JP2017177051A - Exhaust gas treatment catalyst and exhaust gas treatment method - Google Patents
Exhaust gas treatment catalyst and exhaust gas treatment method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 74
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 19
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 16
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 239000010955 niobium Substances 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 18
- 239000011206 ternary composite Substances 0.000 abstract description 2
- -1 halide compound Chemical class 0.000 abstract 2
- 230000006866 deterioration Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 229910006774 Si—W Inorganic materials 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 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 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000012736 aqueous medium Substances 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
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000349 titanium oxysulfate 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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、排ガス中の窒素酸化物や有機ハロゲン化合物を除去するための排ガス処理触媒に関する。詳しくは、硫黄酸化物が含まれる排ガスの処理において耐久性を著しく向上させた排ガス処理用触媒に関する。 The present invention relates to an exhaust gas treatment catalyst for removing nitrogen oxides and organic halogen compounds in exhaust gas. Specifically, the present invention relates to an exhaust gas treatment catalyst that has significantly improved durability in the treatment of exhaust gas containing sulfur oxides.
窒素酸化物（ＮＯｘ）は人体にとって有害な物質である他、酸性雨や光化学スモッグの原因物質であり、その対策技術として、アンモニアまたは尿素などの還元剤を用いて排ガス中の窒素酸化物を触媒上で接触還元して窒素と水に分解する選択的触媒還元法（ＳＣＲ法）が一般的に用いられている。また、ダイオキシン類に代表される有機ハロゲン化合物も人体に深刻な影響を及ぼす有害物質であるが、その処理においても触媒による分解除去が広く用いられている。特に都市ごみ焼却炉など廃棄物処理施設から排出される排ガスでは、窒素酸化物と有機ハロゲン化合物の両方を除去することが必要になる場合も多い。 Nitrogen oxides (NOx) are harmful to the human body and are the cause of acid rain and photochemical smog. As a countermeasure, nitrogen oxides in exhaust gas are catalyzed using a reducing agent such as ammonia or urea. A selective catalytic reduction method (SCR method) in which catalytic reduction is carried out to decompose into nitrogen and water is generally used. Organohalogen compounds represented by dioxins are harmful substances that have a serious effect on the human body, and catalytic decomposition and removal are widely used in the treatment. In particular, exhaust gas discharged from waste treatment facilities such as municipal waste incinerators often needs to remove both nitrogen oxides and organic halogen compounds.
このような用途に用いられる排ガス処理触媒としては、例えば、チタン酸化物、バナジウム酸化物およびタングステン酸化物を含有する触媒（特許文献１、２）、またはチタン酸化物、バナジウム酸化物およびモリブデン酸化物を含有する触媒（特許文献３、４）について開示されている。 Examples of the exhaust gas treatment catalyst used for such applications include catalysts containing titanium oxide, vanadium oxide and tungsten oxide (Patent Documents 1 and 2), or titanium oxide, vanadium oxide and molybdenum oxide. The catalyst (patent documents 3 and 4) which contains is disclosed.
一方、近年では排ガス再加熱にかかるＣＯ２排出の低減などの観点から、排ガス処理温度の低温化が望まれており、例えば都市ごみ焼却炉排ガスの処理では２００℃未満の低温度域においても優れた除去性能および耐久性を有する触媒が求められている。これに関しては、性能および耐久性をより向上させた触媒として、チタン系酸化物、バナジウム酸化物、および銅、コバルトなどの金属の硫酸塩を含有する触媒について提案されているが（特許文献５）、このような触媒を用いたとしても排ガスの処理温度が２００℃未満になると硫黄酸化物による性能低下が大きく、要求される処理性能を維持する為には触媒を頻繁に交換する必要があった。 On the other hand, in recent years, from the viewpoint of reducing CO 2 emission due to exhaust gas reheating, it has been desired to lower the exhaust gas treatment temperature. For example, municipal waste incinerator exhaust gas treatment is excellent even in a low temperature range of less than 200 ° C. There is a need for a catalyst having excellent removal performance and durability. In this regard, as a catalyst with further improved performance and durability, a catalyst containing a titanium oxide, a vanadium oxide, and a sulfate of a metal such as copper or cobalt has been proposed (Patent Document 5). Even when such a catalyst is used, if the treatment temperature of the exhaust gas is less than 200 ° C., the performance degradation due to sulfur oxides is large, and the catalyst must be frequently replaced in order to maintain the required treatment performance. .
本発明の目的は、硫黄酸化物を含有する排ガスの処理において従来の触媒に比べて性能低下が少なく、より長時間にわたって排ガス中の窒素酸化物や有機ハロゲン化合物を除去することができる排ガス処理触媒、および該触媒を用いた排ガス処理方法を提供することにある。 An object of the present invention is to provide an exhaust gas treatment catalyst capable of removing nitrogen oxides and organic halogen compounds in the exhaust gas over a longer period of time with less performance degradation compared to conventional catalysts in the treatment of exhaust gas containing sulfur oxides. And an exhaust gas treatment method using the catalyst.
本発明者らは、上記課題を解決する為に鋭意検討を行った結果、以下に示す組成の触媒が有効であることを見出した。すなわち本発明の排ガス処理触媒は、触媒Ａ成分としてチタン、タングステンおよびケイ素の三元系複合酸化物または混合酸化物、触媒Ｂ成分としてバナジウム、ニオブまたはタンタルの少なくとも１種の元素の化合物ならびに触媒Ｃ成分としてモリブデンまたはタングステンの少なくとも１種の元素の化合物を含有し、かつ硫黄化合物が硫黄原子換算で触媒の全体量に対し０．４〜１．０質量％含まれていることを特徴とするものである。 As a result of intensive studies to solve the above problems, the present inventors have found that a catalyst having the following composition is effective. That is, the exhaust gas treatment catalyst of the present invention comprises a ternary composite oxide or mixed oxide of titanium, tungsten and silicon as the catalyst A component, a compound of at least one element of vanadium, niobium or tantalum as the catalyst B component and the catalyst C. It contains at least one elemental compound of molybdenum or tungsten as a component, and the sulfur compound is contained in an amount of 0.4 to 1.0% by mass in terms of sulfur atom with respect to the total amount of the catalyst. It is.
本発明を用いることで、低温度域においても硫黄酸化物による性能低下を抑制することが可能になり、排ガス中に含まれるＮＯｘや有機ハロゲン化合物を長時間にわたって安定的に処理することができる。 By using this invention, it becomes possible to suppress the performance fall by a sulfur oxide also in a low temperature range, and NOx and organic halogen compound contained in waste gas can be processed stably over a long time.
本発明の排ガス処理触媒は、触媒Ａ成分としてチタン、タングステンおよびケイ素の三元系複合酸化物または混合酸化物、触媒Ｂ成分としてバナジウム、ニオブ、タンタルの少なくとも１種の元素の化合物ならびに触媒Ｃ成分としてモリブデン、タングステンの少なくとも１種の元素の化合物を含み、さらに硫黄化合物を硫黄原子換算で触媒の全質量に対し０．４〜１．０質量％を含むものである。 The exhaust gas treatment catalyst of the present invention comprises a ternary complex oxide or mixed oxide of titanium, tungsten and silicon as a catalyst A component, a compound of at least one element of vanadium, niobium, and tantalum as a catalyst B component, and a catalyst C component As a compound containing at least one element of molybdenum and tungsten, and further containing 0.4 to 1.0% by mass of a sulfur compound in terms of sulfur atom with respect to the total mass of the catalyst.
本発明の触媒のＡの成分は出発原料として、各元素の酸化物、水酸化物、無機塩、有機塩などを用いることができる。たとえばチタン供給源としては、硫酸チタニル、四塩化チタン、テトライソプロピルチタネートなどが用いられ、ケイ素供給源としてはシリカゾル、水ガラス、四塩化ケイ素などが用いられ、タングステン源としてはパラタングステン酸アンモニウム、メタタングステン酸アンモニウム、タングステン酸などを用いることができる。触媒Ａ成分の調製方法としてはゾル―ゲル法、水熱合成、共沈法、沈着法、混練法などを用いることができる。 As the component A of the catalyst of the present invention, oxides, hydroxides, inorganic salts, organic salts and the like of each element can be used as starting materials. For example, titanyl sulfate, titanium tetrachloride, tetraisopropyl titanate, etc. are used as the titanium source, silica sol, water glass, silicon tetrachloride, etc. are used as the silicon source, and ammonium paratungstate, Ammonium tungstate, tungstic acid, or the like can be used. As a preparation method of the catalyst A component, a sol-gel method, hydrothermal synthesis, a coprecipitation method, a deposition method, a kneading method and the like can be used.
本発明の触媒のＢ成分はバナジウム、ニオブまたはタンタルの少なくとも１種の元素の化合物であるが、酸化物の形態で触媒に含有されているのが除去性能の点から好ましい。またその含有量も除去性能に大きく影響し、触媒Ａ成分と触媒Ｂ成分と触媒Ｃ成分の合計質量に対して酸化物換算で１〜２０質量％であるのが好ましく、より好ましくは３〜１５質量％、更に好ましくは５〜１０質量％であるのがよい。触媒Ｂ成分の含有量が１質量％未満では充分な除去性能が得られず、２０質量％を超えて多くすると金属種のシンタリングによって却って性能低下を引き起こす恐れがあるからである。なお、触媒Ｂ成分としてバナジウム、ニオブ、タンタルのうちから複数の元素の化合物を用いる場合には、各化合物の酸化物換算での合計量が上記範囲にあるのがよい。また、触媒Ｂ成分を調製する際の出発原料としては、各元素の酸化物、水酸化物、無機塩、有機塩などが用いられ、例えばバナジウム源としてはメタバナジン酸アンモニウムが好適に用いられ、ニオブ源としてはシュウ酸ニオブやそのアンモニウム塩を用いることができる。 The component B of the catalyst of the present invention is a compound of at least one element of vanadium, niobium or tantalum, but is preferably contained in the form of an oxide from the viewpoint of removal performance. Further, the content greatly affects the removal performance, and it is preferably 1 to 20% by mass in terms of oxide with respect to the total mass of the catalyst A component, the catalyst B component and the catalyst C component, more preferably 3 to 15%. It is good that it is 5 mass%, More preferably, it is 5-10 mass%. This is because if the content of the catalyst B component is less than 1% by mass, sufficient removal performance cannot be obtained, and if it exceeds 20% by mass, there is a risk of performance degradation due to sintering of the metal species. In addition, when using the compound of a some element from vanadium, niobium, and a tantalum as a catalyst B component, it is good that the total amount in conversion of the oxide of each compound exists in the said range. Further, as starting materials for preparing the catalyst B component, oxides, hydroxides, inorganic salts, organic salts, and the like of each element are used. For example, ammonium metavanadate is preferably used as the vanadium source. As a source, niobium oxalate or its ammonium salt can be used.
本発明の触媒のＣ成分はモリブデンまたはタングステンの少なくとも１種の元素の化合物であるが、酸化物の形態で触媒に含有されているのが除去性能の点から好ましい。また、その含有量は除去性能および耐久性に大きく影響し、触媒Ａ成分と触媒Ｂ成分と触媒Ｃ成分の合計質量に対して酸化物換算で２〜１０質量％であるのが好ましく、より好ましくは３〜８質量％、更に好ましくは４〜６質量％であるのがよい。含有量が２質量％未満では充分な耐久性が得られず、１０質量％を超えて多くすると除去性能が低下する場合があるからである。なお触媒Ｃ成分としてモリブデン、タングステンの複数の元素の化合物を用いる場合には、各化合物の酸化物換算での合計量が上記範囲にあるのがよい。また、触媒Ｃ成分を調製する際の出発原料としては、各元素の酸化物、水酸化物、無機塩、有機塩などが用いられ、例えばモリブデン源としては酸化モリブデン、パラモリブデン酸アンモニウムおよびモリブデン酸が好適に用いられる。 The component C of the catalyst of the present invention is a compound of at least one element of molybdenum or tungsten, but is preferably contained in the catalyst in the form of an oxide from the viewpoint of removal performance. The content greatly affects removal performance and durability, and is preferably 2 to 10% by mass in terms of oxide with respect to the total mass of the catalyst A component, the catalyst B component, and the catalyst C component, and more preferably. Is 3 to 8% by mass, more preferably 4 to 6% by mass. This is because if the content is less than 2% by mass, sufficient durability cannot be obtained, and if the content exceeds 10% by mass, the removal performance may deteriorate. In addition, when using the compound of the some element of molybdenum and tungsten as a catalyst C component, the total amount in conversion of the oxide of each compound is good to exist in the said range. Further, as starting materials for preparing the catalyst C component, oxides, hydroxides, inorganic salts, organic salts and the like of each element are used. For example, molybdenum oxide, ammonium paramolybdate and molybdic acid are used as a molybdenum source. Are preferably used.
さらに、本発明の実施形態としては、触媒Ｂ成分としてバナジウム酸化物、触媒Ｃ成分としてモリブデン酸化物を用いるのが特に好ましく、これらを必須成分として含有することによって除去性能および耐久性に優れた触媒を得ることができる。 Furthermore, as an embodiment of the present invention, it is particularly preferable to use vanadium oxide as the catalyst B component and molybdenum oxide as the catalyst C component. By containing these as essential components, a catalyst having excellent removal performance and durability. Can be obtained.
本発明の触媒中の硫黄化合物の含有量は除去性能および耐久性に大きく影響し、具体的には硫黄化合物が硫黄原子換算で触媒の全質量に対し、０．４〜１．０質量％であるのがよく、より好ましくは０．５〜０．９質量％であるのがよい。硫黄化合物が０．４質量％未満では充分な耐久性が得られず、１．０質量％を超えて多くするとＮＯｘや有機ハロゲン化合物の除去性能が低くなるからである。硫黄化合物の原料としては、硫酸アンモニウム、硫酸、亜硫酸アンモニウム、過硫酸アンモニウムなどを用いる事ができ、好適には硫酸アンモニウムである。硫黄化合物はＡ成分調製時、Ａ成分にＢ成分・Ｃ成分添加時、３成分の混合時などに導入することができる。 The content of the sulfur compound in the catalyst of the present invention greatly affects the removal performance and durability. Specifically, the sulfur compound is 0.4 to 1.0% by mass with respect to the total mass of the catalyst in terms of sulfur atoms. It is good that it is 0.5 to 0.9% by mass. If the sulfur compound is less than 0.4% by mass, sufficient durability cannot be obtained, and if it exceeds 1.0% by mass, the removal performance of NOx and organic halogen compounds is lowered. As a raw material for the sulfur compound, ammonium sulfate, sulfuric acid, ammonium sulfite, ammonium persulfate, and the like can be used, and ammonium sulfate is preferable. The sulfur compound can be introduced when the A component is prepared, when the B component / C component is added to the A component, or when the three components are mixed.
なお、本発明にかかる触媒の性能を損なわないものであれば更に他の化合物を添加することもできる。 In addition, another compound can also be added as long as the performance of the catalyst according to the present invention is not impaired.
本発明の排ガス処理触媒の比表面積は、５０〜２００ｍ２／ｇの範囲にあるのがよく、より好ましくは６０〜１５０ｍ２／ｇ、更に好ましくは７０〜１２０ｍ２／ｇの範囲にあるのがよい。触媒の比表面積が低すぎると十分な触媒性能が得られない他、活性成分のシンタリングが起こりやすくなり、高すぎても触媒性能はそれほど向上しないが、被毒物質の蓄積量が多くなって性能低下が大きくなる場合があるからである。 The specific surface area of the exhaust gas treatment catalyst of the present invention should be in the range of 50 to 200 m 2 / g, more preferably 60 to 150 m 2 / g, and still more preferably in the range of 70 to 120 m 2 / g. Good. If the specific surface area of the catalyst is too low, sufficient catalyst performance cannot be obtained, and active component sintering is likely to occur, and if it is too high, the catalyst performance will not improve much, but the accumulated amount of poisonous substances will increase. This is because there is a case where the performance degradation becomes large.
また、本発明で用いる脱硝触媒の細孔容積は、全細孔容積が０．２０〜０．７０ｍＬ／ｇの範囲にあるのがよく、より好ましくは０．２５〜０．６０ｍＬ／ｇ、更に好ましくは０．３０〜０．５０ｍＬ／ｇの範囲にあるのがよい。触媒の細孔容積が小さすぎると十分な触媒性能が得られず、大きすぎても触媒性能はそれほど向上しないが、触媒の機械的強度が低下してハンドリングに支障をきたすことや耐摩耗性が低くなるなどの弊害が生じるおそれがあるので好ましくない。 The pore volume of the denitration catalyst used in the present invention is such that the total pore volume is in the range of 0.20 to 0.70 mL / g, more preferably 0.25 to 0.60 mL / g, Preferably it is in the range of 0.30 to 0.50 mL / g. If the pore volume of the catalyst is too small, sufficient catalyst performance will not be obtained, and if it is too large, the catalyst performance will not be improved so much, but the mechanical strength of the catalyst will be reduced, causing trouble in handling and wear resistance. This is not preferable because there is a risk that it may be lowered.
（触媒製造方法）
本発明の触媒の調製方法としては、（１）触媒Ａ成分にかかる三元系複合酸化物または混合酸化物を上記の方法で得た後、触媒Ｂ成分および触媒Ｃ成分の水性液を加えニーダーなどで十分混合し所定形状に成形し乾燥、焼成する方法、（２）触媒Ａ成分、触媒Ｂ成分および触媒Ｃ成分の原料を一度に混合し、乾燥、焼成し、更に水性媒体を加えスラリーとした後に所定形状に成形し乾燥、焼成する方法、（３）触媒Ａ成分、触媒Ｂ成分および触媒Ｃ成分の原料を一度に混合し、場合によってはｐＨ調整することで沈殿物を得た後、当該沈殿物を乾燥、焼成し、更に水性媒体を加えスラリーとした後に所定形状に成形し乾燥、焼成する方法、（４）（２）または（３）で得られたスラリーを通常触媒用担体として用いられる担体に被覆することもできる。（５）なお、（１）、（２）または（３）で成形する場合、ハニカム、ペレット、粒体に成形し乾燥、焼成し触媒とすることもできる。
(Catalyst production method)
As a method for preparing the catalyst of the present invention, (1) after obtaining the ternary complex oxide or mixed oxide relating to the catalyst A component by the above method, an aqueous solution of the catalyst B component and the catalyst C component is added to the kneader. (2) Catalyst A component, Catalyst B component and Catalyst C component raw materials are mixed at one time, dried and fired, and further added with an aqueous medium to form a slurry. After that, after forming into a predetermined shape, drying and firing, (3) mixing the raw materials of the catalyst A component, the catalyst B component and the catalyst C component at a time, and adjusting the pH in some cases to obtain a precipitate, A method in which the precipitate is dried and calcined, further added with an aqueous medium to form a slurry, then shaped into a predetermined shape, dried and calcined, and the slurry obtained in (4), (2) or (3) is usually used as a catalyst carrier Coating the carrier used It can be. (5) In addition, when shape | molding by (1), (2) or (3), it can also shape | mold into a honeycomb, a pellet, and a granule, can be dried and baked, and can also be set as a catalyst.
本発明にかかる触媒は、押し出し成形、打錠成形、転動造粒などにより、サドル状、ペレット、球体、ハニカム状に成形して用いることができる。またサドル状、ペレット、球体、ハニカム状の担体に触媒の成分を被覆して用いることもできる。排ガス処理装置の圧力損失を少なくするにはハニカム状が好ましい。また、触媒の調製においては各種金属化合物を用いた一般的な調製方法を用いることができ、例えば、触媒Ａ成分の成形体に触媒Ｂ成分および触媒Ｃ成分の溶液を含浸する方法や、触媒Ａ成分の粉体に触媒Ｂ成分および触媒Ｃ成分の溶液または粉体を混合した後に混練する方法などが挙げられるが、細孔容積の制御などの点から混練法が好適に用いられる。 The catalyst according to the present invention can be formed into a saddle, pellet, sphere, or honeycomb by extrusion molding, tableting, rolling granulation, or the like. Further, a catalyst component may be coated on a saddle, pellet, sphere, or honeycomb carrier. A honeycomb shape is preferable for reducing the pressure loss of the exhaust gas treatment apparatus. Further, in the preparation of the catalyst, a general preparation method using various metal compounds can be used. For example, a method of impregnating a molded product of the catalyst A component with a solution of the catalyst B component and the catalyst C component, Examples of the method include kneading after mixing the solution or powder of the catalyst B component and the catalyst C component to the component powder, and the kneading method is preferably used from the viewpoint of controlling the pore volume.
本発明は、前記本発明の触媒を用いて排ガス中のＮＯｘおよび／または有機ハロゲン化合物を除去する排ガス処理方法でもある。本発明の排ガスの処理温度は、１５０〜４００℃、好ましくは１５０〜３００℃、より好ましくは１６０〜２５０℃、更に好ましくは１６０〜１９０℃の範囲にあるのがよい。排ガスの処理温度が１５０℃未満ではＮＯｘや有機ハロゲン化合物の十分な除去効率が得られず、４００℃を超えるとモリブデンの飛散による触媒性能の低下や後流機器への悪影響を引き起こす場合があるからである。 The present invention is also an exhaust gas treatment method for removing NOx and / or organic halogen compounds in exhaust gas using the catalyst of the present invention. The treatment temperature of the exhaust gas of the present invention is in the range of 150 to 400 ° C, preferably 150 to 300 ° C, more preferably 160 to 250 ° C, and still more preferably 160 to 190 ° C. If the treatment temperature of the exhaust gas is less than 150 ° C., sufficient removal efficiency of NOx and organic halogen compounds cannot be obtained, and if it exceeds 400 ° C., the catalyst performance may be deteriorated due to the scattering of molybdenum and the downstream equipment may be adversely affected. It is.
（排ガス処理方法）
本発明にかかる触媒が処理対象とする排ガスは窒素酸化物（ＮＯｘ）および／または有機ハロゲン化合物を含むものであり、排ガス中のＮＯｘ濃度は５〜１０００ｐｐｍ（容量基準）であるのが好ましく、より好ましくは１０〜５００ｐｐｍ、更に好ましくは２０〜３００ｐｐｍの範囲にあるのがよい。排ガス中のＮＯｘ濃度が５ｐｐｍ未満では充分のＮＯｘ除去性能が発揮されず、一方、１０００ｐｐｍを超えると排ガス中に硫黄酸化物が含まれている場合、硫安化合物の蓄積量が増加して性能低下が大きくなるため好ましくないからである。
(Exhaust gas treatment method)
The exhaust gas to be treated by the catalyst according to the present invention contains nitrogen oxide (NOx) and / or an organic halogen compound, and the NOx concentration in the exhaust gas is preferably 5 to 1000 ppm (volume basis), more Preferably it is in the range of 10 to 500 ppm, more preferably 20 to 300 ppm. If the NOx concentration in the exhaust gas is less than 5 ppm, sufficient NOx removal performance will not be exhibited. On the other hand, if it exceeds 1000 ppm, if the exhaust gas contains sulfur oxides, the accumulated amount of ammonium sulfate compounds will increase and the performance will deteriorate. This is because the size is not preferable.
排ガス中の有機ハロゲン化合物の濃度は０．１ｐｐｔ〜３０００ｐｐｍ（容量基準）であるのが好ましく、より好ましくは０．５ｐｐｔ〜１０００ｐｐｍ、更に好ましくは１ｐｐｔ〜５００ｐｐｍの範囲にあるのがよい。排ガス中の有機ハロゲン化合物の濃度が０．１ｐｐｔ未満では充分な分解性能が発揮されず、一方、３０００ｐｐｍを超えると反応による発熱が大きくなり、触媒が熱的ダメージを受ける場合があるためである。 The concentration of the organic halogen compound in the exhaust gas is preferably 0.1 ppt to 3000 ppm (volume basis), more preferably 0.5 ppt to 1000 ppm, and still more preferably 1 ppt to 500 ppm. If the concentration of the organic halogen compound in the exhaust gas is less than 0.1 ppt, sufficient decomposition performance is not exhibited. On the other hand, if it exceeds 3000 ppm, heat generated by the reaction increases and the catalyst may be thermally damaged.
排ガスを処理する場合には排ガス中にアンモニアまたは尿素（アンモニア等とも称する）を添加することができる。特に排ガス中に窒素酸化物が含まれている場合には効果的である。アンモニア等の添加量は、窒素酸化物（ＮＯｘ換算）１モルに対して、アンモニア換算（尿素の場合は１／２モル）で０．２〜２０モル、好ましくは０．５〜１．０モルである。 In the case of treating exhaust gas, ammonia or urea (also referred to as ammonia or the like) can be added to the exhaust gas. This is particularly effective when the exhaust gas contains nitrogen oxides. The addition amount of ammonia and the like is 0.2 to 20 mol, preferably 0.5 to 1.0 mol in terms of ammonia (1/2 mol in the case of urea) with respect to 1 mol of nitrogen oxide (NOx conversion). It is.
有機ハロゲン化合物が排ガス中に含まれる場合はアンモニア等を加える必要はないが、アンモニア等が排ガス中に加えられても本発明にかかる触媒の効果は損なわれるものではない。 When the organic halogen compound is contained in the exhaust gas, it is not necessary to add ammonia or the like, but even if ammonia or the like is added to the exhaust gas, the effect of the catalyst according to the present invention is not impaired.
排ガス中に含まれる成分として酸素、水、ＳＯｘなどがある。例えば、排ガス中に酸素が存在する条件下で好適に用いられるが、この場合の酸素濃度は、０．１〜５０容量％の範囲にあるのが好ましく、より好ましくは０．３〜２０容量％、更に好ましくは０．５〜１６容量％の範囲にあるのがよい。酸素濃度が０．１容量％未満では除去効率が低下し、５０容量％を超えると副反応であるＳＯ２酸化が促進されるため、好ましくない。また、排ガス中に水分を含む場合には、その濃度は５０容量％以下であるのが好ましく、より好ましくは４０容量％以下、更に好ましくは３０容量％以下であるのがよい。排ガス中の水分濃度が５０容量％を超えると除去効率が低下する他、場合によっては性能低下が大きくなるからである。 Examples of components contained in the exhaust gas include oxygen, water, and SOx. For example, it is preferably used under conditions where oxygen is present in the exhaust gas. In this case, the oxygen concentration is preferably in the range of 0.1 to 50% by volume, more preferably 0.3 to 20% by volume. More preferably, it is in the range of 0.5 to 16% by volume. If the oxygen concentration is less than 0.1% by volume, the removal efficiency decreases, and if it exceeds 50% by volume, SO 2 oxidation as a side reaction is promoted, which is not preferable. When the exhaust gas contains moisture, the concentration is preferably 50% by volume or less, more preferably 40% by volume or less, and further preferably 30% by volume or less. This is because when the moisture concentration in the exhaust gas exceeds 50% by volume, the removal efficiency is lowered and, in some cases, the performance is greatly lowered.
排ガス中に硫黄酸化物（ＳＯｘ）を含有している場合であっても本発明にかかる触媒は好適に用いられるが、ＳＯｘ濃度としては０．１〜２０００ｐｐｍ（容量基準）、好ましくは０．２〜５００ｐｐｍ、より好ましくは０．５〜１００ｐｐｍ、更に好ましくは１〜５０ｐｐｍの範囲にあるのがよい。ＳＯｘ濃度が０．１ｐｐｍ以上である排ガスの処理において本発明の効果が発揮される。一方、排ガス中にＳＯｘ濃度が２０００ｐｐｍを超えるとＳＯｘによる性能低下が大きくなるため、好ましくない。 Even if the exhaust gas contains sulfur oxide (SOx), the catalyst according to the present invention is preferably used, but the SOx concentration is 0.1 to 2000 ppm (volume basis), preferably 0.2. It should be in the range of ˜500 ppm, more preferably 0.5 to 100 ppm, and still more preferably 1 to 50 ppm. The effect of the present invention is exhibited in the treatment of exhaust gas having a SOx concentration of 0.1 ppm or more. On the other hand, if the SOx concentration in the exhaust gas exceeds 2000 ppm, the performance degradation due to SOx increases, which is not preferable.
また、本発明の排ガス処理に際しての空間速度は、１００〜５０，０００ｈ−１（ＳＴＰ）、好ましくは２００〜１０，０００ｈ−１（ＳＴＰ）、より好ましくは５００〜５，０００ｈ−１（ＳＴＰ）の範囲にあるのがよい。空間速度が５０，０００ｈ−１（ＳＴＰ）を超えるとＮＯｘや有機ハロゲン化合物の十分な除去効率が得られず、１００ｈ−１（ＳＴＰ）未満では除去効率は大きく変わらないが排ガス処理装置の圧力損失が高くなり、また装置自体も大きくなって非効率だからである。更に本発明の排ガス処理に際しての触媒層を通過するガスの線速度は、０．１〜１０ｍ／ｓ（Ｎｏｒｍａｌ）、好ましくは０．５〜７ｍ／ｓ（Ｎｏｒｍａｌ）、より好ましくは０．７〜４ｍ／ｓ（Ｎｏｒｍａｌ）の範囲にあるのがよい。線速度が０．１ｍ／ｓ（Ｎｏｒｍａｌ）未満では充分な除去効率が得られず、１０ｍ／ｓ（Ｎｏｒｍａｌ）を超えると除去効率は大きくはらないが、排ガス処理装置の圧力損失が高くなるからである。 The space velocity during the exhaust gas treatment of the present invention is 100 to 50,000 h −1 (STP), preferably 200 to 10,000 h −1 (STP), more preferably 500 to 5,000 h −1 (STP). It is good to be in the range. Pressure loss of sufficient removal efficiency can not be obtained, it is less than 100h -1 (STP) but removal efficiency does not change greatly the exhaust gas treatment apparatus of the space velocity exceeds 50,000h -1 (STP) NOx and organic halogen compounds And the device itself becomes larger and inefficient. Furthermore, the linear velocity of the gas passing through the catalyst layer in the exhaust gas treatment of the present invention is 0.1 to 10 m / s (Normal), preferably 0.5 to 7 m / s (Normal), more preferably 0.7 to It should be in the range of 4 m / s (Normal). If the linear velocity is less than 0.1 m / s (Normal), sufficient removal efficiency cannot be obtained, and if it exceeds 10 m / s (Normal), the removal efficiency does not increase, but the pressure loss of the exhaust gas treatment device increases. is there.
以下に実施例により発明を詳細に説明するが、本発明の効果を奏するものであれば以下の実施例に限定されるものではない。 The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples as long as the effects of the present invention are achieved.
（実施例１）
＜触媒の製造＞
４Ｌの水にメタバナジン酸アンモニウム１．４２ｋｇとシュウ酸２．５５ｋｇ、さらにモノエタノールアミン０．７７ｋｇを混合し、溶解させ、均一溶液を調製した。硫黄化合物が硫黄原子換算で０．８質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体（質量比がＴｉＯ２：ＳｉＯ２：ＷＯ３＝９３：５：２）２１．１ｋｇとモリブデン酸（Ｈ２ＭｏＯ４・Ｈ２Ｏ）１．１８ｋｇをニーダーに投入後、有機バインダーなどの成形助剤とともにバナジウム含有均一溶液を加え、よく撹拌した。さらに適量の水を加えつつブレンダ―でよく混合した後、連続ニーダーで充分混練りし、外形８０ｍｍ角、長さ５５０ｍｍ、目開き２．９０ｍｍ、肉厚０．４ｍｍのハニカム状に押し出し成形した。得られた成形物を６０℃で１．５時間乾燥後、４２０℃で５時間焼成して触媒Ａを得た。この触媒Ａの組成は、ＴｉＯ２：ＳｉＯ２：ＷＯ３：ＭｏＯ３：Ｖ２Ｏ５＝７８：７：２：６：７（質量比）であり、ＢＥＴ比表面積は７３ｍ２／ｇ、全細孔容積は０．４０ｍＬ／ｇ、であった。また触媒Ａに含有される硫黄化合物は硫黄原子換算で触媒Ａの全体量に対し０．５質量％であった。
Example 1
<Manufacture of catalyst>
In 4 L of water, 1.42 kg of ammonium metavanadate, 2.55 kg of oxalic acid, and 0.77 kg of monoethanolamine were mixed and dissolved to prepare a uniform solution. Ti-Si-W complex oxide powder (mass ratio is TiO 2 : SiO 2 : WO 3 = 93: 5: 2) 20.8 kg and molybdic acid (0.8% by mass in terms of sulfur atom) after introducing H 2 MoO 4 · H 2 O ) 1.18kg in a kneader, a vanadium-containing homogeneous solution was added with a molding aid such as an organic binder, followed by thorough stirring. Further, after mixing well with a blender while adding an appropriate amount of water, the mixture was sufficiently kneaded with a continuous kneader and extruded into a honeycomb shape having an outer shape of 80 mm square, a length of 550 mm, an opening of 2.90 mm, and a wall thickness of 0.4 mm. The obtained molded product was dried at 60 ° C. for 1.5 hours and then calcined at 420 ° C. for 5 hours to obtain Catalyst A. The composition of the catalyst A is TiO 2 : SiO 2 : WO 3 : MoO 3 : V 2 O 5 = 78: 7: 2: 6: 7 (mass ratio), and the BET specific surface area is 73 m 2 / g. The pore volume was 0.40 mL / g. Moreover, the sulfur compound contained in the catalyst A was 0.5 mass% with respect to the total amount of the catalyst A in terms of sulfur atoms.
（実施例２）
実施例１において、硫黄化合物が硫黄原子換算で２．０質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体２１．１ｋｇの代わりに硫黄化合物が硫黄原子換算で２．０質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体２１．１ｋｇを使用した以外は実施例１と同様にして、触媒Ｂを得た。この触媒Ｂの組成は、ＴｉＯ２：ＳｉＯ２：ＷＯ３：ＭｏＯ３：Ｖ２Ｏ５＝７８：７：２：６：７（質量比）であり、ＢＥＴ比表面積は７５ｍ２／ｇ、全細孔容積は０．４１ｍＬ／ｇ、であった。また触媒Ｂに含有される硫黄化合物は硫黄原子換算で触媒Ｂの全体量に対し質量０．８％であった。
(Example 2)
In Example 1, instead of 21.1 kg of the Ti—Si—W composite oxide powder containing 2.0 mass% of the sulfur compound in terms of sulfur atom, Ti containing 2.0 mass% of the sulfur compound in terms of sulfur atom A catalyst B was obtained in the same manner as in Example 1 except that 21.1 kg of the Si-W composite oxide powder was used. The composition of the catalyst B is TiO 2 : SiO 2 : WO 3 : MoO 3 : V 2 O 5 = 78: 7: 2: 6: 7 (mass ratio), and the BET specific surface area is 75 m 2 / g. The pore volume was 0.41 mL / g. Further, the sulfur compound contained in the catalyst B was 0.8% by mass with respect to the total amount of the catalyst B in terms of sulfur atoms.
（比較例１）
実施例１において、硫黄化合物が硫黄原子換算で０．６質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体２１．１ｋｇの代わりに硫黄化合物が硫黄原子換算で０．６質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体２１．１ｋｇを使用した以外は実施例１と同様にして、触媒Ｃを得た。この触媒Ｃの組成は、ＴｉＯ２：ＳｉＯ２：ＷＯ３：ＭｏＯ３：Ｖ２Ｏ５＝７８：７：２：６：７（質量比）であり、ＢＥＴ比表面積は７９ｍ２／ｇ、全細孔容積は０．４５ｍＬ／ｇ、であった。また触媒Ｃに含有される硫黄化合物は硫黄原子換算で触媒Ｃの全体量に対し０．３質量％であった。
(Comparative Example 1)
In Example 1, instead of 21.1 kg of the Ti—Si—W composite oxide powder containing 0.6 mass% of the sulfur compound in terms of sulfur atom, Ti containing 0.6 mass% of the sulfur compound in terms of sulfur atom A catalyst C was obtained in the same manner as in Example 1 except that 21.1 kg of the Si-W composite oxide powder was used. The composition of this catalyst C is TiO 2 : SiO 2 : WO 3 : MoO 3 : V 2 O 5 = 78: 7: 2: 6: 7 (mass ratio), BET specific surface area is 79 m 2 / g, all The pore volume was 0.45 mL / g. Moreover, the sulfur compound contained in the catalyst C was 0.3 mass% with respect to the total amount of the catalyst C in terms of sulfur atoms.
（比較例２）
実施例１において、硫黄化合物が硫黄原子換算で３．１質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体２１．１ｋｇの代わりに硫黄化合物が硫黄原子換算で３．０質量％含まれるＴｉ−Ｓｉ−Ｗ複合酸化物粉体２１．１ｋｇを使用した以外は実施例１と同様にして、触媒Ｄを得た。この触媒Ｄの組成は、ＴｉＯ２：ＳｉＯ２：ＷＯ３：ＭｏＯ３：Ｖ２Ｏ５＝７８：７：２：６：７（質量比）であり、ＢＥＴ比表面積は８４ｍ２／ｇ、全細孔容積は０．４１ｍＬ／ｇ、であった。また触媒Ｄに含有される硫黄化合物は硫黄原子換算で触媒Ｄの全体量に対し１．３質量％であった。
(Comparative Example 2)
In Example 1, instead of 21.1 kg of Ti-Si-W composite oxide powder containing 3.1% by mass of sulfur compound in terms of sulfur atom, Ti containing 3.0% by mass of sulfur compound in terms of sulfur atom A catalyst D was obtained in the same manner as in Example 1 except that 21.1 kg of the Si-W composite oxide powder was used. The composition of the catalyst D is TiO 2 : SiO 2 : WO 3 : MoO 3 : V 2 O 5 = 78: 7: 2: 6: 7 (mass ratio), and the BET specific surface area is 84 m 2 / g, The pore volume was 0.41 mL / g. Further, the sulfur compound contained in the catalyst D was 1.3% by mass with respect to the total amount of the catalyst D in terms of sulfur atoms.
（ＮＯｘ除去試験）
実施例１〜２および比較例１〜２で得た触媒Ａ〜Ｄを用い、下記性能評価条件でＮＯｘ除去性能の評価を行った。
(NOx removal test)
Using the catalysts A to D obtained in Examples 1-2 and Comparative Examples 1-2, the NOx removal performance was evaluated under the following performance evaluation conditions.
（ＳＯ２曝露耐久試験）
下記条件で３００時間曝露した後、ＮＯｘ除去性能の評価を行った。
(SO2 exposure durability test)
After exposure for 300 hours under the following conditions, the NOx removal performance was evaluated.
［ＮＯｘ除去性能評価条件］
ＮＯｘ：３００ｐｐｍ，ＮＨ３：３００ｐｐｍ，Ｏ２：１２容量％，Ｈ２Ｏ：１０容量％，Ｎ２：ｂａｌａｎｃｅ，ガス温度：２５０℃，空間速度：２３，０００ｈ−１（ＳＴＰ），ガス線速度：１．０ｍ／ｓ（Ｎｏｒｍａｌ）
［曝露条件］
ＮＯｘ：１，０００ｐｐｍ，ＮＨ３：１，０００ｐｐｍ，ＳＯｘ：６００ｐｐｍ，ＳＯ３：１０ｐｐｍ，Ｏ２：１２容量％，Ｈ２Ｏ：１０容量％，Ｎ２：ｂａｌａｎｃｅ，ガス温度：２５０℃，空間速度：１２，５００ｈ−１（ＳＴＰ），ガス線速度：０．５ｍ／ｓ（Ｎｏｒｍａｌ）
次に、触媒入口および触媒出口のＮＯｘ濃度を測定し、次式に従って脱硝率（ＮＯｘ除去率）を算出した。結果を表１に示す。
[NOx removal performance evaluation conditions]
NOx: 300 ppm, NH3: 300 ppm, O2: 12 vol%, H2O: 10 vol%, N2: balance, gas temperature: 250 ° C, space velocity: 23,000 h-1 (STP), gas linear velocity: 1.0 m / s (Normal)
[Exposure conditions]
NOx: 1,000 ppm, NH3: 1,000 ppm, SOx: 600 ppm, SO3: 10 ppm, O2: 12 vol%, H2O: 10 vol%, N2: balance, gas temperature: 250 ° C, space velocity: 12,500 h-1 (STP), gas linear velocity: 0.5 m / s (Normal)
Next, the NOx concentrations at the catalyst inlet and the catalyst outlet were measured, and the denitration rate (NOx removal rate) was calculated according to the following equation. The results are shown in Table 1.
（クロロトルエン分解試験）
実施例１〜２触媒Ａ〜Ｂを用い、下記条件でクロロトルエン分解性能評価を行った。
(Chlorotoluene decomposition test)
Examples 1-2 The chlorotoluene decomposition performance evaluation was performed on the following conditions using catalyst AB.
［クロロトルエン分解性能評価条件］
クロロトルエン：３０ｐｐｍ，Ｏ２：１０容量％，Ｈ２Ｏ：１５容量％，Ｎ２：ｂａｌａｎｃｅ，ガス温度：２００℃，空間速度：８２５０ｈ−１（ＳＴＰ），ガス線速度０．５ｍ／ｓ（Ｎｏｒｍａｌ）
次に、触媒入口および触媒出口のクロロトルエン（ＣＴ）濃度を測定し、次式に従ってクロロトルエン（ＣＴ）分解率を算出した。結果を表１に示す。
[Chlorotoluene decomposition performance evaluation conditions]
Chlorotoluene: 30 ppm, O2: 10% by volume, H2O: 15% by volume, N2: balance, gas temperature: 200 ° C., space velocity: 8250 h −1 (STP), gas linear velocity 0.5 m / s (Normal)
Next, the chlorotoluene (CT) concentration at the catalyst inlet and the catalyst outlet was measured, and the chlorotoluene (CT) decomposition rate was calculated according to the following equation. The results are shown in Table 1.
比較例１の触媒Ｃは、Ｓ含有率が低いため曝露前の脱硝率は高いものの、３００時間曝露後の脱硝率が大きく低下し十分な耐久性を有していない。比較例２の触媒Ｄは、Ｓ含有率が高いために、曝露前の脱硝率が低く、３００時間曝露後の脱硝率も大きく低下した。これに対して、本発明の実施例１、２の触媒Ａ、Ｂは、いずれも３００時間曝露後に高い脱硝率を有しており、暴露前後の脱硝率の低下割合が触媒Ｃ、Ｄよりも小さいことから十分な耐久性を有していることが分かる。このように本発明の触媒では硫黄酸化物による性能低下が軽減されるので触媒交換の頻度が減り、排ガス処理装置のランニングコストを低減することが可能になる。 Although the catalyst C of Comparative Example 1 has a low S content, the denitration rate before exposure is high, but the denitration rate after exposure for 300 hours is greatly reduced and does not have sufficient durability. Since the catalyst D of Comparative Example 2 has a high S content, the denitration rate before exposure was low, and the denitration rate after exposure for 300 hours was greatly reduced. On the other hand, the catalysts A and B of Examples 1 and 2 of the present invention both have a high denitration rate after exposure for 300 hours, and the rate of decrease in the denitration rate before and after exposure is higher than that of the catalysts C and D. Since it is small, it turns out that it has sufficient durability. As described above, in the catalyst of the present invention, the performance degradation due to sulfur oxide is reduced, so the frequency of catalyst replacement is reduced, and the running cost of the exhaust gas treatment device can be reduced.
また、触媒Ａと触媒Ｂのクロロトルエン分解率はそれぞれ７２．０％、６６．４％であり、本発明の触媒は有機ハロゲン化合物の分解においても有効であることが分かる。 Moreover, the chlorotoluene decomposition rates of the catalyst A and the catalyst B are 72.0% and 66.4%, respectively, which shows that the catalyst of the present invention is also effective in the decomposition of the organic halogen compound.
本発明は排ガス処理に関する技術であり、各種産業排ガスの処理、特に窒素酸化物や有機ハロゲン化合物を含む排ガスの処理に用いることができる。更に詳しくは、都市ごみや産業廃棄物を処理する焼却施設、重油焚きボイラや石炭焚きボイラ、ディーゼルエンジン、火力発電所および各種工業プロセスから排出される排ガス中に含まれる窒素酸化物（ＮＯｘ）および／または有機ハロゲン化合物を接触還元または分解除去する為の排ガス処理触媒、およびこの触媒を用いた排ガス処理方法に応用することができる。 The present invention is a technology related to exhaust gas treatment, and can be used for treatment of various industrial exhaust gases, particularly for treatment of exhaust gas containing nitrogen oxides and organic halogen compounds. More specifically, incineration facilities for treating municipal waste and industrial waste, heavy oil fired boilers, coal fired boilers, diesel engines, thermal power plants, and nitrogen oxides (NOx) contained in exhaust gas discharged from various industrial processes and The present invention can be applied to an exhaust gas treatment catalyst for catalytic reduction or decomposition removal of organic halogen compounds and an exhaust gas treatment method using this catalyst.
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| JP2005144299A (en) * | 2003-11-13 | 2005-06-09 | Nippon Shokubai Co Ltd | Nitrogen oxide removal catalyst and nitrogen oxide removal method |
| JP2006320803A (en) * | 2005-05-18 | 2006-11-30 | Nippon Shokubai Co Ltd | Catalyst and method for treating exhaust gas |
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| JP2019072663A (en) * | 2017-10-16 | 2019-05-16 | 株式会社日本触媒 | Method for producing organic composite oxide and method for treating exhaust gas using the same |
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