比較例1とする。本試料をNa−酸化チタン−ゼオライト複合体と表記する。
比較例2はCa−酸化チタン−ゼオライト複合体である。その製造方法として、実施例1でのAg−酸化チタン−ゼオライト複合体の製造工程におけるAgNO3水溶液を0.5MのCaCl2水溶液に置き換えて実施例1と同じ方法によりCa−酸化チタン−ゼオライト複合体を得た。
比較例3はFe−酸化チタン−ゼオライト複合体である。その製造方法として、比較例2で得たCa置換−酸化チタン−ゼオライト複合体1gと0.01MのFe2(N03)3水溶液30mlを50ml遠沈管に入れ、実施例1と同じ方法によりFe−酸化チタン−ゼオライト複合体を得た。
比較例4はCu−酸化チタン−ゼオライト複合体である。その製造方法として、実施例1でのAg−酸化チタン−ゼオライト複合体の製造工程におけるAgNO3水溶液を0.5MのCuCl2水溶液に置き換えて実施例1と同じ方法によりCu−酸化チタン−ゼオライト複合体を得た。
非極性分子としてトルエンを選び、実施例1及び参考例の吸着分解素材と比較例1〜4の酸化チタン−ゼオライト複合体についてトルエン吸着分解試験を行った。
Claims (2)
- 酸化チタンとゼオライトからなる骨格構造に銀イオンが結合している吸着分解素材において、
前記骨格構造はゼオライトの結晶体中に酸化チタンが分散してなる酸化チタン−ゼオライト複合体からなり、
該吸着分解素材はトルエン又はキシレンからなる低極性有機化合物のための吸着分解素材であることを特徴とする吸着分解素材。 - 前記ゼオライトはケイバン比が10未満のものである請求項1に記載の吸着分解素材。
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