JP4061464B2 - Catalyst for treating organic compounds - Google Patents
Catalyst for treating organic compounds Download PDFInfo
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- JP4061464B2 JP4061464B2 JP2002018734A JP2002018734A JP4061464B2 JP 4061464 B2 JP4061464 B2 JP 4061464B2 JP 2002018734 A JP2002018734 A JP 2002018734A JP 2002018734 A JP2002018734 A JP 2002018734A JP 4061464 B2 JP4061464 B2 JP 4061464B2
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- catalyst
- zinc
- atomic
- manganese
- spinel
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- 239000003054 catalyst Substances 0.000 title claims description 76
- 150000002894 organic compounds Chemical class 0.000 title claims description 54
- 239000002245 particle Substances 0.000 claims description 85
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 239000011701 zinc Substances 0.000 claims description 35
- 239000011572 manganese Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 30
- 229910052748 manganese Inorganic materials 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- 239000011029 spinel Substances 0.000 claims description 11
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- 239000007771 core particle Substances 0.000 description 27
- 239000002351 wastewater Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 14
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000011941 photocatalyst Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 6
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006247 magnetic powder Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000036284 oxygen consumption Effects 0.000 description 3
- 238000009283 thermal hydrolysis Methods 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HYKDWGUFDOYDGV-UHFFFAOYSA-N 4-anilinobenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=CC=C1 HYKDWGUFDOYDGV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101000845012 Macrovipera lebetina Disintegrin lebein-1-alpha Proteins 0.000 description 1
- 101000845007 Macrovipera lebetina Disintegrin lebein-1-beta Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- ZZNMWGVMOBOREI-VQTJNVASSA-N chembl464952 Chemical compound C1([C@H]2OC=3C4=C(C=5C=CC(C)(C)OC=5C=3C(=O)[C@@H]2O)OC(C=C4)(C)C)=CC=CC=C1 ZZNMWGVMOBOREI-VQTJNVASSA-N 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
【０００１】
【産業上の利用分野】
本発明は、農業集落廃水及び食品・水産加工廃水等の廃水中の有機化合物や大気中に含まれるアンモニア及びアセトアルデヒド等の有機化合物を短時間裡に効果的に吸着・分解することができるとともに工業的、経済的に有利に処理ができる有機化合物処理用触媒に関する。
【０００２】
【従来の技術】
人口が増加し、経済が成長、発展することにより生活活動や産業活動に伴うさまざまな廃水や臭気成分が多量に排出されている。
近年、殊に、わが国の経済は飛躍的な成長をみせ、農業集落、水産集落、食品加工業、水産加工業等から有機化合物含有廃水が大量に排出され、一方、技術革新に伴って臭気成分であるアンモニア及びアセトアルデヒド等の有機化合物が大気中に排出され、生活環境の破壊が急速に進んでいる。
そこで、これら廃水中の有機化合物や大気中の有機化合物を短時間裡に効果的に処理することができる触媒の開発が強く要求される。
【０００３】
従来、廃水中や大気中の有機化合物を処理する触媒としては、有機化合物を物理化学的に吸着させるものや酸化チタン等の光触媒反応をする光触媒を用いて紫外線を照射し、光触媒を活性化して光触媒の強力な酸化作用を利用して有機化合物を分解させる光触媒等が広く知られている。
【０００４】
前者の方法は、触媒として活性炭やゼオライトを用いるものであり、広く実用化されているが、廃水や大気中の有機化合物を物理化学的に吸着させて処理するものであるから、吸着が飽和に達した後は有機化合物が吸着している触媒をそのまま廃棄しなければならず、生活環境を改善することにはならない。そこで、廃水や大気中の有機化合物を吸着し、吸着した有機化合物を分解して浄化する作用を有すると共に、触媒自体の再利用や再生が可能である後者の光触媒が注目をあびている。
【０００５】
従来、光触媒としては、例えば、▲１▼チタン、ケイ素及びジルコニウムよりなる群から選ばれる少なくとも２種の元素の酸化物とマンガン・鉄・コバルト・ニッケル・セリウム・タングステン・銅・銀・金・白金・パラジウム・ロジウム・ルテニウム及びイニジウムよりなる群から選ばれる少なくとも１種の元素とを含有する触媒（特許第３２２６５６５号公報）、▲２▼磁性粉の表面に、光触媒作用を有する物質を被覆した磁性を有する光触媒（特開平６−１５４６２０号公報）、▲３▼マンガンの酸化物と鉄の酸化物および／またはマンガンと鉄の複合酸化物を含有する触媒（特開平７−２３２０６３号公報）、▲４▼軟磁性粉末表面にアナターゼ型チタニア又は酸化亜鉛をコーティングした光触媒（特開平１１−１７９２１２号公報)、▲５▼Ｍｎ−Ｚｎフェライト等の磁性酸化物粉末の表面に光触媒を被覆した光触媒被覆磁性酸化物粉末（特開２０００−２３７５４２号公報）等が知られている。
【０００６】
【発明が解決しようとする課題】
廃水中や大気中の有機化合物を短時間裡に効果的に処理することができる触媒は現在最も要求されているところであるが、前出公知の触媒は未だ十分なものとは言い難いものである。
【０００７】
即ち、前出▲１▼記載の触媒は、触媒の存在下、廃水を高温高圧下で分子状酸素に接触させることにより酸化処理するものであり、オートクレーブ等の設備が必要であり、工業的、経済的とはいえない。
【０００８】
前出▲２▼記載の触媒は、溶媒中での光触媒反応後、溶媒中から光触媒を磁石に吸引して除去するために具体的には、マグネタイト等の酸化鉄を磁性粉として使用しており、該マグネタイト粒子は通常Ｆｅ2+がＦｅ3+に対し４０原子％以上と多く、後出比較例に示す通り、十分な処理効果を得ることが困難である。
【０００９】
前出▲３▼記載の触媒は、上記▲１▼記載の触媒と同様の処理条件下で使用するものであり、工業的、経済的とはいえない。また、触媒の存在下において１００〜５００時間の長時間処理しても、有機化合物の量は化学的酸素消費量（ＣＯＤ）濃度で示した場合、１７０ｍｇ／ｌ程度までにしか浄化されない。その為、例えば農業用用水の基準値である５ｍｇ／ｌ以下にすることは困難であり、処理効率が悪いという問題がある。
【００１０】
前出▲４▼記載の触媒は、芯粒子である軟磁性粉末がＦｅ2Ｏ3、ＺｎＯ、ＭｇＯを所定の配合比で混合し、次いで、９００℃で仮焼後粉砕する、所謂、乾式法により製造されているため後出比較例に示す通り、通常、Ｆｅ2+を含んでいないか又は含んでいるとしてもＦｅ3+に対し高々２原子％未満の少量であり、しかも平均粒子径が３〜１００μｍと大きいため、後出比較例に示す通り、有機化合物の処理効果が十分とは言い難い。
【００１１】
前出▲５▼記載の触媒は、芯粒子であるＭｎ−Ｚｎフェライトを、粒径１００μｍ以下に粉砕していることから、所謂、乾式法により得られたものであり、同様に、Ｆｅ2+を含んでいないか又は含んでいるとしても少量であり、しかも平均粒子径も大きいものであるから、後出比較例に示す通り、有機化合物の処理効果が十分とは言い難い。
【００１２】
そこで、本発明は、廃水中や大気中の有機化合物を短時間裡に効果的に処理することができるとともに、オートクレーブ等の特殊な装置を使用することなく工業的、経済的に有利に処理することができる触媒を得ることを技術的課題とする。
【００１３】
【課題を解決する為の手段】
前記技術的課題は、次の通りの本発明によって達成できる。
【００１４】
即ち、本発明は、マンガン及び亜鉛を含むスピネル型酸化鉄粒子の粒子表面に酸化チタンが被覆されている複合酸化物粒子からなる平均粒子径が０.０３〜０.８μｍの複合酸化物粒子粉末であり、上記スピネル型酸化鉄粒子はＦｅ3+に対し２〜２０原子％のＦｅ2+を有し、且つ、上記マンガン及び亜鉛を含むスピネル型酸化鉄粒子がＦｅ 3+ に対し５〜２５原子％のマンガン及びＦｅ 3+ に対し５〜２５原子％の亜鉛を含んでいることを特徴とする有機化合物の吸着又は分解用触媒。（発明１）
また、本発明は、酸化チタンの量が、マンガン及び亜鉛を含むスピネル型酸化鉄粒子１重量に対し０.１〜２０重量比であることを特徴とする発明１記載の有機化合物の吸着又は分解用触媒。（発明２）
また、本発明は、複合酸化物粒子粉末のＢＥＴ比表面積が８０〜２５０ｍ2／ｇであることを特徴とする発明１乃至発明２のいずれかに記載の有機化合物の吸着又は分解用触媒（発明３）である。
【００１５】
本発明の構成をより詳しく説明すれば、次の通りである。
【００１６】
先ず、本発明に係る有機化合物処理用触媒について述べる。
本発明に係る有機化合物処理用触媒は、マンガン及び亜鉛を含むスピネル型酸化鉄粒子を芯粒子とし、該芯粒子の表面に酸化チタンが被覆されている複合酸化物粒子からなる複合酸化物粒子粉末である。
【００１７】
本発明における芯粒子は、Ｆｅ3+に対し２〜２０原子％のＦｅ2+を有している。２原子％未満の場合、２０原子％を越える場合のいずれの場合にも、本発明の目的とする有機化合物処理用触媒を得ることができない。有機化合物の処理効果を考慮すると、３〜１６原子％が好ましく、より好ましくは３〜１３原子％である。
【００１８】
本発明における芯粒子の粒子形状は等方的形状の粒子であれば、球状、立方体状、八面体状、多面体状等のいずれでもよい。ＢＥＴ比表面積の大きさを考慮すれば球状が最も好ましい。
【００１９】
本発明における芯粒子は、平均粒子径が０.０３〜０.８μｍである。
０.０３μｍ未満の場合には、酸化チタン被覆工程時に微粒子であることによって溶解し、複合酸化物粒子粉末を得ることができない。
０.８μｍを越える場合には、ＢＥＴ比表面積が８０ｍ2／ｇ以上の複合酸化物粒子粉末を得ることが困難となる。有機化合物の処理効果を考慮すると、０.０５〜０.８μｍが好ましく、より好ましくは０.０８〜０.７μｍである。
【００２０】
本発明における芯粒子のマンガン量は、Ｆｅ3+に対しＭｎ換算で５〜２５原子％が好ましく、より好ましくは１０〜２５原子％である。
５原子％未満の場合、２５原子％を越える場合のいずれの場合も本発明の目的とする有機化合物処理用触媒を得ることが困難である。
【００２１】
本発明における芯粒子の亜鉛量は、Ｆｅ3+に対しＺｎ換算で５〜２５原子％が好ましく、より好ましくは８〜２５原子％、更に好ましくは１３〜２５原子％である。
５原子％未満の場合、２５原子％を越える場合のいずれの場合にも、本発明の目的とする有機化合物処理用触媒を得ることが困難である。
【００２２】
本発明における芯粒子のマンガンと亜鉛の合計量は、Ｆｅ3+に対しＭｎ及びＺｎ換算で３０〜４８原子％が好ましく、より好ましくは３５〜４８原子％である。３０原子％未満の場合には、Ｆｅ2+の量が２０原子％を越えるため本発明の目的とする有機化合物処理用触媒を得ることが困難である。４８原子％を越える場合には、Ｆｅ2+の量が２原子％未満となるため、本発明の目的とする有機化合物処理用触媒を得ることが困難である。
【００２３】
本発明における酸化チタン被覆量は芯粒子に対し、０.１〜２０重量比である。
０.１重量比未満の場合、２０重量比を越える場合のいずれの場合にも、本発明の目的とする有機化合物処理用触媒を得ることが困難である。
有機化合物の処理効果を考慮すると０.１３〜２０重量比が好ましく、より好ましくは０.１５〜２０重量比である。
【００２４】
本発明における複合酸化物粒子粉末の粒子形状は芯粒子の粒子形状をほぼ保持している。
【００２５】
本発明における複合酸化物粒子粉末は、平均粒子径が０.０３〜０.８μｍである。
０.０３μｍ未満の複合酸化物粒子粉末を得ることは困難である。
０.８μｍを越える場合には、目的とするＢＥＴ比表面積が８０ｍ2／ｇ以上の複合酸化物粒子粉末を得ることが困難となる。有機化合物の処理効果を考慮すると０.０５〜０.８μｍが好ましく、より好ましくは０.０８〜０.７μｍである。
【００２６】
本発明における複合酸化物粒子粉末は、ＢＥＴ比表面積が８０〜２５０ｍ2／ｇである。
８０ｍ2／ｇ未満の場合には、酸化チタン被覆量が芯粒子に対し０.１重量比未満となり、本発明の目的とする有機化合物処理用触媒を得ることが困難である。
２５０ｍ2／ｇを越える場合には、酸化チタン被覆量は十分であるが、芯粒子の大きさが相対的に小さくなり、酸化チタン被覆量が２０重量比を超え、本発明の目的とする有機化合物処理用触媒を得ることが困難となる。
【００２７】
本発明に係る有機化合物処理用触媒を臭気成分であるアンモニアやアセトアルデヒド等を含む大気ガスの処理に用いた場合には、臭気成分がアンモニアである場合、処理開始後１時間で１７０ｐｐｍ以下、より好ましくは１６０ｐｐｍ以下にすることができる。処理時に紫外線照射した場合には、処理開始後３０分間で１５０ｐｐｍ以下、より好ましくは１４０ｐｐｍ以下にすることができる。
【００２８】
臭気成分がアセトアルデヒドである場合、処理開始後１時間で１６０ｐｐｍ以下、より好ましくは１５０ｐｐｍ以下にすることができる。処理時に紫外線照射した場合には、処理開始後３０分間で１５０ｐｐｍ以下、より好ましくは１４０ｐｐｍ以下にすることができる。
【００２９】
本発明に係る有機化合物処理用触媒を廃水中の有機化合物の処理に用いた場合には、オートクレーブ等の特殊な装置を使用することなく簡単な装置で格段に速く浄化することができ、また、処理水からの使用済触媒の分離も容易である。即ち、攪拌１５分後には、１０ｍｇ／ｌ以下、好ましくは８ｍｇ／ｌ以下とすることができる。攪拌４５分後には、８ｍｇ／ｌ以下、好ましくは６ｍｇ／ｌ以下とすることができる。処理時に紫外線照射した場合には、攪拌１５分後に６ｍｇ／ｌ以下、好ましくは５ｍｇ／ｌ以下にすることができる。
【００３０】
次に、本発明に係る有機化合物処理用触媒の製造法について述べる。
【００３１】
本発明における芯粒子であるマンガン及び亜鉛を含むスピネル型酸化鉄粒子は、第一鉄塩水溶液とアルカリ水溶液とを反応して得られた水酸化第一鉄コロイド又は鉄含有沈殿物を含む反応懸濁液に空気等の酸素含有ガスを通気して上記水酸化第一鉄又は鉄含有沈殿物を酸化することによりスピネル型酸化鉄を製造するにあたり、酸素含有ガスを通気する前にあらかじめ所定量のマンガン及び亜鉛を存在させておくことにより製造する（以下、「湿式法」という。）ことができる。
【００３２】
スピネル型酸化鉄粒子を製造するにあたり、酸化反応時のｐＨを調製することにより各種の等方的形状を有する粒子を得ることができる。
【００３３】
なお、乾式法、即ち、ヘマタイト粒子等の酸化鉄粒子とマンガン酸化物粒子又は加熱によりマンガン酸化物となり得るマンガン化合物と亜鉛酸化物又は加熱により亜鉛酸化物となり得る亜鉛化合物とを混合した後１０００〜１３００℃で加熱焼成後粉砕して得られるマンガン−亜鉛フェライト粒子粉末は、前述した通り、通常Ｆｅ2+をほとんど有していないため後出比較例に示す通り、有機物処理用触媒として十分な効果を得ることは困難である。
【００３４】
本発明における芯粒子の酸化チタンによる被覆は、芯粒子と水溶性チタン水溶液とを混合して得られた懸濁液を温度７０〜１００℃の範囲内で５〜３０時間加熱して熱加水分解反応した後、沈殿物を常法により濾別・水洗・乾燥すればよい。
【００３５】
水溶性チタン化合物溶液としては、硫酸チタン水溶液や塩化チタンと硫酸水溶液との混合溶液等を使用することができる。
水溶性チタン化合物の添加量は、芯粒子に対しＴｉＯ2換算で０.１〜２０重量比である。
【００３６】
次に、本発明に係る有機化合物処理用触媒は、後出実施例に示す通り、常温、常圧下において使用することができるので、被処理大気と接触する場所や位置に設置したり、廃液中に添加後、攪拌等すればよい。触媒は、粉末状態のままでも使用することができ、必要により、各種形状や各種サイズに成形して使用することもできる。
【００３７】
【発明の実施の形態】
本発明の代表的な実施の形態は、次の通りである。
尚、以下の実施の形態並びに後出実施例及び比較例におけるマンガン及び／又は亜鉛を含むスピネル型酸化鉄粒子粉末、マンガン−亜鉛フェライト粒子粉末及び複合酸化物粒子粉末の平均粒子径は、透過型電子顕微鏡により撮影した写真（×１００００）を拡大した写真（×４００００）に示されている３００個の粒子について測定したマーチン径により求めた値である。
【００３８】
マンガン及び／又は亜鉛を含むスピネル型酸化鉄粒子粉末、マンガン−亜鉛フェライト粒子粉末及び複合酸化物粒子粉末のＢＥＴ比表面積値は、「Ｍｏｎｏ Ｓｏｒｂ ＭＳ−ＩＩ」（商品名：湯浅アイオニックス株式会社（製））を用いてＢＥＴ法により求めた値で示した。
【００３９】
マンガン及び／又は亜鉛を含むスピネル型酸化鉄粒子粉末、マンガン−亜鉛フェライト粒子粉末及び複合酸化物粒子粉末のＦｅ2+量は、下記の化学分析法により求めた値で示した。
【００４０】
即ち、不活性ガス雰囲気下において、スピネル型酸化鉄粒子粉末０.５ｇに対しリン酸と硫酸を２：１の割合で含む混合溶液２５ｃｃを添加し、スピネル型酸化鉄粒子粉末を溶解する。この溶解水溶液の希釈液に指示薬としてジフェニルアミンスルホン酸を数滴加えた後、重クロム酸カリウム水溶液を用いた酸化還元滴定を行った。希釈液が紫色を呈した時を終点とし、該終点に至るまでに使用した重クロム酸水溶液の量から計算して求めた。
【００４１】
マンガン及び／又は亜鉛を含むスピネル型酸化鉄粒子粉末、マンガン−亜鉛フェライト粒子粉末及び複合酸化物粒子粉末の全鉄量、Ｍｎ量及びＺｎ量は、ＩＣＰ発光分光分析装置ＳＰＳ４０００（セイコー電子工業株式会社（製））を用いてプラズマ発光分光法により求めた。
【００４２】
マンガン及び／又は亜鉛を含むスピネル型酸化鉄粒子粉末、マンガン−亜鉛フェライト粒子粉末及び複合酸化物粒子粉末のＦｅ3+量は、上記全鉄量から上記Ｆｅ2+量を差し引いた値で示した。
【００４３】
容器中のＮＨ3量は、アンモニアガス検知管Ｎｏ.３Ｍ及びＮｏ.３Ｌａ（株式会社ガステック（製））を用いて測定した値で示した。
なお、ＮＨ3濃度が３０〜５００ｐｐｍの場合にＮｏ.３Ｍを使用し、ＮＨ3濃度が１００ｐｐｍ以下の場合、Ｎｏ.３Ｌａを使用した。
【００４４】
容器中のアセトアルデヒド量は、アセトアルデヒドガス検知管Ｎｏ.９２（株式会社ガステック（製））を用いて測定した値で示した。
【００４５】
廃水中の有機化合物の量は、廃水中の有機化合物含有量の指標の１つである化学的酸素消費量（以下、ＣＯＤとする。）をＪＩＳ Ｋ０１０２−１９９３の「１７．１００℃における過マンガン酸カリウムによる酸素消費量（ＣＯＤ）」に従って測定した値で示した。
【００４６】
＜有機化合物処理用触媒の製造＞
湿式法で製造した平均粒子径が０.３μｍであって、ＢＥＴ比表面積が１１.７ｍ2／ｇであって、Ｆｅ2+をＦｅ3+に対し７.５原子％含有している球状のマンガン及び亜鉛を含むスピネル型酸化鉄粒子（Ｍｎ量はＦｅ3+に対し２２.５原子％、Ｚｎ量はＦｅ3+に対し１４.６原子％)（以下、「芯粒子Ａ」とする。)１００ｇを含む懸濁液１ ｌと硫酸チタニル（ＴｉＯＳＯ4）１５１ｇ（ＴｉＯ2換算で５０ｇに相当）を純水２ ｌに溶解した硫酸チタニル溶液とを混合して全容３ ｌとした後、昇温し、温度９５℃で２０時間攪拌して硫酸チタニルの熱加水分解反応を行うことにより上記芯粒子の粒子表面にアナターゼ型酸化チタンを被覆させた。
粒子表面がアナターゼ型酸化チタンで被覆されている芯粒子粉末を常法により濾別、水洗した後乾燥して複合酸化物粒子粉末Ａ（以下、「触媒Ａ」とする。）を得た。得られた触媒Ａは、芯粒子に対し１重量比のアナターゼ型酸化チタンで被覆されている球状粒子であって平均粒子径が０.３μｍであってＢＥＴ比表面積が１７６ｍ2／ｇであり、Ｆｅ2+量は、Ｆｅ3+に対し７.５原子％であった。Ｍｎ量は、Ｆｅ3+に対し２２.５重量原子％、Ｚｎ量はＦｅ3+に対し１４.６原子％であった。
【００４７】
＜アンモニアを含む大気への使用▲１▼＞
使用例１
上面が石英ガラスからなり、底面及び側面がアクリル製樹脂からなる容量５ ｌの密閉可能な容器を準備し、該容器の内部にファンと五徳状のサンプル台を設置した。そして、上記触媒Ａ１００ｍｇをアルミ箔に盛り、サンプル台の上に置いた。
上記容器の側面上部に設けられたガス導入口からアンモニアガスを大気中に導入し、密閉した後ファンを回転させ、５分後にアンモニアガス検知管でアンモニア濃度を測定したところ、当初のアンモニア濃度は２５０ｐｐｍであった。その後、１５分間隔でアンモニア濃度を測定したところアンモニア濃度は時間の経過にともなって減少し、１時間後には６０ｐｐｍとなり飽和した。
【００４８】
＜アンモニアを含む大気への使用▲２▼＞
使用例２
サンプル台の上に置いた触媒Ａ上で紫外線強度が１.０(ｍＷ／ｃｍ2）となる様にブラックライトを照射をした以外は、上記使用例１と同様にして大気中のアンモニア濃度を測定した。
当初のアンモニア濃度は使用例１と同様に２５０ｐｐｍであり、紫外線照射３０分間経過後には４４ｐｐｍとなった。
【００４９】
＜アセトアルデヒドを含む大気への使用▲１▼＞
使用例３
上記触媒Ａを１０００ｍｇを用いるとともに、アセトアルデヒドを含む大気を用いた以外は使用例１と同様にして操作を行った。
アセトアルデヒドガスを導入開始後５分間経過した時にアセトアルデヒドガス検知管でアセトアルデヒド濃度を測定したところ、当初のアセトアルデヒド濃度は２４０ｐｐｍであり、１時間経過後には１００ｐｐｍとなった。
【００５０】
＜アセトアルデヒドを含む大気への使用▲２▼＞
使用例４
サンプル台の上に置いた触媒Ａ上で紫外線強度が１.０(ｍＷ／ｃｍ2)となる様にブラックライトを照射した以外は、使用例３と同様にして操作を行った。
アセトアルデヒドガスを導入開始後５分間経過した時にガス検知管でアセトアルデヒド濃度を測定したところ、当初のアセトアルデヒド濃度は２４０ｐｐｍであり、紫外線照射３０分間経過後には５０ｐｐｍとなった。
【００５１】
＜廃水中のＣＯＤ成分への使用▲１▼＞
使用例５
ＣＯＤ成分が７０ｍｇ／ｌの廃水５００ｍｌを準備し、該廃水中に上記触媒１０ｇを添加し、１５分間攪拌した後静置した。
１５分間静置して廃水中の懸濁物が沈降した後、上澄液を採取しＣＯＤ成分を測定したところ５ｍｇ／ｌであった。
＜廃水中のＣＯＤ成分への使用▲２▼＞
使用例６
水面上で紫外線強度が１.０(ｍＷ／ｃｍ2）となる様にブラックライトを照射した以外は、使用例５と同様にして操作を行った。
上澄液中のＣＯＤ成分は３ｍｇ／ｌであった。
【００５２】
【作用】
本発明において最も重要な点は、Ｆｅ3+に対しＦｅ2+を２〜２０原子％有するマンガン及び亜鉛を含むスピネル型酸化鉄粒子を用い、該酸化鉄粒子の粒子表面に特定量の酸化チタンを被覆した複合酸化物粒子からなる平均粒子径が０.０３〜０.８μｍの複合酸化物粒子粉末は、有機化合物処理用触媒として用いた場合、大気中の臭気成分や廃水中のＣＯＤ成分等の有機化合物を短時間裡に効果的に処理することができるという事実である。
【００５３】
有機化合物を短時間裡に効果的に処理することができる理由については、未だ明らかではないが、本発明者は、後出比較例に示す通り、マンガン及び亜鉛を含むスピネル型酸化鉄粒子のＦｅ2+が特定範囲外である複合酸化物粒子粉末を触媒として用いた場合、平均粒子径が特定範囲外である複合酸化物粒子粉末を触媒として用いた場合、亜鉛を含んでおらずマンガンのみを含むスピネル型酸化鉄粒子を触媒として用いた場合、マンガンを含んでおらず亜鉛のみを含むスピネル型酸化鉄粒子を触媒として用いた場合、酸化チタンによって被覆されていないＦｅ2+を特定量有するマンガン及び亜鉛を含むスピネル型酸化鉄粒子を触媒として用いた場合、酸化チタン微粒子粉末単独を触媒として用いた場合、乾式法で得られたマンガン−亜鉛フェライト粒子を触媒として用いた場合のいずれの場合にも、大気中の臭気成分や廃水中のＣＯＤ成分等の有機化合物を効果的に処理して浄化することができないことから、芯粒子としてＦｅ2+を特定量有するマンガン及び亜鉛を含むスピネル型酸化鉄粒子を用いたことと該スピネル型酸化鉄粒子の粒子表面に被覆されている特定量の酸化チタンとの相乗効果によるものと考えている。
【００５４】
【実施例】
次に、実施例並びに比較例により本発明を説明する。
【００５５】
＜有機化合物の吸着・分解触媒の製造＞
芯粒子Ｂ〜Ｊ
芯粒子としてマンガン及び／又は亜鉛を含むスピネル型酸化鉄粒子粉末Ｂ乃至Ｊを準備した。このマンガン及び亜鉛を含むスピネル型酸化鉄粒子粉末の該特性を表１に示す。
【００５６】
【表１】
実施例１〜１０、比較例１〜９
芯粒子の種類、被覆酸化チタンの量を種々変化させた以外は、前記発明の実施の形態と同様にして触媒Ｂ〜Ｒを得た。
このときの主要製造条件及び得られた触媒の諸特性を表２及び表３に示す。
【００５８】
比較の為、比較例８として前記芯粒子Ａを酸化チタンで被覆することなくそのまま触媒Ｓとして用いた。また、比較例９として硫酸チタニル１５１ｇ（ＴｉＯ2換算で５０ｇに相当）を純水２ ｌに溶解した硫酸チタニルを全容３ ｌとした後、昇温し、温度９５℃で２０時間攪拌して硫酸チタニルの熱加水分解反応を行うことにより得られた平均粒子径０.００８μｍであってＢＥＴ比表面積２１２ｍ2／ｇの酸化チタン粒子粉末を触媒Ｔとして別途準備した。
【００５９】
【表２】
【表３】
＜アンモニアを含む大気への使用＞
使用例７〜使用例１６、比較使用例１〜１０
触媒の種類及び触媒の有無を種々変化させた以外は、前記使用例１及び前記使用例２と同様の操作を行った。その結果を表４に示す。
【００６２】
【表４】
＜アセトアルデヒドを含む大気への使用＞
使用例１７〜２６、比較使用例１１〜２０
触媒の種類及び触媒の有無を種々変化させた以外は、前記使用例３及び前記使用例４と同様の操作を行った。その結果を表５に示す。
【００６４】
【表５】
＜廃水中のＣＯＤ成分への使用＞
使用例２７〜３６、比較使用例２１〜３０
触媒の種類及び触媒の有無を種々変化させた以外は、前記使用例５及び前記使用例６と同様の操作を行った。その結果を表６に示す。
【００６６】
【表６】
【発明の効果】
本発明に係る触媒は、前出実施例に示した通り、廃水中のＣＯＤ成分や大気中の臭気成分等の有機化合物を短時間裡に効果的に処理することができるとともに、オートクレーブ等の特殊な装置を使用することなく工業的、経済的に有利に処理することができるので、有機化合物処理用触媒として好適である。
【００６８】
更に、本発明に係る上記触媒は、吸着した有機化合物を分解することができるので、触媒を廃棄することなく再利用や再生が可能であり、生活環境の改善に大いに役立つことが期待できる。
【００６９】
なお、本発明に係る上記触媒を廃水に用いた場合、使用済触媒は処理後の浄化水中において容易に沈殿するので濾別、分離が容易である。[0001]
[Industrial application fields]
INDUSTRIAL APPLICABILITY The present invention is capable of effectively adsorbing and decomposing organic compounds in wastewater such as agricultural settlement wastewater and food / fishery processing wastewater and organic compounds such as ammonia and acetaldehyde contained in the air in a short time and industrial The present invention relates to a catalyst for treating an organic compound that can be advantageously treated economically and economically.
[0002]
[Prior art]
As the population increases and the economy grows and develops, various wastewater and odorous components accompanying daily activities and industrial activities are discharged in large quantities.
In recent years, especially Japan's economy has shown dramatic growth, and a large amount of organic compound-containing wastewater has been discharged from agricultural communities, fishery communities, food processing industries, fishery processing industries, etc. Organic compounds such as ammonia and acetaldehyde are discharged into the atmosphere, and the destruction of the living environment is rapidly progressing.
Therefore, there is a strong demand for the development of a catalyst that can effectively treat organic compounds in waste water and organic compounds in the atmosphere in a short time.
[0003]
Conventionally, as a catalyst for treating organic compounds in wastewater or in the atmosphere, photocatalysts that adsorb organic compounds physicochemically or photocatalytic reactions such as titanium oxide are used to irradiate ultraviolet rays to activate the photocatalyst. Photocatalysts for decomposing organic compounds using the strong oxidizing action of photocatalysts are widely known.
[0004]
The former method uses activated carbon or zeolite as a catalyst and is widely put to practical use. However, the adsorption is saturated because organic compounds in wastewater and air are adsorbed physicochemically. After reaching, the catalyst on which the organic compound is adsorbed must be discarded as it is, and the living environment will not be improved. Therefore, the latter photocatalyst has attracted attention because it has an action of adsorbing organic compounds in wastewater and air, decomposing and purifying the adsorbed organic compounds, and enabling reuse and regeneration of the catalyst itself.
[0005]
Conventionally, as photocatalysts, for example, (1) oxides of at least two elements selected from the group consisting of titanium, silicon and zirconium and manganese, iron, cobalt, nickel, cerium, tungsten, copper, silver, gold, platinum・ A catalyst containing at least one element selected from the group consisting of palladium, rhodium, ruthenium and inidium (Japanese Patent No. 3226565), (2) Magnetic property in which the surface of the magnetic powder is coated with a substance having a photocatalytic action (3) A catalyst containing a manganese oxide and an iron oxide and / or a composite oxide of manganese and iron (Japanese Patent Application Laid-Open No. 7-232033), 4) Photocatalyst with soft magnetic powder surface coated with anatase titania or zinc oxide (Japanese Patent Laid-Open No. 11-179212) (5) A photocatalyst-coated magnetic oxide powder (Japanese Patent Laid-Open No. 2000-237542) or the like in which the surface of a magnetic oxide powder such as Mn—Zn ferrite is coated with a photocatalyst is known.
[0006]
[Problems to be solved by the invention]
Catalysts that can effectively treat organic compounds in wastewater and air in a short time are currently in great demand, but the above-mentioned known catalysts are still inadequate. .
[0007]
That is, the catalyst described in the above item (1) is an oxidation treatment by contacting waste water with molecular oxygen under high temperature and high pressure in the presence of a catalyst, which requires equipment such as an autoclave, industrial, It is not economical.
[0008]
Specifically, the catalyst described in (2) above uses iron oxide such as magnetite as magnetic powder in order to remove the photocatalyst from the solvent by attracting it to the magnet after the photocatalytic reaction in the solvent. The magnetite particles usually have a large amount of Fe 2+ of 40 atom% or more with respect to Fe 3+, and it is difficult to obtain a sufficient treatment effect as shown in a comparative example.
[0009]
The catalyst described in (3) above is used under the same treatment conditions as the catalyst described in (1) above, and is not industrial or economical. Further, even if the treatment is performed for a long time of 100 to 500 hours in the presence of the catalyst, the amount of the organic compound can be purified only to about 170 mg / l in terms of chemical oxygen consumption (COD) concentration. Therefore, for example, it is difficult to make it 5 mg / l or less, which is the reference value for agricultural water, and there is a problem that processing efficiency is poor.
[0010]
The catalyst described in (4) above is a so-called dry method in which soft magnetic powder as core particles is mixed with Fe 2 O 3 , ZnO, and MgO at a predetermined blending ratio, then calcined at 900 ° C. and then pulverized. As shown in the comparative example below, normally, Fe 2+ is not contained or is contained in a small amount of less than 2 atomic% at the most with respect to Fe 3+ , and the average particle size is Since it is as large as 3 to 100 μm, it is difficult to say that the treatment effect of the organic compound is sufficient as shown in a comparative example.
[0011]
The catalyst described in the above item (5) is obtained by a so-called dry method because Mn—Zn ferrite as a core particle is pulverized to a particle size of 100 μm or less. Similarly, Fe 2+ Therefore, it is difficult to say that the treatment effect of the organic compound is sufficient as shown in Comparative Examples below.
[0012]
Therefore, the present invention can effectively treat organic compounds in waste water and the atmosphere in a short time, and can be advantageously treated industrially and economically without using a special device such as an autoclave. It is a technical problem to obtain a catalyst that can be used.
[0013]
[Means for solving the problems]
The technical problem can be achieved by the present invention as follows.
[0014]
That is, the present invention provides a composite oxide particle powder having an average particle size of 0.03 to 0.8 μm comprising composite oxide particles in which titanium oxide is coated on the surface of spinel iron oxide particles containing manganese and zinc. The spinel-type iron oxide particles have 2 to 20 atomic% of Fe 2+ with respect to Fe 3+ , and the spinel-type iron oxide particles containing manganese and zinc have 5 to 25 with respect to Fe 3+. A catalyst for adsorbing or decomposing an organic compound , comprising 5 to 25 atomic percent of zinc with respect to atomic percent of manganese and Fe3 + . (Invention 1)
Further, the present invention is that the amount of titanium oxide, adsorption of the organic compounds of the invention 1 Symbol mounting, characterized in that a spinel-type iron oxide particles 1 wt relative 0.1-20 weight containing manganese and zinc or Catalyst for decomposition . (Invention 2 )
Further, the present invention is adsorbed or cracking catalyst (invention of the organic compound according to any one of Inventions 1 to invention 2, wherein the BET specific surface area of the composite oxide particles is 80~250m 2 / g 3 ).
[0015]
The configuration of the present invention will be described in more detail as follows.
[0016]
First, the organic compound treatment catalyst according to the present invention will be described.
The catalyst for treating an organic compound according to the present invention is a composite oxide particle powder comprising composite oxide particles in which spinel iron oxide particles containing manganese and zinc are used as core particles, and the surface of the core particles is coated with titanium oxide. It is.
[0017]
The core particle in this invention has 2-20 atomic% Fe <2+> with respect to Fe < 3+ >. In any case of less than 2 atomic% or exceeding 20 atomic%, the target organic compound treatment catalyst of the present invention cannot be obtained. Considering the treatment effect of the organic compound, 3 to 16 atomic% is preferable, and 3 to 13 atomic% is more preferable.
[0018]
As long as the particle shape of the core particle in the present invention is an isotropic particle, it may be spherical, cubic, octahedral, polyhedral or the like. Considering the size of the BET specific surface area, the spherical shape is most preferable.
[0019]
The core particles in the present invention have an average particle diameter of 0.03 to 0.8 μm.
When it is less than 0.03 μm, it dissolves due to the fine particles during the titanium oxide coating step, and composite oxide particle powder cannot be obtained.
When it exceeds 0.8 μm, it becomes difficult to obtain a composite oxide particle powder having a BET specific surface area of 80 m 2 / g or more. Considering the treatment effect of the organic compound, the thickness is preferably 0.05 to 0.8 μm, more preferably 0.08 to 0.7 μm.
[0020]
The amount of manganese in the core particles in the present invention is preferably 5 to 25 atomic%, more preferably 10 to 25 atomic% in terms of Mn with respect to Fe 3+ .
In the case of less than 5 atomic% and in the case of exceeding 25 atomic%, it is difficult to obtain an organic compound treatment catalyst that is the object of the present invention.
[0021]
In the present invention, the amount of zinc in the core particles is preferably 5 to 25 atomic%, more preferably 8 to 25 atomic%, and still more preferably 13 to 25 atomic% in terms of Zn with respect to Fe 3+ .
In the case of less than 5 atomic% and in the case of exceeding 25 atomic%, it is difficult to obtain the target organic compound treatment catalyst of the present invention.
[0022]
In the present invention, the total amount of manganese and zinc in the core particles is preferably 30 to 48 atomic%, more preferably 35 to 48 atomic% in terms of Mn and Zn with respect to Fe 3+ . If it is less than 30 atomic%, the amount of Fe 2+ exceeds 20 atomic%, and it is difficult to obtain the organic compound treatment catalyst of the present invention. When it exceeds 48 atomic%, the amount of Fe 2+ is less than 2 atomic%, and it is difficult to obtain the organic compound treatment catalyst of the present invention.
[0023]
The coating amount of titanium oxide in the present invention is 0.1 to 20 weight ratio with respect to the core particles.
In the case of less than 0.1 weight ratio or in the case of exceeding 20 weight ratio, it is difficult to obtain the target organic compound treatment catalyst of the present invention.
In consideration of the treatment effect of the organic compound, a 0.13 to 20 weight ratio is preferable, and a 0.15 to 20 weight ratio is more preferable.
[0024]
The particle shape of the composite oxide particle powder in the present invention substantially retains the particle shape of the core particle.
[0025]
The composite oxide particle powder in the present invention has an average particle size of 0.03 to 0.8 μm.
It is difficult to obtain a composite oxide particle powder of less than 0.03 μm.
When it exceeds 0.8 μm, it becomes difficult to obtain a composite oxide particle powder having a target BET specific surface area of 80 m 2 / g or more. Considering the treatment effect of the organic compound, the thickness is preferably 0.05 to 0.8 μm, more preferably 0.08 to 0.7 μm.
[0026]
The composite oxide particle powder in the present invention has a BET specific surface area of 80 to 250 m 2 / g.
When the amount is less than 80 m 2 / g, the titanium oxide coating amount is less than 0.1 weight ratio with respect to the core particles, and it is difficult to obtain the target organic compound treatment catalyst of the present invention.
If it exceeds 250 m 2 / g, the amount of titanium oxide coating is sufficient, but the size of the core particles becomes relatively small, and the amount of titanium oxide coating exceeds 20 weight ratio. It becomes difficult to obtain a compound processing catalyst.
[0027]
When the organic compound treatment catalyst according to the present invention is used for treatment of atmospheric gas containing ammonia, acetaldehyde, and the like as odor components, when the odor component is ammonia, 170 ppm or less, more preferably 1 hour after the start of treatment. Can be made 160 ppm or less. When ultraviolet rays are irradiated during the treatment, it can be reduced to 150 ppm or less, more preferably 140 ppm or less in 30 minutes after the treatment starts.
[0028]
When the odor component is acetaldehyde, it can be 160 ppm or less, more preferably 150 ppm or less in 1 hour after the start of treatment. When ultraviolet rays are irradiated during the treatment, it can be reduced to 150 ppm or less, more preferably 140 ppm or less in 30 minutes after the treatment starts.
[0029]
When the organic compound treatment catalyst according to the present invention is used for treatment of organic compounds in wastewater, it can be purified much faster with a simple device without using a special device such as an autoclave, The spent catalyst can be easily separated from the treated water. That is, after 15 minutes of stirring, it can be 10 mg / l or less, preferably 8 mg / l or less. After 45 minutes of stirring, it can be 8 mg / l or less, preferably 6 mg / l or less. In the case of irradiation with ultraviolet rays during the treatment, it can be reduced to 6 mg / l or less, preferably 5 mg / l or less after 15 minutes of stirring.
[0030]
Next, a method for producing an organic compound treatment catalyst according to the present invention will be described.
[0031]
Spinel iron oxide particles containing manganese and zinc as core particles in the present invention are ferrous hydroxide colloids obtained by reacting a ferrous salt aqueous solution and an alkaline aqueous solution or a reaction suspension containing iron-containing precipitates. In producing spinel-type iron oxide by aerating an oxygen-containing gas such as air through the suspension to oxidize the ferrous hydroxide or iron-containing precipitate, a predetermined amount is required before aeration of the oxygen-containing gas. Manganese and zinc can be produced (hereinafter referred to as “wet method”).
[0032]
In producing spinel-type iron oxide particles, particles having various isotropic shapes can be obtained by adjusting the pH during the oxidation reaction.
[0033]
In addition, after mixing the dry method, that is, iron oxide particles such as hematite particles and manganese oxide particles or manganese compound that can be converted to manganese oxide by heating and zinc oxide or zinc compound that can be converted to zinc oxide by heating, 1000 to 1000 As described above, the manganese-zinc ferrite particle powder obtained by pulverization after heating and firing at 1300 ° C. usually has almost no Fe 2+ , so that it is sufficiently effective as a catalyst for treating organic substances, as shown in a comparative example. It is difficult to get.
[0034]
In the present invention, the core particles are coated with titanium oxide by thermal hydrolysis by heating a suspension obtained by mixing the core particles and a water-soluble titanium aqueous solution within a temperature range of 70 to 100 ° C. for 5 to 30 hours. After the reaction, the precipitate may be filtered, washed with water and dried by a conventional method.
[0035]
As the water-soluble titanium compound solution, a titanium sulfate aqueous solution, a mixed solution of titanium chloride and a sulfuric acid aqueous solution, or the like can be used.
The addition amount of the water-soluble titanium compound is 0.1 to 20% by weight in terms of TiO 2 with respect to the core particles.
[0036]
Next, the organic compound treatment catalyst according to the present invention can be used at room temperature and under normal pressure as shown in the following examples. After the addition, it may be stirred. The catalyst can be used even in a powder state, and can be used after being molded into various shapes and various sizes as required.
[0037]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is as follows.
In addition, the average particle diameter of the spinel type iron oxide particle powder, manganese-zinc ferrite particle powder, and composite oxide particle powder containing manganese and / or zinc in the following embodiments and the following examples and comparative examples is a transmission type. This is a value obtained from the Martin diameter measured for 300 particles shown in an enlarged photograph (× 40000) of a photograph (× 10000) taken with an electron microscope.
[0038]
The BET specific surface area values of spinel-type iron oxide particles containing manganese and / or zinc, manganese-zinc ferrite particles and composite oxide particles are “Mono Sorb MS-II” (trade name: Yuasa Ionics Co., Ltd. ( The value obtained by the BET method was used.
[0039]
The amount of Fe 2+ in the spinel type iron oxide particles containing manganese and / or zinc, the manganese-zinc ferrite particles and the composite oxide particles was shown by the value obtained by the following chemical analysis method.
[0040]
That is, in an inert gas atmosphere, 25 cc of a mixed solution containing phosphoric acid and sulfuric acid in a ratio of 2: 1 is added to 0.5 g of spinel-type iron oxide particle powder to dissolve the spinel-type iron oxide particle powder. After adding several drops of diphenylamine sulfonic acid as an indicator to the diluted solution of the aqueous solution, redox titration using an aqueous potassium dichromate solution was performed. The end point was when the diluted solution was purple, and the amount was calculated from the amount of dichromic acid aqueous solution used up to the end point.
[0041]
The total iron content, Mn content, and Zn content of spinel-type iron oxide particles containing manganese and / or zinc, manganese-zinc ferrite particles, and composite oxide particles were measured using an ICP emission spectroscopic analyzer SPS4000 (Seiko Electronics Co., Ltd.). (Manufactured)) was determined by plasma emission spectroscopy.
[0042]
The amount of Fe 3+ of the spinel type iron oxide particle powder containing manganese and / or zinc, the manganese-zinc ferrite particle powder and the composite oxide particle powder is shown by subtracting the Fe 2+ amount from the total iron amount. .
[0043]
The amount of NH 3 in the container was indicated by a value measured using ammonia gas detector tubes No. 3M and No. 3La (Gastech Co., Ltd.).
Incidentally, NH 3 concentration using No.3M if the 30～500Ppm, if NH 3 concentration of 100ppm or less, was used Nanba3La.
[0044]
The amount of acetaldehyde in the container was indicated by a value measured using an acetaldehyde gas detector tube No. 92 (Gastech Co., Ltd.).
[0045]
The amount of organic compounds in wastewater is defined as chemical oxygen consumption (hereinafter referred to as COD), which is one of the indicators of organic compound content in wastewater, according to JIS K0102-1993 “17.100 ° C. permanganese. It was shown by the value measured according to “Oxygen consumption by potassium acid (COD)”.
[0046]
<Manufacture of catalyst for organic compound treatment>
Spherical particles produced by a wet method having an average particle size of 0.3 μm, a BET specific surface area of 11.7 m 2 / g, and containing Fe 2+ of 7.5 atomic% with respect to Fe 3+ spinel-type iron oxide particles containing manganese and zinc (Mn amount is 22.5 atomic% to Fe 3+, Zn amount 14.6 atomic% with respect to the Fe 3+) (hereinafter referred to as "core particles a". ) After mixing 1 l of a suspension containing 100 g and titanyl sulfate (TiOSO 4 ) 151 g (corresponding to 50 g in terms of TiO 2 ) dissolved in 2 l of pure water to a total volume of 3 l, The core particles were coated with anatase-type titanium oxide by heating and stirring at a temperature of 95 ° C. for 20 hours to conduct a thermal hydrolysis reaction of titanyl sulfate.
The core particle powder whose particle surface was coated with anatase-type titanium oxide was filtered, washed with water and then dried to obtain a composite oxide particle powder A (hereinafter referred to as “catalyst A”). The obtained catalyst A is a spherical particle coated with anatase-type titanium oxide in a weight ratio of 1 to the core particle, has an average particle diameter of 0.3 μm, and a BET specific surface area of 176 m 2 / g. The amount of Fe 2+ was 7.5 atomic% with respect to Fe 3+ . The amount of Mn was 22.5% by weight with respect to Fe 3+ , and the amount of Zn was 14.6% with respect to Fe 3+ .
[0047]
<Use to atmosphere containing ammonia (1)>
Example 1
A sealable container having a capacity of 5 liters having a top surface made of quartz glass and a bottom surface and side surfaces made of an acrylic resin was prepared, and a fan and a five-virtual sample stage were installed inside the container. Then, 100 mg of the catalyst A was put on an aluminum foil and placed on a sample table.
Ammonia gas was introduced into the atmosphere from the gas inlet provided in the upper part of the side of the container, sealed, and then the fan was rotated. After 5 minutes, the ammonia concentration was measured with an ammonia gas detector tube. It was 250 ppm. Thereafter, when the ammonia concentration was measured at intervals of 15 minutes, the ammonia concentration decreased with the passage of time, and became saturated at 60 ppm after 1 hour.
[0048]
<Use to atmosphere containing ammonia (2)>
Example 2
The ammonia concentration in the atmosphere was adjusted in the same manner as in Example 1 above, except that the black light was irradiated on the catalyst A placed on the sample stage so that the ultraviolet intensity became 1.0 (mW / cm 2 ). It was measured.
The initial ammonia concentration was 250 ppm as in Use Example 1, and was 44 ppm after 30 minutes of ultraviolet irradiation.
[0049]
<Use to atmosphere containing acetaldehyde (1)>
Example 3
The operation was performed in the same manner as in Use Example 1 except that 1000 mg of Catalyst A was used and an atmosphere containing acetaldehyde was used.
When 5 minutes passed after the introduction of acetaldehyde gas, the acetaldehyde concentration was measured with an acetaldehyde gas detector tube. As a result, the initial acetaldehyde concentration was 240 ppm, and it reached 100 ppm after 1 hour.
[0050]
<Use in air containing acetaldehyde (2)>
Example 4
The operation was performed in the same manner as in Use Example 3 except that the black light was irradiated on the catalyst A placed on the sample stage so that the ultraviolet intensity became 1.0 (mW / cm 2 ).
When the acetaldehyde concentration was measured with a gas detector tube when 5 minutes had passed after the introduction of acetaldehyde gas was started, the initial acetaldehyde concentration was 240 ppm, and after 30 minutes of UV irradiation, it became 50 ppm.
[0051]
<Use for COD components in wastewater (1)>
Example 5
500 ml of waste water having a COD component of 70 mg / l was prepared, 10 g of the catalyst was added to the waste water, and the mixture was stirred for 15 minutes and allowed to stand.
After standing for 15 minutes and the suspension in the wastewater settled, the supernatant was collected and the COD component was measured and found to be 5 mg / l.
<Use for COD components in wastewater (2)>
Example 6
The operation was carried out in the same manner as in Use Example 5, except that the black light was irradiated so that the ultraviolet intensity became 1.0 (mW / cm 2 ) on the water surface.
The COD component in the supernatant was 3 mg / l.
[0052]
[Action]
The most important point in the present invention is that spinel iron oxide particles containing manganese and zinc having 2 to 20 atomic percent of Fe 2+ with respect to Fe 3+ are used, and a specific amount of titanium oxide is formed on the surface of the iron oxide particles. Composite oxide particles having an average particle size of 0.03 to 0.8 μm composed of composite oxide particles coated with an odor component when used as a catalyst for treating organic compounds, odor components in the atmosphere, COD components in wastewater, etc. This is the fact that the organic compound can be effectively processed in a short time.
[0053]
The reason why the organic compound can be effectively treated in a short time is not yet clear, but the present inventor, as shown in a comparative example described later, presents Fe of spinel-type iron oxide particles containing manganese and zinc. When the composite oxide particle powder whose 2+ is outside the specified range is used as a catalyst, when the composite oxide particle powder whose average particle size is outside the specified range is used as a catalyst, only manganese without containing zinc is used. When using spinel-type iron oxide particles containing as a catalyst, when using spinel-type iron oxide particles containing only zinc but not containing manganese as a catalyst, manganese having a specific amount of Fe 2+ not coated with titanium oxide When the spinel type iron oxide particles containing zinc and zinc are used as a catalyst, when the titanium oxide fine particle powder alone is used as a catalyst, the manganese-zinc ferrule obtained by the dry method is used. When the door particle of any when used as catalysts, from the inability to purify process the organic compound such as COD components odorous and wastewater in the air effectively, Fe 2 as core particles This is considered to be due to the synergistic effect of using spinel-type iron oxide particles containing manganese and zinc having a specific amount of + and a specific amount of titanium oxide coated on the surface of the spinel-type iron oxide particles.
[0054]
【Example】
Next, the present invention will be described with reference to examples and comparative examples.
[0055]
<Manufacture of organic compound adsorption / decomposition catalyst>
Core particles B to J
Spinel-type iron oxide particle powders B to J containing manganese and / or zinc as core particles were prepared. The characteristics of the spinel type iron oxide particles containing manganese and zinc are shown in Table 1.
[0056]
[Table 1]
Examples 1-10, Comparative Examples 1-9
Catalysts B to R were obtained in the same manner as in the above embodiment except that the type of core particles and the amount of coated titanium oxide were variously changed.
Tables 2 and 3 show main production conditions and various characteristics of the obtained catalyst.
[0058]
For comparison, as Comparative Example 8, the core particle A was used as it was as the catalyst S without being coated with titanium oxide. Further, as Comparative Example 9, after titanyl sulfate 151 g (corresponding to 50 g in terms of TiO 2 ) dissolved in 2 l of pure water was made up to 3 l in total volume, the temperature was raised and stirred at 95 ° C. for 20 hours. A titanium oxide particle powder having an average particle diameter of 0.008 μm and a BET specific surface area of 212 m 2 / g obtained by carrying out a thermal hydrolysis reaction of titanyl was separately prepared as catalyst T.
[0059]
[Table 2]
[Table 3]
<Use in air containing ammonia>
Use Examples 7 to 16 and Comparative Use Examples 1 to 10
The same operation as in the usage example 1 and the usage example 2 was performed except that the type of catalyst and the presence or absence of the catalyst were variously changed. The results are shown in Table 4.
[0062]
[Table 4]
<Use in air containing acetaldehyde>
Use Examples 17-26, Comparative Use Examples 11-20
The same operation as in the usage example 3 and the usage example 4 was performed except that the type of catalyst and the presence or absence of the catalyst were variously changed. The results are shown in Table 5.
[0064]
[Table 5]
<Use for COD components in wastewater>
Use Examples 27 to 36, Comparative Use Examples 21 to 30
The same operation as in the usage example 5 and the usage example 6 was performed except that the type of catalyst and the presence or absence of the catalyst were variously changed. The results are shown in Table 6.
[0066]
[Table 6]
【The invention's effect】
The catalyst according to the present invention can effectively treat organic compounds such as COD components in waste water and odor components in the atmosphere in a short time, as shown in the previous examples, and can be used for special purposes such as autoclaves. Therefore, it can be advantageously treated industrially and economically without using a simple apparatus, and is therefore suitable as a catalyst for treating organic compounds.
[0068]
Furthermore, since the above-mentioned catalyst according to the present invention can decompose the adsorbed organic compound, it can be reused and regenerated without discarding the catalyst, and can be expected to greatly contribute to the improvement of the living environment.
[0069]
In addition, when the said catalyst based on this invention is used for wastewater, since a used catalyst precipitates easily in the purified water after a process, it is easy to filter and isolate | separate.
Claims (3)
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