JP3803851B2 - Dioxin oxidation catalyst - Google Patents
Dioxin oxidation catalyst Download PDFInfo
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- JP3803851B2 JP3803851B2 JP20485599A JP20485599A JP3803851B2 JP 3803851 B2 JP3803851 B2 JP 3803851B2 JP 20485599 A JP20485599 A JP 20485599A JP 20485599 A JP20485599 A JP 20485599A JP 3803851 B2 JP3803851 B2 JP 3803851B2
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- Prior art keywords
- titania
- carrier
- oxidation catalyst
- catalyst
- dioxin
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- 239000003054 catalyst Substances 0.000 title claims description 44
- 230000003647 oxidation Effects 0.000 title claims description 21
- 238000007254 oxidation reaction Methods 0.000 title claims description 21
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title claims 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 101
- 239000011148 porous material Substances 0.000 claims description 23
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 19
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- -1 organic acid salt Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002697 manganese compounds Chemical class 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 150000002013 dioxins Chemical class 0.000 description 14
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- 230000010718 Oxidation Activity Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007865 diluting Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、都市ごみおよび産業廃棄物のごみ焼却炉で発生する燃焼排ガス中に含まれるダイオキシン類を酸化分解するための触媒に関する。
【０００２】
【従来の技術】
ゴミ焼却炉排ガス中のダイオキシン類の分解は、一般に、ダイオキシン類を共存する酸素で酸化し、無害な二酸化炭素、炭化水素、塩素ガスなどに変性することで行われている。ダイオキシン類の酸化には触媒が使用されるが、その触媒は２００℃前後の低温で有効に機能し、微量共存する塩化水素、ＳＯｘ、ＮＯｘなどに被毒されないことが必要条件である。
【０００３】
アナターゼチタニアにバナジウム酸化物ならびにタングステン酸化物を必須成分として担持させた触媒が上記条件を満たすものとして知られている（特許第２６３３３１６号公報参照）。
【０００４】
しかし、タングステン酸化物はチタニア、バナジウム酸化物と比較して高価な物質であり、触媒調製法、工程管理法なども複雑になることから、バナジウム酸化物／チタニアの２成分系の触媒開発が望まれているが、従来、タングステン酸化物の添加なしには十分な触媒性能を発揮できないとされていた。
【０００５】
【発明が解決しようとする課題】
本発明は、上記実状に鑑み、タングステン酸化物の添加なしでも高い触媒活性を発揮させることができるダイオキシン類酸化触媒を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本明細書において、吸着担持とは金属溶液に担体を所要時間浸漬しておき、金属を担体に吸着させる手法をいう。浸漬時間は金属濃度、溶液温度などの条件にも依り、通常は１時間〜数１０時間の範囲で選択される。
【０００８】
タングステン酸化物の添加なしに高いダイオキシン類酸化活性を発揮させるには、チタニア結晶表面に担持されるバナジウム酸化物を高度に分散させる必要がある。同時に、バナジウム酸化物を担体上の固体酸性点との強い相互作用下に置き、結晶表面酸素としてＯ- を多量に保有させることが望まれる。
【０００９】
即ち、チタニア結晶の表面に多数散在する酸性点にバナジウム化合物を吸着させ、これを４００℃〜３００℃の比較的低温で焼成することにより、バナジウム酸化物を高度に分散した状態で担体に担持させる。こうして得られたアナターゼチタニア触媒は高いダイオキシン類酸化活性を発揮する。
【００１０】
高活性の発現は、バナジウムの高分散に依る接ガス面積の増大と、直下にある酸性点との強い相互作用に依ると考えられる。また、触媒細孔内で、バナジウム酸化物は数分子層以下の厚さで細孔壁に密着しており、担持されたバナジウム酸化物よる細孔の閉塞がなくダイオキシン類は細孔深部まで容易に拡散できるので、触媒全体が有効に機能しうることも、高活性発現の理由である。
【００１１】
上記現象は、担体表面の固体酸酸性点の量および酸強度を増加させればより高いダイオキシン類の酸化活性が発現することを示唆する。発明者等はこの示唆に従って、アナターゼチタニア結晶の表面をマンガン酸化物または珪素酸化物との複合酸化物とすることにより得られる表面改質チタニア担体にバナジウム酸化物を吸着担持することにより、更に高いダイオキシン類の酸化活性を有する触媒を開発した。
【００１２】
本発明による第１のダイオキシン類酸化触媒は、アナターゼチタニアにマンガン化合物を含浸させ、該チタニアを焼成することによって得られた表面改質チタニア担体に、バナジウム酸化物を吸着担持させた触媒である。
【００１３】
本発明による第２のダイオキシン類酸化触媒は、アナターゼチタニアに珪素化合物を含浸させ、該チタニアを焼成することによって得られた表面改質チタニア担体に、バナジウム酸化物を吸着担持させた触媒である。
【００１４】
第１のダイオキシン類酸化触媒において、表面改質チタニア担体は、好ましくは、アナターゼチタニアをマンガンの有機酸塩または無機酸塩の水溶液に浸漬し、ついで乾燥・焼成することにより得られたものである。マンガンの有機酸塩としては酢酸マンガンが例示され、無機酸塩としては塩化マンガン、硝酸マンガンが例示される。
【００１５】
第２のダイオキシン類酸化触媒において、表面改質チタニア担体は、好ましくは、乾燥アナターゼチタニアを有機シリカ化合物の有機溶媒希釈液に浸漬して細孔内に含浸させ、ついで有機溶媒を蒸発させた後、チタニア含有担体を水に浸漬して細孔内の有機シリカ化合物を加水分解させてから同担体を乾燥・焼成することにより得られたものである。有機溶媒も乾燥したものを用いる。有機溶媒は特に限定されないがアルコール類がよく用いられる。
【００１６】
担体にバナジウム酸化物を吸着担持させるには、担体をメタバナジン酸アンモンの水溶液に所要時間浸漬しておき、ついで乾燥・焼成する。
【００１７】
アナターゼチタニアは、同チタニアの水性ゾル溶液にセラミクス繊維からなるシート状、ペーパー状などのプレフォーム体を浸漬し、繊維間マトリックスにゾルを保持させた状態でプレフォーム体を乾燥したものであってもよい。
【００１８】
【発明の実施の形態】
参考製造例１
（１）固形分濃度３５ｗｔ％のチタニアゾル（石原産業社製「ＣＳＮゾル」）にセラミックス繊維からなるシート状のプレフォーム体（日本無機社製「ＭＣＳ０２５」、厚さ：０．３ｍｍ）を浸漬し、液から取り出した後１２０℃で乾燥し、平板状の担体（これをＴ担体と呼ぶ）を得た。
【００１９】
Ｔ担体は、チタニアを１４６ｇ／ｍ2 （坪量）保持し、チタニアの比表面積３６５ｍ2 ／ｇを有するものであった。また、この状態ではチタニアはＸ線回折計測で明確なアナターゼ結晶型を示さなかった。窒素吸着法で計測したＴ担体の細孔分布は半径３ｎｍ以下にピークが認められるものであった。
【００２０】
（２）Ｔ担体を空気中４５０℃で２時間焼成した。焼成後のチタニアは明確なアナターゼ結晶型を示し、比表面積は１１６ｍ2 ／ｇに低下した。細孔分布は半径８〜１０ｎｍにピークが認められるものに変化した。
【００２１】
（３）焼成後のＴ担体１００ｃｍ2 （坪量）を、バナジウムが１ｇ／リットル含まれるように調製したメタバナジン酸アンモン水溶液０．４リットルに９時間浸漬しておき、その後１２０℃で乾燥し、空気気流中３５０℃で２時間焼成した。こうしてダイオキシン類酸化触媒Ａを得た。
【００２２】
触媒ＡのＶ2 Ｏ5 ／ＴｉＯ2 重量比は０．０２８〜０．０３６であった。
【００２３】
この触媒の比表面積はチタニア１ｇ当たり１０６ｍ2 であり、細孔分布も殆どバナジウム担持前から変化せず、バナジウム担持による細孔の閉塞などは殆どないと考えられる。
【００２４】
また、メタバナジン酸アンモン水溶液として０．０１ｍｏｌ／リットル、０．０２ｍｏｌ／リットルおよび０．０４ｍｏｌ／リットルの各濃度のものを用いた点を除いて、上記と同様の操作を行い、Ｖ吸着量を異にするダイオキシン類酸化触媒Ａ−１、Ａ−２およびＡ−３を得た。
【００２５】
製造例１
（１）参考製造例１の工程（１）で得られたＴ担体を１ｍｏｌ／リットルの硝酸マンガン水溶液に３０分浸漬し、液から取り出した後１２０℃で２時間乾燥した。
【００２６】
（２）このマンガン含有チタニア担体を空気気流中４５０℃で３時間焼成し、平板状の担体（これをＭＴ担体と呼ぶ）を得た。
【００２７】
ＭＴ担体は、比表面積が９５ｍ2 ／ｇで、細孔分布はＴ担体とほぼ同様のものであった。また、この担体のＭｎＯ2 ／ＴｉＯ2 は０．０４〜０．０５であった。
【００２８】
（３）焼成後のＭＴ担体１００ｃｍ2 （坪量）に参考製造例１の工程（３）と同様の方法でバナジウム酸化物を吸着担持させ、ダイオキシン類酸化触媒Ｂを得た。
【００２９】
触媒ＢのＶ2 Ｏ5 ／ＴｉＯ2 重量比は０．０６０〜０．０９５であった。
【００３０】
この触媒の比表面積はチタニア１ｇ当たり９１ｍ2 であり、細孔分布も殆どバナジウム担持前から変化せず、バナジウム担持による細孔の閉塞などは殆どないと考えられる。
【００３１】
また、硝酸マンガン水溶液として０．５ｍｏｌ／リットル、０．１ｍｏｌ／リットルおよび２．０ｍｏｌ／リットルの各濃度のものを用いた点を除いて、上記と同様の操作を行い、Ｍｎ含量を異にするダイオキシン類酸化触媒Ｂ−１、Ｂ−２およびＢ−３を得た。
【００３２】
製造例２
（１）参考製造例１の工程（１）で得られたＴ担体を１２０℃で乾燥し、シリカゲルデシケーター中で冷却し、乾燥Ｔ担体を得た。
【００３３】
（２）ゼオライト充填層を通過させ乾燥させたイソプロピルアルコールに、４−イソプロピルシリケートを加え、６０ｖｏｌ％の希釈液を調製した。
【００３４】
（３）この液に乾燥Ｔ担体を３０分浸漬した。浸漬中に気相から湿分が液に溶解しないよう、浸漬容器を塩化ビニリデンフィルムで密閉しておいた。Ｔ担体を液から引き上げ、そのまま大気中に１６時間放置した。
【００３５】
（４）その後の担体を純水中に１０分間浸漬した。担体を液から引き上げ、１２０℃で乾燥し空気気流中４５０℃で３時間焼成し、平板状の担体（これをＳＴ担体と呼ぶ）を得た。ＳＴ担体は１２６ｍ2 ／ｇの比表面積を有し、細孔分布には、ＳｉＯ2 に由来する小径の細孔は認められず、焼成後のＴ担体とほぼ同様のものであった。
【００３６】
この担体のＳｉＯ2 ／ＴｉＯ2 重量比は０．０２５〜０．０３８であった。
【００３７】
（５）焼成後のＳＴ担体１００ｃｍ2 （坪量）に参考製造例１の工程（３）と同様の方法でバナジウム酸化物を吸着担持させ、ダイオキシン類酸化触媒Ｃを得た。
【００３８】
触媒ＣのＶ2 Ｏ5 ／ＴｉＯ2 重量比は０．０４５〜０．０７０であった。
【００３９】
この触媒の比表面積はチタニア１ｇ当たり１２０ｍ2 であり、細孔分布も殆どバナジウム担持前から変化せず、バナジウム担持による細孔の閉塞などは殆どないと考えられる。
【００４０】
また、４−イソプロピルシリケート希釈液として３０ｖｏｌ％、６０ｖｏｌ％および１００ｖｏｌ％の各濃度のものを用いた点を除いて、上記と同様の操作を行い、Ｓｉ含量を異にするダイオキシン類酸化触媒Ｂ−１、Ｂ−２およびＢ−３を得た。
【００４１】
比較製造例１
（１）Ｔ担体を空気中４５０℃で２時間焼成した。焼成後のチタニアは明確なアナターゼ結晶型を示し、比表面積は１１６ｍ2 ／ｇに低下した。
【００４２】
細孔分布は半径８〜１０ｎｍにピークが認められるものに変化した。
【００４３】
（２）１ｍｏｌ／リットルの蓚酸水溶液０．４リットルにメタバナジン酸アンモン９．４ｇを溶解し、バナジウムが１０ｇ／リットル含まれる浸漬液を調製した。
【００４４】
この液に焼成後のＴ担体１００ｃｍ2 （坪量）を６時間浸漬しておき、その後１５０℃乾燥し、空気気流中３５０℃で２時間焼成してダイオキシン類酸化触媒Ｄを得た。
【００４５】
触媒ＤのＶ2 Ｏ5 ／ＴｉＯ2 重量比は０．１５〜０．１８であった。
【００４６】
この触媒の比表面積はチタニア１ｇ当たり７７ｍ2 であり、細孔分布は焼成後Ｔ担体と比べ、細孔半径５ｎｍ前後が増加しており、バナジウム担持による細孔の閉塞、それによるインクボトルの形成が認められた。
【００４７】
使用例１
(1) 参考製造例１および製造例１〜２および比較製造例１で得られた各ダイオキシン類分解触媒について、下記条件で分解率を計測した。
【００４８】
【００４９】
【表１】
表１から判るように、触媒Ｂ−１、Ｂ−２、Ｂ−３、Ｃ−１、Ｃ−２およびＣ−３では、チタニア表面をマンガン酸化物または珪素酸化物との複合酸化物とし、表面酸性点の強度、点数を向上させると、バナジウム酸化物の吸着量が増加し、それに比例してダイオキシン類の酸化活性が上昇した。
【００５３】
上記のような処理を行うと、バナジウム酸化物吸着量表面酸性点の上限は、Ｖ／Ｔｉ（原子比）で０．０６前後であるらしく、Ｍｎ、Ｓｉ等の担持量を増加させてもバナジウムの吸着担持量は増加せず、ダイオキシン類の酸化活性もそれ以上には向上しない。
【００５４】
触媒Ｃ−１、Ｃ−２およびＣ−３の比表面積（ＳＡ）は、高い比表面積を有するＳｉＯ2 の影響で、Ｓｉ分の増加に従って増加する傾向にある。ただし、比表面積の増加はダイオキシン類酸化活性には殆ど寄与しない。
【００５５】
【発明の効果】
以上の次第で、本発明によれば、タングステン酸化物の添加なしでも高い触媒活性を発揮させることができるダイオキシン類酸化触媒を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for oxidatively decomposing dioxins contained in combustion exhaust gas generated in municipal waste and industrial waste incinerators.
[0002]
[Prior art]
The decomposition of dioxins in waste incinerator exhaust gas is generally performed by oxidizing the dioxins with oxygen in the presence of dioxins and modifying them into harmless carbon dioxide, hydrocarbons, chlorine gas, and the like. A catalyst is used for the oxidation of dioxins, but the catalyst is required to function effectively at a low temperature of around 200 ° C. and be not poisoned by trace amounts of hydrogen chloride, SOx, NOx, and the like.
[0003]
A catalyst in which vanadium oxide and tungsten oxide are supported as essential components on anatase titania is known to satisfy the above conditions (see Japanese Patent No. 2633316).
[0004]
However, tungsten oxide is an expensive material compared to titania and vanadium oxide, and the catalyst preparation method and process control method are complicated, so the development of a two-component catalyst of vanadium oxide / titania is desired. However, it has been conventionally considered that sufficient catalytic performance cannot be exhibited without addition of tungsten oxide.
[0005]
[Problems to be solved by the invention]
In view of the above circumstances, an object of the present invention is to provide a dioxin oxidation catalyst that can exhibit high catalytic activity without the addition of tungsten oxide.
[0007]
[Means for Solving the Problems]
In this specification, the adsorption carrying means a technique in which a carrier is immersed in a metal solution for a required time and the metal is adsorbed on the carrier. The immersion time depends on conditions such as the metal concentration and the solution temperature, and is usually selected in the range of 1 hour to several tens of hours.
[0008]
In order to exhibit high oxidation activity of dioxins without adding tungsten oxide, it is necessary to highly disperse vanadium oxide supported on the titania crystal surface. At the same time, the vanadium oxide was placed under strong interaction with the solid acid sites on the carrier, O as a crystal surface oxygen - be a large amount of holdings is desired.
[0009]
That is, a vanadium compound is adsorbed on acidic points scattered on the surface of a titania crystal and calcined at a relatively low temperature of 400 ° C. to 300 ° C., thereby supporting the vanadium oxide on the support in a highly dispersed state. . The anatase titania catalyst thus obtained exhibits a high dioxin oxidation activity.
[0010]
The expression of high activity is thought to be due to an increase in the gas contact area due to the high dispersion of vanadium and a strong interaction with the acidic point directly below. In addition, vanadium oxide adheres to the pore wall with a thickness of several molecular layers or less within the catalyst pores, and there is no blockage of pores by the supported vanadium oxide, and dioxins can be easily penetrated to the deep pores. It is also a reason for the high activity expression that the entire catalyst can function effectively.
[0011]
The above phenomenon suggests that if the amount of acid acid point on the surface of the support and the acid strength are increased, higher oxidation activity of dioxins is expressed. In accordance with this suggestion, the inventors of the present invention further increased the adsorption of vanadium oxide on a surface-modified titania support obtained by making the surface of anatase titania crystals a composite oxide with manganese oxide or silicon oxide. We have developed a catalyst with oxidation activity for dioxins.
[0012]
The first dioxin oxidation catalyst according to the present invention is a catalyst in which vanadium oxide is adsorbed and supported on a surface-modified titania support obtained by impregnating anatase titania with a manganese compound and calcining the titania.
[0013]
The second dioxin oxidation catalyst according to the present invention is a catalyst in which vanadium oxide is adsorbed and supported on a surface-modified titania support obtained by impregnating anatase titania with a silicon compound and firing the titania.
[0014]
In the first dioxin oxidation catalyst, the surface-modified titania carrier is preferably obtained by immersing anatase titania in an organic salt or inorganic acid salt aqueous solution of manganese, followed by drying and firing. . Examples of the organic acid salt of manganese include manganese acetate, and examples of the inorganic acid salt include manganese chloride and manganese nitrate.
[0015]
In the second dioxin oxidation catalyst, the surface-modified titania support is preferably obtained by immersing dry anatase titania in an organic solvent diluted solution of an organic silica compound to impregnate the pores, and then evaporating the organic solvent. The titania-containing carrier was obtained by immersing the titania-containing carrier in water to hydrolyze the organic silica compound in the pores and then drying and firing the carrier. A dried organic solvent is also used. The organic solvent is not particularly limited, but alcohols are often used.
[0016]
In order to adsorb and support the vanadium oxide on the support, the support is immersed in an aqueous solution of ammonium metavanadate for a required time, and then dried and fired.
[0017]
Anatase titania is obtained by immersing a preform body made of ceramic fibers in an aqueous sol solution of the same titania and drying the preform body in a state where the sol is held in a matrix between fibers. Also good.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Reference production example 1
(1) A sheet-like preform body (“MCS025” manufactured by Nippon Mining Co., Ltd., thickness: 0.3 mm) made of ceramic fibers is immersed in a titania sol (“CSN sol” manufactured by Ishihara Sangyo Co., Ltd. ) having a solid content of 35 wt%. After taking out from the liquid, it was dried at 120 ° C. to obtain a flat carrier (referred to as T carrier).
[0019]
The T carrier retained titania at 146 g / m 2 (basis weight) and had a titania specific surface area of 365 m 2 / g. In this state, titania did not show a clear anatase crystal form by X-ray diffraction measurement. The T carrier pore distribution measured by the nitrogen adsorption method had a peak with a radius of 3 nm or less.
[0020]
(2) The T carrier was calcined in air at 450 ° C. for 2 hours. The titania after calcination showed a clear anatase crystal form, and the specific surface area decreased to 116 m 2 / g. The pore distribution changed to one having a peak at a radius of 8 to 10 nm.
[0021]
(3) The T carrier 100 cm 2 (basis weight) after firing was immersed for 9 hours in 0.4 liter of ammonium metavanadate prepared so as to contain 1 g / liter of vanadium, and then dried at 120 ° C., Firing was performed at 350 ° C. for 2 hours in an air stream. A dioxin oxidation catalyst A was thus obtained.
[0022]
Catalyst A had a V 2 O 5 / TiO 2 weight ratio of 0.028 to 0.036.
[0023]
The specific surface area of this catalyst is 106 m 2 per gram of titania, and the pore distribution hardly changes from before vanadium loading, and it is considered that there is almost no blockage of pores due to vanadium loading.
[0024]
Further, except that the ammonium metavanadate aqueous solution having a concentration of 0.01 mol / liter, 0.02 mol / liter, and 0.04 mol / liter was used, the same operation as described above was performed, and the V adsorption amount was changed. Dioxins oxidation catalysts A-1, A-2 and A-3 were obtained.
[0025]
Production Example 1
(1) The T carrier obtained in step (1) of Reference Production Example 1 was immersed in a 1 mol / liter manganese nitrate aqueous solution for 30 minutes, taken out from the solution, and dried at 120 ° C. for 2 hours.
[0026]
(2) This manganese-containing titania support was calcined in an air stream at 450 ° C. for 3 hours to obtain a flat support (referred to as an MT support).
[0027]
The MT carrier had a specific surface area of 95 m 2 / g and the pore distribution was almost the same as that of the T carrier. In addition, MnO 2 / TiO 2 of this support was 0.04 to 0.05.
[0028]
(3) A vanadium oxide was adsorbed and supported on the MT carrier 100 cm 2 (basis weight) after firing in the same manner as in Step (3) of Reference Production Example 1 to obtain a dioxin oxidation catalyst B.
[0029]
Catalyst 2 had a V 2 O 5 / TiO 2 weight ratio of 0.060 to 0.095.
[0030]
The specific surface area of this catalyst is 91 m 2 per gram of titania, and the pore distribution hardly changes from before vanadium loading, and it is considered that there is almost no blockage of pores due to vanadium loading.
[0031]
Further, except that the manganese nitrate aqueous solution having a concentration of 0.5 mol / liter, 0.1 mol / liter or 2.0 mol / liter was used, the same operation as described above was performed, and the Mn content was changed. Dioxins oxidation catalysts B-1, B-2 and B-3 were obtained.
[0032]
Production Example 2
(1) The T carrier obtained in step (1) of Reference Production Example 1 was dried at 120 ° C. and cooled in a silica gel desiccator to obtain a dry T carrier.
[0033]
(2) 4-Isopropyl silicate was added to isopropyl alcohol that had been passed through the zeolite packed bed and dried to prepare a 60 vol% diluted solution.
[0034]
(3) A dry T carrier was immersed in this solution for 30 minutes. The immersion container was sealed with a vinylidene chloride film so that moisture did not dissolve in the liquid during the immersion. The T carrier was pulled up from the liquid and left in the atmosphere for 16 hours.
[0035]
(4) The subsequent carrier was immersed in pure water for 10 minutes. The carrier was pulled up from the liquid, dried at 120 ° C., and fired at 450 ° C. for 3 hours in an air stream to obtain a plate-like carrier (referred to as ST carrier). The ST carrier had a specific surface area of 126 m 2 / g, and small pores derived from SiO 2 were not observed in the pore distribution, and was almost the same as the T carrier after firing.
[0036]
SiO 2 / TiO 2 weight ratio of the carrier was 0.025 to 0.038.
[0037]
(5) A vanadium oxide was adsorbed and supported on the ST support 100 cm 2 (basis weight) after firing in the same manner as in Step (3) of Reference Production Example 1 to obtain a dioxin oxidation catalyst C.
[0038]
V 2 O 5 / TiO 2 weight ratio of catalyst C was 0.045 to 0.070.
[0039]
The specific surface area of this catalyst is 120 m 2 per gram of titania, and the pore distribution hardly changes from before vanadium loading, and it is considered that there is almost no blockage of pores due to vanadium loading.
[0040]
Further, the dioxins oxidation catalyst B- having the same Si content as the above except that 4-isopropyl silicate diluting solutions having concentrations of 30 vol%, 60 vol% and 100 vol% were used. 1, B-2 and B-3 were obtained.
[0041]
Comparative production example 1
(1 ) The T carrier was calcined in air at 450 ° C. for 2 hours. The titania after calcination showed a clear anatase crystal form, and the specific surface area decreased to 116 m 2 / g.
[0042]
The pore distribution changed to one having a peak at a radius of 8 to 10 nm.
[0043]
(2) 9.4 g of ammonium metavanadate was dissolved in 0.4 liter of a 1 mol / liter oxalic acid aqueous solution to prepare an immersion liquid containing 10 g / liter of vanadium.
[0044]
100 cm 2 (basis weight) of the baked T carrier was immersed in this liquid for 6 hours, then dried at 150 ° C., and baked at 350 ° C. for 2 hours in an air stream to obtain a dioxin oxidation catalyst D.
[0045]
V 2 O 5 / TiO 2 weight ratio of catalyst D was from 0.15 to 0.18.
[0046]
The specific surface area of this catalyst is 77 m 2 per gram of titania, and the pore distribution is increased by a pore radius of around 5 nm as compared with the T carrier after calcination. The pores are blocked by vanadium loading, thereby forming an ink bottle. Was recognized.
[0047]
Example 1
(1) About each dioxin decomposition catalyst obtained by reference manufacture example 1, manufacture example 1-2, and comparative manufacture example 1, the decomposition rate was measured on condition of the following.
[0048]
[0049]
[Table 1]
As can be seen from Table 1 , in the catalysts B-1, B-2, B-3, C-1, C-2 and C-3, the titania surface is a complex oxide with manganese oxide or silicon oxide, When the strength and score of the surface acidic point were improved, the amount of vanadium oxide adsorbed increased, and the oxidation activity of dioxins increased proportionally.
[0053]
The treatment described above line UTO, the upper limit of the vanadium oxide adsorption surface acidic sites are seems is 0.06 and forth V / Ti (atomic ratio), Mn, also to increase the supported amount of Si or the like vanadium The amount of adsorbed and supported oxygen does not increase, and the oxidation activity of dioxins is not further improved.
[0054]
The specific surface areas (SA) of the catalysts C-1, C-2 and C-3 tend to increase as the Si content increases due to the influence of SiO 2 having a high specific surface area. However, an increase in specific surface area hardly contributes to dioxin oxidation activity.
[0055]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a dioxin oxidation catalyst capable of exhibiting high catalytic activity without addition of tungsten oxide.
Claims (6)
Priority Applications (1)
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| JP20485599A JP3803851B2 (en) | 1999-07-19 | 1999-07-19 | Dioxin oxidation catalyst |
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|---|---|---|---|
| JP20485599A JP3803851B2 (en) | 1999-07-19 | 1999-07-19 | Dioxin oxidation catalyst |
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| JP3803851B2 true JP3803851B2 (en) | 2006-08-02 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110302800A (en) * | 2019-04-30 | 2019-10-08 | 杭州星宇炭素环保科技有限公司 | For decomposing the synthesis technology of the catalyst activity carbon composite of dioxin |
| US10624564B1 (en) | 2008-07-03 | 2020-04-21 | Masimo Corporation | Multi-stream data collection system for noninvasive measurement of blood constituents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4502349B2 (en) * | 2001-02-23 | 2010-07-14 | 三井造船株式会社 | Exhaust gas treatment apparatus and exhaust gas treatment method |
| KR100686381B1 (en) * | 2005-09-27 | 2007-02-22 | 한국전력기술 주식회사 | Vanadium/titania-based catalysts comprising of nmo(natural manganese ore) for removing nitrogen oxides and dioxine at wide operation temperature region, and using thereof |
| FR3124406A1 (en) * | 2021-06-24 | 2022-12-30 | Luma/Arles | Crystallization support, crystallization assembly comprising a frame and such a support, salt panel comprising such a support and method of manufacturing such a salt panel |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10624564B1 (en) | 2008-07-03 | 2020-04-21 | Masimo Corporation | Multi-stream data collection system for noninvasive measurement of blood constituents |
| CN110302800A (en) * | 2019-04-30 | 2019-10-08 | 杭州星宇炭素环保科技有限公司 | For decomposing the synthesis technology of the catalyst activity carbon composite of dioxin |
| CN110302800B (en) * | 2019-04-30 | 2022-03-11 | 杭州星宇炭素环保科技有限公司 | Synthesis process of catalyst activated carbon composite material for decomposing dioxin |
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