JP3785558B2 - Organochlorine compound removal catalyst and organochlorine compound removal method - Google Patents
Organochlorine compound removal catalyst and organochlorine compound removal method Download PDFInfo
- Publication number
- JP3785558B2 JP3785558B2 JP32629397A JP32629397A JP3785558B2 JP 3785558 B2 JP3785558 B2 JP 3785558B2 JP 32629397 A JP32629397 A JP 32629397A JP 32629397 A JP32629397 A JP 32629397A JP 3785558 B2 JP3785558 B2 JP 3785558B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- organic chlorine
- chlorine compound
- exhaust gas
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 109
- 150000004045 organic chlorine compounds Chemical class 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 25
- 239000011572 manganese Substances 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 50
- 229910052720 vanadium Inorganic materials 0.000 claims description 45
- 229910052748 manganese Inorganic materials 0.000 claims description 41
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 39
- 239000010936 titanium Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- -1 aromatic organic chlorine compound Chemical class 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 5
- 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 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 150000004826 dibenzofurans Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000010801 sewage sludge Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000005078 molybdenum compound Substances 0.000 claims description 2
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000003658 tungsten compounds Chemical class 0.000 claims description 2
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical class C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 24
- 230000000694 effects Effects 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910004688 Ti-V Inorganic materials 0.000 description 7
- 229910010968 Ti—V Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- OGBQILNBLMPPDP-UHFFFAOYSA-N 2,3,4,7,8-Pentachlorodibenzofuran Chemical compound O1C2=C(Cl)C(Cl)=C(Cl)C=C2C2=C1C=C(Cl)C(Cl)=C2 OGBQILNBLMPPDP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 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
- 239000003550 marker Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910018380 Mn(NO3)2.6H2 O Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 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 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- QGBLCIBATKETJC-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;manganese(2+) Chemical compound [Mn+2].O1B([O-])OB2OB([O-])OB1O2 QGBLCIBATKETJC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 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
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- BHNNQDMHEYBMIJ-UHFFFAOYSA-N [Mn].CC(=O)OC(C)=O Chemical compound [Mn].CC(=O)OC(C)=O BHNNQDMHEYBMIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- HYFPVPNWNRFTMP-UHFFFAOYSA-N formic acid;manganese Chemical compound [Mn].OC=O HYFPVPNWNRFTMP-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UIEFJQCTTAOVNA-UHFFFAOYSA-N manganese octane Chemical compound CCCCCCCC.[Mn] UIEFJQCTTAOVNA-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UORLFMNCHYTQSD-UHFFFAOYSA-N manganese(2+) tetranitrate Chemical compound [Mn++].[Mn++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O UORLFMNCHYTQSD-UHFFFAOYSA-N 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
- QMZIDZZDMPWRHM-UHFFFAOYSA-L manganese(2+);dibenzoate Chemical compound [Mn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QMZIDZZDMPWRHM-UHFFFAOYSA-L 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Landscapes
- 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、排ガス中に含まれる有害成分の塩素化合物を効率よく除去する排ガスの有機塩素化合物除去触媒及び有機塩素化合物除去方法に関する。
【０００２】
【従来の技術】
都市ごみ、産業廃棄物、下水汚泥等を焼却する焼却炉から発生する排ガス中には、有害成分の窒素酸化物（以下ＮＯｘと記載）、炭化水素（以下ＨＣと記載）及び一酸化炭素（以下ＣＯと記載）等の可燃性ガスと共に極めて微量であるが猛毒の有機塩素化合物、例えば芳香族系のポリ塩化ジベンゾダイオキシン（以下ＰＣＤＤと記載）、ポリ塩化ジベンゾフラン（以下ＰＣＤＦと記載）、クロロベンゼンが含まれており、これらの有害成分を除去し排ガスを浄化することは環境保全上重要である。
排ガス中に含まれる芳香族系有機塩素化合物を浄化する技術に触媒を用い酸化分解する方法があり、公知例としての特開平２−３５９１４号公報には排ガスを１５０℃以上に昇温し、酸化チタン、酸化バナジウム、酸化タングステン、白金、パラジウムの中から選ばれた少なくとも一種の成分を含む触媒を用いる方法が開示されている。
また、排ガス中に含まれるＮＯｘ、有機塩素化合物及びＣＯを浄化する技術の公知例として特開平５−２４５３４３号公報にはＡ成分としてＴｉ、Ｓｉ、Ｚｒ、Ａｌ、Ｖから選択し、Ｖを必ず含む一種の金属の単独系酸化物または二種以上の金属の複合多元系酸化物群から選ばれる一種以上と、Ｂ成分としてＰｔ、Ｐｄ、Ｒｕから選ばれる一種またはその酸化物を含む触媒を用いる方法が開示されている。
【０００３】
【発明が解決しようとする課題】
しかしながら従来の技術は必ずしもその性能が十分とは云えず、除去率を向上させるために触媒量を増加すること、触媒層の反応温度を高めることが必要となる。触媒量を増加する方法は、設備が大型になり触媒のコストが上昇する。そして触媒層の温度を高める方法は排ガスを昇温するための熱エネルギが増加し運転コストが上昇する。何れにしても排ガス浄化のためのコストが大幅に増加することは避けられない。本発明の目的は、排ガス中に含まれる有害成分の有機塩素化合物を効率よく除去することにある。
【０００４】
【課題を解決するための手段】
上記目的は、主たる構成元素の原子比が、Ｔｉ５０〜９５％、Ｍｎ０．０１〜２０％、Ｖ０．５〜４０％、Ｗ０〜２０％、Ｍｏ０〜２０％である有機塩素化合物除去用触媒により達成される。上記有機塩素化合物除去用触媒が、格子面間隔で４．３７±０．２Å、３．５４±０．２Å、３．２８±０．２Å、３．１６±０．２Å、３．０９±０．２Å、３．０４±０．２Åのいずれかに対応するＸ線回析ピークを含むことが望ましい。上記目的は、バナジウム酸化物及びマンガン酸化物に溶媒を加えて混練し、該第１の混合物を乾燥後に焼成し、該焼成物にチタン酸化物とモリブデン化合物或いはタングステン化合物と溶媒を加えて混練し、該第２の混合物を乾燥後に焼成することにより触媒を製造する有機塩素化合物除去用触媒の製造方法によっても達成される。有機塩素化合物及び酸素を含む排ガスを温度５０〜６００℃で上記の触媒に接触させて酸化分解して浄化することが望ましい。有機塩素化合物及び酸素を含む排ガスを温度１００〜３００℃で上記の触媒に接触させて酸化分解して浄化することが望ましい。有機塩素化合物、窒素酸化物及び可燃性ガスを含む排ガスに窒素酸化物還元剤を添加し、温度５０〜６００℃で上記の触媒に接触させて酸化分解して浄化することが望ましい。有機塩素化合物、窒素酸化物及び可燃性ガスを含む排ガスに窒素酸化物還元剤を添加し、温度１００〜３００℃で上記の触媒に接触させて酸化分解して浄化することが望ましい。上記の触媒を有機塩素化合物のうちの芳香族有機塩素化合物に適用することが望ましい。上記の触媒を有機塩素化合物のうちのポリ塩化ジベンゾダイオキシンまたはポリ塩化ジベンゾフランに適用することが望ましい。上記の触媒を下水汚泥焼却炉またはごみ焼却炉から排出される排ガスに適用することが望ましい。上記構成の触媒に含まれるＭｎとＶの複合酸化物は、ＭｎとＶの相互作用が強まり、活性成分であるＶの酸化還元反応速度が大きくなり、ＭｎとＶの複合酸化物の形態がＭｎ（ＶＯ３）２，ＭｎＶ２Ｏ６，ＭｎＶＯ３であれば有害成分の高い除去率が得られる。触媒活性成分の原子比がＭｎ１〜１６％、Ｖ０．５〜４０％で高い除去率を長期に維持できる。Ｍｎの原子比が２０％、Ｖの原子比が４０％を超えるとＴｉ上でＭｎ、Ｖまたは複合酸化物が高分散しにくくなり高い触媒活性が得られない。また、Ｗ、Ｍｏの原子比が２０％以下であればＴｉ−（Ｍｎ−Ｖ）系の活性を保持したまま対ＳＯｘ性が向上して触媒の寿命が長くなり、ハニカム成型性も向上する。Ｗ、Ｍｏの原子比が２０％以上であればＷまたはＭｏが触媒表面の活性点を被覆し、活性が低下する。そして上記構成の触媒は反応温度５０〜６００℃、好ましくは１００〜３００℃で排ガス中に含まれる有害成分の有機塩素化合物、窒素酸化物及び可燃性ガスを効率よく除去することができる。
【０００５】
【発明の実施の形態】
以下、本発明の基本的な実施の形態を説明する。
本発明の触媒は極めて高い性能を有しているが、製造に関して特に困難な点は無く通常の製造技術である沈殿法、酸化物混合法、混練法、担持法、含浸法等が適用できる。触媒の成型には通常の押出し成型法、打錠成型法、転動造粒法等の目的に応じた成型技術を適用できる。触媒の形状は、円柱状、円管状、板状、リボン状、ハニカム状、ペレット状に成型できる。特に板状、ハニカム状に成型すれば排ガス中に含まれるダストが触媒表面に付着することを防止でき、活性の低下及び圧力損失の増加を低減できる。また、触媒成分の少量をシリカ、アルミナ、ジルコニア等に担持したり、シリカ、アルミナ、ジルコニア、マグネシア、酸性白土、活性白土、珪藻土の担体成分と触媒成分とを十分に混練し触媒に混合して使用できる。そして、担体成分の水溶性塩から触媒成分と同時に共沈させたり、担体成分の水酸化物を混練して使用できる。特に担体または担体成分の使用は触媒コストを低減せしめる点からも好ましい。
本発明の触媒の活性成分であるマンガンの原料としては、各種の酸化マンガン、酢酸マンガン、硝酸マンガン、硝酸マンガンアンモニウム、硫酸マンガン、炭酸マンガン、塩化マンガン、硼酸マンガン、蓚酸マンガン、安息香酸マンガン、蟻酸マンガン、燐酸マンガン、ステアリン酸マンガン、ナフテン酸マンガン、マンガンアセチルアセテート、エチルヘキサンマンガンが使用できる。
バナジウムの原料としては、各種の酸化バナジウム、メタバナジン酸塩及び硫酸バナジル、蓚酸バナジル、ハロゲン化バナジウムが使用できる。
更に、上記マンガンの原料、バナジウムの原料をそれぞれ水、蓚酸を用いて溶解させ両者を混合した後、その混合液を蒸発乾固させること、またはアンモニア水で沈殿を生成させることにより、マンガンとバナジウムを原子レベルで均一に混合できマンガンとバナジウムの複合酸化物を調整する上で好ましい。
チタンの原料としては、酸化チタンまたは加熱により酸化チタンを生成する各種の化合物、例えばチタン酸、水酸化チタン、硫酸チタンが使用できる。
触媒製造時に汎用される各種のチタン化合物、例えばハロゲン化チタン、硫酸チタンを水、アンモニア水、苛性アルカリ、炭酸アルカリで沈殿させ水酸化物とした後加熱分解により酸化物を生成することもできる。
【０００６】
ここで、触媒製造の一例を挙げてその内容を説明する。
所定量のメタバナジン酸アンモニウム （ＮＨ4ＶＯ3）、硝酸マンガン Ｍｎ（ＮＯ3）2・６Ｈ2Ｏに蒸留水を加え、この混合物を十分に混練する。得られたペースト状の混合物を乾燥させた後、３００〜８００℃の温度で１〜１０時間焼成する。
本発明の触媒を用いる有機塩素化合物系の除去反応の適用対象としては、ＰＣＤＤ、ＰＣＤＦ、クロロベンゼン、クロロフェノール、ポリ塩テトラクロロエチレンの塩素を含むものであり、特に芳香族塩素化合系が好適な除去反応の対象となる。排ガス中に含まれる有害成分の有機塩素化合物、窒素酸化物及び可燃性ガスを除去する際の排ガス空間速度は１００，０００／ｈ以下とし、好ましくは １，０００〜５０，０００／ｈの範囲に設定する。反応温度は５０〜６００℃、好ましくは１００〜３００℃とし、反応圧力は特に限定しない。排ガスに添加する窒素酸化物還元剤は、アンモニアまたは尿素が好ましい。そして、触媒を保有する反応器の形式は固定床、移動床、流動床の何れでも適用できる。
【０００７】
次に、本発明の詳細な実施の形態を比較例と対比しながら説明する。
実施の形態１
メタバナジン酸アンモニウム （ＮＨ4ＶＯ3）２．２ｇに硝酸マンガン Ｍｎ（ＮＯ3）2・６Ｈ2Ｏ２．１６ｇ及び蒸留水１０ｍｌを加え十分に混練する。得られたペースト状の混合物を１２０℃で乾燥させた後、５００℃の温度で２時間焼成する。この焼成品に酸化チタン（ＴｉＯ2）２０ｇ及び蒸留水３０ｍｌを加え十分に混練する。得られたペースト状の混合物を１２０℃で乾燥させた後、５００℃の温度で２時間焼成して触媒を得た。以後この触媒をＴｉ−（Ｍｎ、Ｖ）触媒と記載する。Ｔｉ−（Ｍｎ、Ｖ）触媒は原子比でＴｉ：Ｍｎ：Ｖ＝１００：３：７．５の組成を有する。
図１は本発明の実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒のＸ線回析結果を表す図表である。
本図の上側図表はＴｉ−（Ｍｎ、Ｖ）触媒のＸ線回析（以後ＸＲＤと記載）ピークを示し、本図の下側図表はＸＲＤスペクトルで最上段はＴｉ−（Ｍｎ、Ｖ）触媒、第２段はマーカとしてのＴｉＯ2であり、第３段はマーカとしてのＭｎＶ2Ｏ6であり、第４段はＭｎ（ＶＯ3）2であり、最下段はマーカとしてのＶ2Ｏ5である。本図に示すＸＲＤスペクトルから明らかなようにＭｎとＶからなる複合酸化物Ｍｎ（ＶＯ3）2及びＭｎＶ2Ｏ6の存在が確認され、格子面間隔で４．３７Å、３．２８Å、３．１６Å、３．０９Å、３．０４Åに対応するＸ線回折ピークを含む。
比較例としてＴｉ、Ｍｎ、Ｖの三元素を本実施の形態のように分離せず同時に混練、焼成したＴｉ−Ｍｎ−Ｖ触媒と、Ｔｉ、Ｖの二元素を混練、焼成したＴｉ−Ｖ触媒のＸＲＤ分析を行ったところ、Ｍｎ、Ｖはそれぞれの単独酸化物で存在し、本実施の形態のようなＭｎとＶからなる複合酸化物は認められなかった。
【０００８】
次に、本実施の形態の触媒の活性試験について説明する。
活性試験装置は常圧流通型であり、反応管は内径１６ｍｍの耐熱ガラス（パイレックス）製で、反応管内に外径５ｍｍの耐熱ガラス（パイレックス）製の熱伝対保護管を挿入している。この反応管を電気炉内に装着して反応温度５０〜６００℃に昇温する。反応管の中央に１０〜２０メッシュに整粒した各種触媒４．５ｍｌを充填し、下記組成の有機塩素化合物としてクロロベンゼンを含む模擬排ガスを空間速度（以下ＳＶと記載）１０，０００／ｈで流通させ、有機塩素化合物の分解率を測定した。
模擬排ガス組成
Ｏ2 １０％
Ｈ2Ｏ ２０％
クロロベンゼン 約１０００ｐｐｍ
ＮＯ ２００ｐｐｍ
ＮＨ3 ２００ｐｐｍ
Ｎ2 残部
図２は本発明の実施の形態及び比較例の触媒活性を示す図表である。
本図に示すように本実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒は、比較例のＴｉ−Ｍｎ−Ｖ触媒、Ｔｉ−Ｖ触媒及びＴｉ−Ａｇ−Ｖ触媒より活性が高い。
【０００９】
実施の形態２
実施の形態１で調整したＴｉ−（Ｍｎ、Ｖ）触媒及び比較例の触媒を用い、実施の形態１の触媒活性試験条件のうちの有機塩素化合物をクロロベンゼンからｏ−ジクロロベンゼン、ｏ−クロロフェノールのそれぞれに変え、下記のガス組成で触媒活性試験を行った。
本図に示すように本実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒（原子比でＴｉ：Ｍｎ：Ｖ＝１００：３：７．５）は、有機塩素化合物のｏ−ジクロロベンゼン、ｏ−クロロフェノールの何れに対しても比較例のＴｉ−Ｍｎ−Ｖ触媒（原子比でＴｉ：Ｍｎ：Ｖ＝１００：３：７．５）、Ｔｉ−Ｖ触媒（原子比でＴｉ：Ｖ＝１００：７．５）より活性が高い。
【００１０】
実施の形態３
実施の形態１で調整したＴｉ−（Ｍｎ、Ｖ）触媒及び実施の形態１と同じ比較例の触媒を用い、模擬排ガス組成以外は実施の形態１と同じ触媒活性試験条件でＮＯｘ除去率に関する触媒活性試験を行った。
模擬排ガス組成
Ｏ2 １０％
Ｈ2Ｏ ２０％
クロロベンゼン 約１０００ｐｐｍ
ＮＯ ２００ｐｐｍ
ＮＨ3 ２４０ｐｐｍ
Ｎ2 残部
図４は本発明の実施の形態及び比較例の触媒活性を示す図表である。
本図に示すように本実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒は、低い温度領域及び高い温度領域でＴｉ−Ｍｎ−Ｖ触媒より活性が高く、脱硝触媒として実用化されているＴｉ−Ｖ触媒よりも活性が高い。本実施の形態によれば排ガス中にクロロベンゼンのような有機塩素化合物が存在してもＮＯｘ除去率には影響せず、Ｔｉ−（Ｍｎ、Ｖ）触媒を用いて有機塩素化合物、ＮＯｘを同時に高い除去率で浄化することができる。
【００１１】
実施の形態４
実施の形態１で調整したＴｉ−（Ｍｎ、Ｖ）触媒及び比較例のＴｉ−Ｍｎ−Ｖ触媒（原子比Ｔｉ：Ｍｎ：Ｖ＝１００：３：７．５）、Ｔｉ−Ｖ触媒（原子比Ｔｉ：Ｖ＝１００：７．５）、Ｔｉ−Ｖ−Ｗ触媒（原子比Ｔｉ：Ｖ：Ｗ＝１００：７．５：５．７）を用い、ＳＶ ２０，０００／ｈ、下記の模擬排ガス組成で炭化水素プロパン（Ｃ3Ｈ8）の除去率に関する触媒活性試験を行った。
模擬排ガス組成
Ｏ2 １０％
Ｈ2Ｏ ２０％
Ｃ3Ｈ8 １５０ｐｐｍ
Ｎ2 残部
図５は本発明の実施の形態及び比較例の触媒活性を示す図表である。
本図に示すように本実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒は、低い温度領域でＴｉ−Ｍｎ−Ｖ触媒、Ｔｉ−Ｗ−Ｖ触媒及びＴｉ−Ｖ触媒よりも格別に活性が高い。本実施の形態によれば排ガス中に炭化水素、一酸化炭素のような可燃性ガスが存在しても高い除去率で浄化することができる。
【００１２】
実施の形態５
Ｔｉ−（Ｍｎ、Ｖ）触媒（原子比でＴｉ：Ｍｎ：Ｖ＝１００：３：７．５）の形状をハニカム及び板状に調整し、比較例のＴｉ−Ｍｎ−Ｖ触媒（原子比でＴｉ：Ｍｎ：Ｖ＝１００：３：７．５）及びＴｉ−Ｖ−Ｗ触媒（原子比でＴｉ：Ｖ：Ｗ＝１００：７．５：５．７）の形状をハニカム及び板状に調整し、実施の形態１の触媒活性試験条件のうちの有機塩素化合物をＰＣＤＤとＰＣＤＦの混合ガスに変えてＳＶ １０，０００／ｈで触媒活性試験を行った。
模擬排ガス組成
Ｏ2 １０％
Ｈ2Ｏ ２０％
ＰＣＤＤ ２００〜１０００ｎｇ／Ｎｍ3
ＰＣＤＦ ２００〜１０００ｎｇ／Ｎｍ3
ＮＯ １００〜２５０ｐｐｍ
ＮＨ3 ２４０ｐｐｍ
Ｎ2 残部
図６は本発明の他の実施の形態及び比較例の触媒活性を示す図表である。
本図の縦軸はＰＣＤＤとＰＣＤＦの混合ガスの分解率を表し、ハニカム及び板状Ｔｉ−（Ｍｎ、Ｖ）触媒は比較例に対し高い活性を有する。
【００１３】
実施の形態６
Ｔｉ−（Ｍｎ、Ｖ）触媒のうちのＴｉに対するＭｎの原子比を変え、実施の形態１と同じ方法で調整し、本実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒および比較例のＴｉ−Ｍｎ−Ｖ触媒について温度２１０℃としそれ以外の条件、模擬排ガス組成、ＳＶは実施の形態１と同じとし有機塩素化合物の分解率を測定した。
図７は本発明の実施の形態及び比較例の触媒活性を示す図表である。
本図に示すように本実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒は、Ｔｉに対するＭｎの原子比０．２〜２０％の範囲で比較例のＴｉ−Ｍｎ−Ｖ触媒より活性が高く、特に１〜１６％の範囲で著しく高くなる。
【００１４】
実施の形態７
本実施の形態のＴｉ−（Ｍｎ、Ｖ）−Ｗ触媒は実施の形態１のＴｉ−（Ｍｎ、Ｖ）触媒にＷを加え原子比でＴｉ：Ｍｎ：Ｖ：Ｗ＝１００：３：７．５：５．７となるように調整し、Ｔｉ−（Ｍｎ、Ｖ）−Ｍｏ触媒は実施の形態１のＴｉ−（Ｍｎ、Ｖ）触媒にＭｏを加え原子比でＴｉ：Ｍｎ：Ｖ：Ｍｏ＝１００：３：７．５：５．７となるように調整し、比較例としてＴｉ−Ｖ触媒（原子比でＴｉ：Ｖ＝１００：７．５）を用い、実施の形態１の模擬排ガスにＳＯｘを加えＳＶは実施の形態１と同じとし５０時間後の有機塩素化合物の分解率を測定した。
模擬排ガス組成
Ｏ2 １０％
Ｈ2Ｏ ２０％
クロロベンゼン 約１０００ｐｐｍ
ＮＯ ２００ｐｐｍ
ＮＨ3 ２００ｐｐｍ
ＳＯ2 ２００ｐｐｍ
Ｎ2 残部
図８は本発明の他の実施の形態の触媒加速劣化試験結果を示す図表である。
本図に示すように比較例のＴｉ−Ｖ触媒は５０時間後に活性が５０％に低下したが、本実施の形態のＴｉ−（Ｍｎ、Ｖ）−Ｗ触媒及びＴｉ−（Ｍｎ、Ｖ）−Ｍｏ触媒は、活性低下が僅かに留まった。Ｗ及びＭｏを含むＴｉ−（Ｍｎ、Ｖ）−Ｗ−Ｍｏ触媒も同様な効果を有する。
【００１５】
【発明の効果】
本発明によれば、触媒に含まれるＭｎとＶの複合酸化物により活性成分であるＶの酸化還元反応速度が大きくなり、排ガス中に含まれる有害成分の有機塩素化合物、窒素酸化物及び可燃性ガスを効率良く除去する効果が得られる。
【図面の簡単な説明】
【図１】本発明の実施の形態のＴｉ−（Ｍｎ、Ｖ）触媒のＸ線回析結果を表す図表である。
【図２】本発明の実施の形態及び比較例の触媒活性を示す図表である。
【図３】本発明の実施の形態及び比較例の触媒活性を示す図表である。
【図４】本発明の実施の形態及び比較例の触媒活性を示す図表である。
【図５】本発明の実施の形態及び比較例の触媒活性を示す図表である。
【図６】本発明の他の実施の形態及び比較例の触媒活性を示す図表である。
【図７】本発明の実施の形態及び比較例の触媒活性を示す図表である。
【図８】本発明の他の実施の形態の触媒加速劣化試験結果を示す図表である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an exhaust gas organochlorine compound removal catalyst and an organochlorine compound removal method for efficiently removing harmful components of chlorine compounds contained in exhaust gas .
[0002]
[Prior art]
In exhaust gas generated from incinerators that incinerate municipal waste, industrial waste, sewage sludge, etc., harmful components such as nitrogen oxides (hereinafter referred to as NOx), hydrocarbons (hereinafter referred to as HC), and carbon monoxide (hereinafter referred to as HC) Contains extremely tiny but highly toxic organochlorine compounds such as aromatic polychlorinated dibenzodioxins (hereinafter referred to as PCDD), polychlorinated dibenzofurans (hereinafter referred to as PCDF), and chlorobenzene together with flammable gases such as CO) It is important for environmental conservation to remove these harmful components and purify the exhaust gas.
As a technique for purifying aromatic organochlorine compounds contained in exhaust gas, there is a method of oxidizing and decomposing using a catalyst. JP-A-2-35914 as a known example raises the temperature of exhaust gas to 150 ° C. or higher and oxidizes it. A method using a catalyst containing at least one component selected from titanium, vanadium oxide, tungsten oxide, platinum, and palladium is disclosed.
In addition, as a known example of a technique for purifying NOx, organochlorine compounds and CO contained in exhaust gas, Japanese Patent Laid-Open No. 5-245343 selects Ti, Si, Zr, Al, V as an A component, and V must be One or more kinds selected from a single oxide of one kind of metal or a composite multi-element oxide group of two or more kinds of metals, and a catalyst containing one kind selected from Pt, Pd, and Ru as the B component or an oxide thereof. A method is disclosed.
[0003]
[Problems to be solved by the invention]
However, the conventional technique is not necessarily sufficient in performance, and it is necessary to increase the amount of catalyst and increase the reaction temperature of the catalyst layer in order to improve the removal rate. In the method of increasing the amount of catalyst, the equipment becomes large and the cost of the catalyst increases. And the method of raising the temperature of a catalyst layer increases the heat energy for heating up exhaust gas, and an operating cost rises. In any case, the cost for exhaust gas purification is inevitably increased. It is an object of the present invention to efficiently remove harmful organic chlorine compounds contained in exhaust gas.
[0004]
[Means for Solving the Problems]
The above object is achieved by a catalyst for removing organic chlorine compounds in which the atomic ratio of main constituent elements is
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a basic embodiment of the present invention will be described.
Although the catalyst of the present invention has extremely high performance, there is no particular difficulty in production, and usual production techniques such as precipitation method, oxide mixing method, kneading method, loading method, impregnation method and the like can be applied. For the molding of the catalyst, a molding technique according to the purpose such as a normal extrusion molding method, a tableting molding method, a rolling granulation method or the like can be applied. The catalyst can be formed into a cylindrical shape, a circular tube shape, a plate shape, a ribbon shape, a honeycomb shape, or a pellet shape. In particular, if it is formed into a plate shape or honeycomb shape, dust contained in the exhaust gas can be prevented from adhering to the catalyst surface, and a decrease in activity and an increase in pressure loss can be reduced. In addition, a small amount of the catalyst component is supported on silica, alumina, zirconia, etc., or the support component and the catalyst component of silica, alumina, zirconia, magnesia, acid clay, activated clay, diatomaceous earth are sufficiently kneaded and mixed with the catalyst. Can be used. Then, it can be coprecipitated from the water-soluble salt of the carrier component at the same time as the catalyst component, or kneaded with the hydroxide of the carrier component. In particular, the use of a carrier or a carrier component is preferable from the viewpoint of reducing the catalyst cost.
As a raw material of manganese which is an active component of the catalyst of the present invention, various manganese oxides, manganese acetate, manganese nitrate, manganese manganese nitrate, manganese sulfate, manganese carbonate, manganese chloride, manganese borate, manganese oxalate, manganese benzoate, formic acid Manganese, manganese phosphate, manganese stearate, manganese naphthenate, manganese acetyl acetate, and ethylhexane manganese can be used.
As a raw material of vanadium, various vanadium oxides, metavanadate, vanadyl sulfate, vanadyl oxalate, and vanadium halide can be used.
Further, after dissolving the above manganese raw material and vanadium raw material using water and oxalic acid respectively and mixing both, manganese and vanadium are produced by evaporating the mixed liquid to dryness or forming a precipitate with aqueous ammonia. Can be mixed uniformly at the atomic level, which is preferable in preparing a complex oxide of manganese and vanadium.
As a raw material of titanium, titanium oxide or various compounds that generate titanium oxide by heating, such as titanic acid, titanium hydroxide, and titanium sulfate can be used.
Various titanium compounds widely used at the time of catalyst production, such as titanium halide and titanium sulfate, can be precipitated with water, aqueous ammonia, caustic alkali, and alkali carbonate to form hydroxides, and then oxides can be generated by thermal decomposition.
[0006]
Here, an example of catalyst manufacture will be given and the content will be described.
Distilled water is added to a predetermined amount of ammonium metavanadate (NH 4 VO 3 ) and manganese nitrate Mn (NO 3 ) 2 .6H 2 O, and this mixture is sufficiently kneaded. The obtained paste-like mixture is dried and then baked at a temperature of 300 to 800 ° C. for 1 to 10 hours.
As an application object of the removal reaction of the organochlorine compound system using the catalyst of the present invention, it contains chlorine of PCDD, PCDF, chlorobenzene, chlorophenol, polysalt tetrachloroethylene, and the removal reaction particularly suitable for the aromatic chlorination system. It becomes the object of. The exhaust gas space velocity when removing the harmful organic chlorine compounds, nitrogen oxides and combustible gas contained in the exhaust gas is 100,000 / h or less, preferably in the range of 1,000 to 50,000 / h. Set. The reaction temperature is 50 to 600 ° C., preferably 100 to 300 ° C., and the reaction pressure is not particularly limited. The nitrogen oxide reducing agent added to the exhaust gas is preferably ammonia or urea. The type of the reactor holding the catalyst can be any of a fixed bed, a moving bed, and a fluidized bed.
[0007]
Next, a detailed embodiment of the present invention will be described in comparison with a comparative example.
Embodiment 1
Add 2.16 g of manganese nitrate Mn (NO 3 ) 2 .6H 2 O and 10 ml of distilled water to 2.2 g of ammonium metavanadate (NH 4 VO 3 ) and knead thoroughly. The obtained paste-like mixture is dried at 120 ° C. and then baked at a temperature of 500 ° C. for 2 hours. To this fired product, 20 g of titanium oxide (TiO 2 ) and 30 ml of distilled water are added and kneaded sufficiently. The obtained paste-like mixture was dried at 120 ° C. and then calcined at a temperature of 500 ° C. for 2 hours to obtain a catalyst. Hereinafter, this catalyst is referred to as a Ti- (Mn, V) catalyst. The Ti- (Mn, V) catalyst has a composition of Ti: Mn: V = 100: 3: 7.5 by atomic ratio.
FIG. 1 is a chart showing the X-ray diffraction results of the Ti— (Mn, V) catalyst according to the embodiment of the present invention.
The upper chart in this figure shows the X-ray diffraction (hereinafter referred to as XRD) peak of the Ti- (Mn, V) catalyst, the lower chart in the figure is the XRD spectrum, and the top stage is the Ti- (Mn, V) catalyst. The second stage is TiO 2 as a marker, the third stage is MnV 2 O 6 as a marker, the fourth stage is Mn (VO 3 ) 2 , and the bottom stage is V 2 O 5 as a marker. It is. As is clear from the XRD spectrum shown in this figure, the presence of the composite oxides Mn (VO 3 ) 2 and MnV 2 O 6 composed of Mn and V was confirmed, and the lattice spacing was 4.37Å, 3.28Å, and 3. X-ray diffraction peaks corresponding to 16Å, 3.09Å, and 3.04Å are included.
As a comparative example, a Ti-Mn-V catalyst in which three elements of Ti, Mn, and V are simultaneously kneaded and calcined as in the present embodiment, and a Ti-V catalyst in which two elements of Ti and V are kneaded and calcined are used. As a result of the XRD analysis, Mn and V were present as individual oxides, and no complex oxide composed of Mn and V as in this embodiment was observed.
[0008]
Next, the activity test of the catalyst of the present embodiment will be described.
The activity test apparatus is a normal pressure flow type, the reaction tube is made of heat-resistant glass (Pyrex) having an inner diameter of 16 mm, and a thermocouple protection tube made of heat-resistant glass (Pyrex) having an outer diameter of 5 mm is inserted into the reaction tube. The reaction tube is mounted in an electric furnace and the reaction temperature is raised to 50 to 600 ° C. In the center of the reaction tube, 4.5 ml of various types of catalysts sized to 10 to 20 mesh are packed, and simulated exhaust gas containing chlorobenzene as an organochlorine compound with the following composition is distributed at a space velocity (hereinafter referred to as SV) of 10,000 / h. The decomposition rate of the organochlorine compound was measured.
Simulated exhaust
H 2 O 20%
About 1000ppm of chlorobenzene
NO 200ppm
NH 3 200ppm
N 2 balance FIG. 2 is a chart showing the catalytic activity of the embodiment of the present invention and the comparative example.
As shown in the figure, the Ti— (Mn, V) catalyst of the present embodiment has higher activity than the Ti—Mn—V catalyst, Ti—V catalyst, and Ti—Ag—V catalyst of the comparative example.
[0009]
Using the Ti- (Mn, V) catalyst prepared in the first embodiment and the catalyst of the comparative example, the organochlorine compound in the catalytic activity test conditions of the first embodiment is changed from chlorobenzene to o-dichlorobenzene, o-chlorophenol. The catalytic activity test was conducted with the following gas composition.
As shown in the figure, the Ti- (Mn, V) catalyst (atomic ratio Ti: Mn: V = 100: 3: 7.5) of the present embodiment is an organochlorine compound, o-dichlorobenzene, o- Ti-Mn-V catalyst of comparative example (Ti: Mn: V = 100: 3: 7.5 in atomic ratio) and Ti-V catalyst (Ti: V = 100 in atomic ratio) for any of chlorophenols More active than 7.5).
[0010]
Using the Ti- (Mn, V) catalyst prepared in the first embodiment and the catalyst of the same comparative example as in the first embodiment, a catalyst relating to the NOx removal rate under the same catalytic activity test conditions as in the first embodiment except for the simulated exhaust gas composition An activity test was performed.
Simulated exhaust
H 2 O 20%
About 1000ppm of chlorobenzene
NO 200ppm
NH 3 240ppm
N 2 balance 4 is a diagram showing the catalytic activity of the embodiments and comparative examples of the present invention.
As shown in the figure, the Ti— (Mn, V) catalyst of the present embodiment has higher activity than the Ti—Mn—V catalyst in a low temperature region and a high temperature region, and is practically used as a denitration catalyst. More active than V catalyst. According to the present embodiment, even if an organic chlorine compound such as chlorobenzene is present in the exhaust gas, the NOx removal rate is not affected, and the Ti- (Mn, V) catalyst is used to simultaneously increase the organic chlorine compound and NOx. It can be purified with a removal rate.
[0011]
Ti- (Mn, V) catalyst prepared in Embodiment 1 and Ti-Mn-V catalyst of comparative example (atomic ratio Ti: Mn: V = 100: 3: 7.5), Ti-V catalyst (atomic ratio) Ti: V = 100: 7.5), Ti—V—W catalyst (atomic ratio Ti: V: W = 100: 7.5: 5.7), SV 20,000 / h, the following simulated exhaust gas A catalytic activity test on the removal rate of hydrocarbon propane (C 3 H 8 ) by composition was performed.
Simulated exhaust
H 2 O 20%
C 3 H 8 150ppm
N 2 balance FIG. 5 is a chart showing the catalytic activity of the embodiment of the present invention and the comparative example.
As shown in the figure, the Ti- (Mn, V) catalyst of the present embodiment has a significantly higher activity than the Ti-Mn-V catalyst, Ti-W-V catalyst, and Ti-V catalyst in a low temperature range. . According to this embodiment, even if a combustible gas such as hydrocarbon or carbon monoxide is present in the exhaust gas, it can be purified with a high removal rate.
[0012]
Embodiment 5
The shape of the Ti- (Mn, V) catalyst (Ti: Mn: V = 100: 3: 7.5 in atomic ratio) was adjusted to a honeycomb and a plate, and the Ti-Mn-V catalyst of Comparative Example (in atomic ratio) Ti: Mn: V = 100: 3: 7.5) and Ti—V—W catalyst (atomic ratio of Ti: V: W = 100: 7.5: 5.7) were adjusted to honeycomb and plate shape. Then, the organochlorine compound in the catalyst activity test conditions of Embodiment 1 was changed to a mixed gas of PCDD and PCDF, and the catalyst activity test was conducted at SV 10,000 / h.
Simulated exhaust
H 2 O 20%
PCDD 200-1000 ng / Nm 3
PCDF 200-1000ng / Nm 3
NO 100-250ppm
NH 3 240ppm
N 2 balance FIG. 6 is a chart showing the catalytic activity of other embodiments of the present invention and comparative examples.
The vertical axis of this figure represents the decomposition rate of the mixed gas of PCDD and PCDF, and the honeycomb and the plate-like Ti— (Mn, V) catalyst have higher activity than the comparative example.
[0013]
The atomic ratio of Mn to Ti in the Ti- (Mn, V) catalyst was changed and adjusted by the same method as in the first embodiment, and the Ti- (Mn, V) catalyst of this embodiment and the Ti- The Mn-V catalyst was set at a temperature of 210 ° C., the other conditions, simulated exhaust gas composition, and SV were the same as those in Embodiment 1, and the decomposition rate of the organic chlorine compound was measured.
FIG. 7 is a chart showing the catalytic activity of the embodiment of the present invention and the comparative example.
As shown in the figure, the Ti- (Mn, V) catalyst of the present embodiment has higher activity than the Ti-Mn-V catalyst of the comparative example in the range of 0.2 to 20% of the atomic ratio of Mn to Ti. In particular, it becomes remarkably high in the range of 1 to 16%.
[0014]
In the Ti— (Mn, V) —W catalyst of the present embodiment, W is added to the Ti— (Mn, V) catalyst of Embodiment 1, and the atomic ratio is Ti: Mn: V: W = 100: 3: 7. The Ti— (Mn, V) —Mo catalyst was adjusted to 5: 5.7, and Mo was added to the Ti— (Mn, V) catalyst of the first embodiment to obtain an atomic ratio of Ti: Mn: V: Mo. = 100: 3: 7.5: 5.7 The simulated exhaust gas according to the first embodiment was prepared using a Ti-V catalyst (atomic ratio Ti: V = 100: 7.5) as a comparative example. SOx was added to SV, and the SV was the same as in Embodiment 1, and the decomposition rate of the organochlorine compound after 50 hours was measured.
Simulated exhaust
H 2 O 20%
About 1000ppm of chlorobenzene
NO 200ppm
NH 3 200ppm
SO 2 200ppm
N 2 balance FIG. 8 is a chart showing the results of the accelerated catalyst degradation test of another embodiment of the present invention.
As shown in the figure, the Ti-V catalyst of the comparative example decreased in activity to 50% after 50 hours. However, the Ti- (Mn, V) -W catalyst and Ti- (Mn, V)-of the present embodiment were used. The Mo catalyst remained slightly reduced in activity. A Ti— (Mn, V) —W—Mo catalyst containing W and Mo has a similar effect.
[0015]
【The invention's effect】
According to the present invention, the redox reaction rate of V, which is an active component, is increased by the composite oxide of Mn and V contained in the catalyst, and harmful organic chlorine compounds, nitrogen oxides, and combustible substances contained in the exhaust gas. The effect of efficiently removing the gas can be obtained.
[Brief description of the drawings]
FIG. 1 is a chart showing X-ray diffraction results of a Ti— (Mn, V) catalyst according to an embodiment of the present invention.
FIG. 2 is a chart showing catalytic activity of embodiments of the present invention and comparative examples.
FIG. 3 is a chart showing catalytic activity of embodiments of the present invention and comparative examples.
FIG. 4 is a chart showing the catalytic activity of the embodiments of the present invention and comparative examples.
FIG. 5 is a chart showing the catalytic activity of the embodiments of the present invention and comparative examples.
FIG. 6 is a chart showing the catalytic activity of other embodiments and comparative examples of the present invention.
FIG. 7 is a chart showing the catalytic activity of the embodiments of the present invention and comparative examples.
FIG. 8 is a chart showing the results of a catalyst accelerated deterioration test according to another embodiment of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32629397A JP3785558B2 (en) | 1997-11-27 | 1997-11-27 | Organochlorine compound removal catalyst and organochlorine compound removal method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32629397A JP3785558B2 (en) | 1997-11-27 | 1997-11-27 | Organochlorine compound removal catalyst and organochlorine compound removal method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11156190A JPH11156190A (en) | 1999-06-15 |
| JP3785558B2 true JP3785558B2 (en) | 2006-06-14 |
Family
ID=18186160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32629397A Expired - Fee Related JP3785558B2 (en) | 1997-11-27 | 1997-11-27 | Organochlorine compound removal catalyst and organochlorine compound removal method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3785558B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4730998B2 (en) * | 2000-07-28 | 2011-07-20 | 京セラ株式会社 | Exhaust gas purification catalyst and exhaust gas purification device |
| CN114602458B (en) * | 2022-03-22 | 2023-05-26 | 江苏理工学院 | Mn (VO 3 ) 2 /V 2 O 5 Catalyst, preparation method and application thereof |
-
1997
- 1997-11-27 JP JP32629397A patent/JP3785558B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11156190A (en) | 1999-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0800420B1 (en) | Method for controlling voc, co and halogenated organic emissions | |
| KR100239294B1 (en) | Catalytic method and device for controlling voc, co and halogenated organic emissions | |
| US5783515A (en) | Catalyst for treating exhaust gases containing dioxines, production process for the catalyst and method of treating the exhaust gases | |
| JP3326836B2 (en) | Catalyst body and method for producing catalyst body | |
| EP1293250B1 (en) | Process for removing organohalogen compounds using a titanium, molybdenum and vanadium containing catalyst and process for producing the catalyst | |
| JP3785558B2 (en) | Organochlorine compound removal catalyst and organochlorine compound removal method | |
| JP3702398B2 (en) | Exhaust gas purification catalyst and purification method | |
| JPH0947661A (en) | Process and catalyst for purifying exhaust gas | |
| KR100402430B1 (en) | Catalyst for decomposition of toxic pollutants and producing process thereof | |
| KR100382050B1 (en) | Catalyst for Removing Dioxin and Nitrogen Oxides in Flue Gas and Method for Treating Combustion Exhaust Gases Using the Same | |
| JP2000000471A (en) | Waste gas treating catalyst, waste gas treatment and treating device | |
| JP3790943B2 (en) | Exhaust gas purification catalyst and exhaust gas purification method | |
| JP2001252562A (en) | Low temperature denitration catalyst and low temperature denitration method | |
| JPH1057760A (en) | Method for decomposing chlorinated organic compound | |
| JP2000126601A (en) | Decomposition catalyst for organic halogen compound and decomposition method | |
| KR100515907B1 (en) | Catalyst for removing dioxin and/or nitrogen oxide, and preparation method thereof | |
| JP2001038206A (en) | Catalyst for treating exhaust gas and method and apparatus for treating exhaust gas | |
| JP3510541B2 (en) | Exhaust gas treatment catalyst, exhaust gas treatment method and treatment apparatus | |
| KR100862272B1 (en) | Catalyst for Removal of Carbon Monoxide and Preparation Method Thereof | |
| JP2000061305A (en) | Catalyst and method for treating exhaust gas | |
| JP3332024B2 (en) | Organic compound combustion removal catalyst and combustion removal method | |
| JP3920612B2 (en) | Exhaust gas treatment method | |
| JPH10216480A (en) | Treatment of waste gas and catalyst for treating waste gas | |
| JP2002001065A (en) | Decomposition catalyst and decomposition method for organic chlorine compound | |
| JP2003053149A (en) | Removing method of organic chlorine compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050531 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050607 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050804 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060214 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060308 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100331 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110331 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120331 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |