JP2008296224A - Nitrogen oxide removing catalyst, nitrogen oxide removing method using it, and nitrogen oxide removing device - Google Patents
Nitrogen oxide removing catalyst, nitrogen oxide removing method using it, and nitrogen oxide removing device Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 37
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004480 active ingredient Substances 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims description 55
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- 229910018173 Al—Al Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、窒素酸化物浄化触媒、並びにそれを用いた窒素酸化物の浄化方法及び窒素酸化物浄化装置に関する。 The present invention relates to a nitrogen oxide purification catalyst, a nitrogen oxide purification method and a nitrogen oxide purification apparatus using the same.
従来、窒素酸化物を浄化（除去）させるために、窒素酸化物をアンモニアの存在下で酸化チタン及び酸化バナジウムを主成分とする触媒と接触させて還元脱硝する技術（下式（１）及び（２）などを参照）が用いられている（例えば、特許文献１参照）。
式（１）・・・ＮＯ２＋２ＮＨ３＋１／２Ｏ２→３／２Ｎ２＋３Ｈ２Ｏ
式（２）・・・ＮＯ＋ＮＨ３＋１／４Ｏ２→Ｎ２＋３／２Ｈ２Ｏ
Formula (1) ... NO 2 + 2NH 3 + 1 / 2O 2 → 3 / 2N 2 + 3H 2 O
Formula (2) ... NO + NH 3 + 1 / 4O 2 → N 2 + 3 / 2H 2 O
しかしながら、上記触媒に含まれているバナジウムはその有害性が指摘されており、触媒成分の排出による環境問題が懸念されている。 However, the vanadium contained in the above catalyst has been pointed out to be harmful, and there are concerns about environmental problems due to the discharge of catalyst components.
また、上記触媒は窒素酸化物を完全に還元脱硝することができず、より効率の高い触媒の開発が求められている。 Further, the above catalyst cannot completely reduce denitration of nitrogen oxides, and development of a more efficient catalyst is demanded.
そこで本発明は、窒素酸化物を高い効率で還元脱硝することが可能な、窒素酸化物浄化触媒、その触媒を用いた窒素酸化物浄化方法、及び、その触媒を備えた窒素酸化物浄化装置を提供することを目的とする。 Therefore, the present invention provides a nitrogen oxide purification catalyst, a nitrogen oxide purification method using the catalyst, and a nitrogen oxide purification apparatus equipped with the catalyst, capable of reducing and denitrating nitrogen oxide with high efficiency. The purpose is to provide.
本発明者らは、酸化タングステン−ジルコニア型複合酸化物にセリウムを添加することにより得られた触媒（以下「Ce-W-Zr系触媒」と称する。）を用いて、アンモニア選択還元脱硝反応を行ったところ、窒素酸化物を効率よく浄化できることを見出した。 The present inventors performed ammonia selective reduction denitration reaction using a catalyst obtained by adding cerium to tungsten oxide-zirconia type composite oxide (hereinafter referred to as “Ce—W—Zr catalyst”). As a result, it was found that nitrogen oxides can be efficiently purified.
また、本発明者らは、チタニア−ジルコニア型複合酸化物にセリウム及び硫黄を添加することにより得られた触媒（以下「Ce-Ti-SO4-Zr系触媒」と称する。）とFe-Si-Al系触媒との混合触媒を用いて、アンモニア選択還元脱硝反応を行ったところ、Ce-Ti-SO4-Zr系触媒を単独で用いた場合に比べ、窒素酸化物をさらに効率よく浄化できることを見出した。このようにして、本発明者らは本発明を完成するに至った。 In addition, the present inventors have prepared a catalyst obtained by adding cerium and sulfur to a titania-zirconia composite oxide (hereinafter referred to as “Ce—Ti—SO 4 —Zr catalyst”) and Fe—Si. Nitrogen oxide can be purified more efficiently than when Ce-Ti-SO 4 -Zr catalyst is used alone when ammonia selective reduction denitration reaction is performed using a mixed catalyst with Al-Al catalyst. I found. Thus, the present inventors have completed the present invention.
すなわち、本発明の窒素酸化物浄化触媒は、少なくとも、酸化タングステン−ジルコニア型複合酸化物と、セリウムと、を有効成分として含有することを特徴とする。 That is, the nitrogen oxide purification catalyst of the present invention is characterized by containing at least a tungsten oxide-zirconia type composite oxide and cerium as active ingredients.
本発明の窒素酸化物浄化触媒は、さらに硫黄又はリンを含有することを特徴とする。 The nitrogen oxide purification catalyst of the present invention further contains sulfur or phosphorus.
本発明の窒素酸化物浄化触媒は、少なくとも、酸化タングステン−ジルコニア型複合酸化物と、セリウムと、を有効成分として含有する第一の複合体と、シリカ、アルミナ、チタニア、ジルコニア、及び酸化タングステンから選ばれる１又は２以上の酸化物と、希土類金属又は遷移金属と、を有効成分として含有する第二の複合体と、を有し、前記第一の複合体と前記第二の複合体とは活性種成分が異なることを特徴とする。 The nitrogen oxide purification catalyst of the present invention comprises at least a first composite containing tungsten oxide-zirconia type composite oxide and cerium as active ingredients, silica, alumina, titania, zirconia, and tungsten oxide. A second composite containing one or two or more selected oxides and a rare earth metal or a transition metal as an active ingredient, wherein the first composite and the second composite are The active species component is different.
本発明の窒素酸化物浄化触媒は、前記第二の複合体における複合酸化物が、シリカ−アルミナ型複合酸化物であることを特徴とする。 The nitrogen oxide purification catalyst of the present invention is characterized in that the complex oxide in the second complex is a silica-alumina complex oxide.
本発明の窒素酸化物浄化触媒は、前記第二の複合体は担体基材に担持されており、前記第一の複合体は前記第二の複合体に担持されていることを特徴とする。 The nitrogen oxide purification catalyst of the present invention is characterized in that the second complex is supported on a carrier substrate, and the first complex is supported on the second complex.
本発明の窒素酸化物の浄化方法は、窒素酸化物浄化触媒に窒素酸化物とアンモニアとを接触させて、還元脱硝することを特徴とする。 The nitrogen oxide purification method of the present invention is characterized in that nitrogen oxide and ammonia are brought into contact with a nitrogen oxide purification catalyst to perform reductive denitration.
本発明の窒素酸化物浄化装置は、窒素酸化物浄化触媒を備えることを特徴とする。 The nitrogen oxide purification apparatus of the present invention is characterized by including a nitrogen oxide purification catalyst.
本発明によれば、窒素酸化物を高い効率で還元脱硝することが可能な、窒素酸化物浄化触媒、その触媒を用いた窒素酸化物浄化方法、及び、その触媒を備えた窒素酸化物浄化装置を提供することができる。 According to the present invention, a nitrogen oxide purification catalyst capable of reducing and denitrating nitrogen oxide with high efficiency, a nitrogen oxide purification method using the catalyst, and a nitrogen oxide purification apparatus including the catalyst Can be provided.
上記知見に基づき完成した本発明を実施するための形態を、実施例を挙げながら詳細に説明する。まず、本発明に係る窒素酸化物浄化触媒について説明する。 An embodiment for carrying out the present invention completed based on the above knowledge will be described in detail with reference to examples. First, the nitrogen oxide purification catalyst according to the present invention will be described.
＝＝＝窒素酸化物浄化触媒について＝＝＝
本発明に係る窒素酸化物浄化触媒は、少なくとも、酸化タングステン−ジルコニア型複合酸化物と、セリウムと、を有効成分として含有するものである。セリウムの含有率は２ｗｔ％〜５０ｗｔ％の範囲内であることが好ましい。
=== About the nitrogen oxide purification catalyst ===
The nitrogen oxide purification catalyst according to the present invention contains at least a tungsten oxide-zirconia type composite oxide and cerium as active ingredients. The content of cerium is preferably in the range of 2 wt% to 50 wt%.
また、本発明に係る窒素酸化物浄化触媒に含ませる酸化タングステン−ジルコニア型複合酸化物は、タングステンとジルコニアとのモル組成比（Ｗ：Ｚｒ）が１：２０〜１：５の範囲内であるものが好ましい。 Moreover, the tungsten oxide-zirconia type composite oxide contained in the nitrogen oxide purification catalyst according to the present invention has a molar composition ratio (W: Zr) of tungsten and zirconia in the range of 1:20 to 1: 5. Those are preferred.
また、本発明に係る窒素酸化物浄化触媒は、少なくとも、酸化タングステン−ジルコニア型複合酸化物と、セリウムと、を有効成分として含有する第一の複合体と、シリカ、アルミナ、チタニア、ジルコニア、及び酸化タングステンから選ばれる１又は２以上の酸化物と、希土類金属又は遷移金属と、を有効成分として含有する第二の複合体と、を有し、前記第一の複合体と前記第二の複合体とは活性種成分が異なるものである。 Further, the nitrogen oxide purification catalyst according to the present invention includes at least a first composite containing tungsten oxide-zirconia type composite oxide and cerium as active ingredients, silica, alumina, titania, zirconia, and A second composite containing one or more oxides selected from tungsten oxide and a rare earth metal or a transition metal as active ingredients, the first composite and the second composite The active species component is different from the body.
第二の複合体における複合酸化物は、シリカ−アルミナ型複合酸化物であることが好ましく、このシリカ−アルミナ型複合酸化物における珪素とアルミニウムのモル組成比（Ｓｉ：Ａｌ）は、５：１〜５００：１の範囲内であることが好ましい。 The composite oxide in the second composite is preferably a silica-alumina composite oxide, and the molar composition ratio (Si: Al) of silicon and aluminum in the silica-alumina composite oxide is 5: 1. It is preferably within the range of ˜500: 1.
前記遷移金属としては、第一遷移金属元素（２１Sc〜２９Cu）、第二遷移金属元素（３９Ｙ〜４７Ag）、及び第三遷移金属元素（７２Hf〜７９Au）がつくる単体のうち、銅（Cu）、コバルト（Co）、ニッケル（Ni）マンガン（Mn）、クロム（Cr）、バナジウム（V）などの有害性金属を除くものであればどのようなものでもよい。なお、本発明に係る窒素酸化物浄化触媒における遷移金属又は希土類金属は、２ｗｔ％〜５０ｗｔ％の範囲内で含まれていることが好ましい。 Among the transition metals, the first transition metal element ( 21 Sc to 29 Cu), the second transition metal element ( 39 Y to 47 Ag), and the third transition metal element ( 72 Hf to 79 Au) are used. Any other material may be used as long as it excludes harmful metals such as copper (Cu), cobalt (Co), nickel (Ni) manganese (Mn), chromium (Cr), and vanadium (V). In addition, it is preferable that the transition metal or rare earth metal in the nitrogen oxide purification catalyst according to the present invention is included in the range of 2 wt% to 50 wt%.
なお、２以上の複合体を有する窒素酸化物浄化触媒において、これら複合体の重量比は窒素酸化物をより高い効率で浄化することが可能な数値であれば特に制限されるものではないが、一方の複合体がセリウム及びチタニア−ジルコニア型複合酸化物を有し、他方の複合体が鉄及びシリカ−アルミナ型複合酸化物を有するものである場合には、前者の複合体と後者の複合体との重量比が０．２：０．８〜０．８：０．２の範囲内であることが好ましい。 In the nitrogen oxide purification catalyst having two or more composites, the weight ratio of these composites is not particularly limited as long as it is a numerical value capable of purifying nitrogen oxide with higher efficiency. When one composite has cerium and titania-zirconia type composite oxide, and the other composite has iron and silica-alumina type composite oxide, the former composite and the latter composite are used. Is preferably in the range of 0.2: 0.8 to 0.8: 0.2.
本発明に係る窒素酸化物浄化触媒に含まれる複合体は、さらに硫黄又はリンを含有していてもよい。複合体における硫黄又はリンの含有率は、１０ｗｔ％以下であることが好ましく、０．５ｗｔ％〜１０％以下の範囲内であることがより好ましい。 The composite contained in the nitrogen oxide purification catalyst according to the present invention may further contain sulfur or phosphorus. The content of sulfur or phosphorus in the composite is preferably 10 wt% or less, and more preferably in the range of 0.5 wt% to 10%.
＝＝＝他の実施形態について＝＝＝
上述のように、本発明に係る窒素酸化物浄化触媒は窒素酸化物を高い効率で浄化することができることから、本発明に係る窒素酸化物浄化触媒を用いた窒素酸化物浄化方法や、本発明に係る窒素酸化物浄化触媒を備えた窒素酸化物浄化装置は、例えば、ディーゼル、石炭などの燃料を燃焼させた際に発生する排ガス中の窒素酸化物を浄化するのに有用である。
=== About other embodiments ===
As described above, since the nitrogen oxide purification catalyst according to the present invention can purify nitrogen oxide with high efficiency, the nitrogen oxide purification method using the nitrogen oxide purification catalyst according to the present invention, and the present invention The nitrogen oxide purification apparatus including the nitrogen oxide purification catalyst according to the present invention is useful for purifying nitrogen oxides in exhaust gas generated when a fuel such as diesel or coal is burned.
なお、本発明に係る窒素酸化物浄化方法又は窒素酸化物浄化装置において、窒素酸化物を浄化するために脱硝還元剤の添加（注入）が必要となるが、添加する脱硝還元剤の添加量としては、窒素酸化物を還元分解するのに必要な量であれば特に制限されるものではない。脱硝還元剤としては、アンモニア、アンモニア水（安水）、液化アンモニアなどのアンモニア源を用いることとしてもよいが、アンモニアを生成することができるアンモニア前駆体を用いることとしてもよい。アンモニア前駆体は、例えば、熱分解によりアンモニアを生成することができる尿素、尿素水などである。なお、環境などの面から尿素や尿素水を脱硝還元剤として用いることが好ましい。 In addition, in the nitrogen oxide purification method or the nitrogen oxide purification apparatus according to the present invention, it is necessary to add (inject) a denitration reducing agent in order to purify the nitrogen oxide. Is not particularly limited as long as it is an amount necessary for reductive decomposition of nitrogen oxides. As the denitration reducing agent, an ammonia source such as ammonia, aqueous ammonia (aqueous water) or liquefied ammonia may be used, but an ammonia precursor capable of generating ammonia may be used. The ammonia precursor is, for example, urea or urea water that can generate ammonia by thermal decomposition. Note that it is preferable to use urea or urea water as a denitration reducing agent from the viewpoint of environment and the like.
脱硝還元剤の注入量としては、窒素酸化物を還元分解するのに必要な量であれば特に制限されるものではなく、窒素酸化物の量及び、触媒の浄化性能等、特性に応じた量を注入することが好ましい。このように脱硝還元剤の量を調節して添加することにより、窒素酸化物を高い効率で浄化することができるようになる。 The injection amount of the denitration reducing agent is not particularly limited as long as it is an amount necessary for reductive decomposition of nitrogen oxides, and the amount according to characteristics such as the amount of nitrogen oxides and the purification performance of the catalyst. Is preferably injected. Thus, by adjusting and adding the amount of the denitration reducing agent, nitrogen oxides can be purified with high efficiency.
また、本発明に係る窒素酸化物浄化方法又は窒素酸化物浄化装置において、還元脱硝する際の反応温度としては、１５０℃〜５００℃の範囲内であることが好ましく、アンモニア還元触媒がアンモニアを効率よく吸着させる点で１８５℃〜５００℃の範囲内であることが特に好ましく、窒素酸化物を効率よく浄化することができる点で２２０℃〜５００℃の範囲内であることが最も好ましい。なお、尿素を添加してアンモニアを生成させる場合には、還元脱硝する際の反応温度はアンモニアを効率よく生成できる点で１７０℃〜２５０℃の範囲内であることが好ましい。 Further, in the nitrogen oxide purification method or nitrogen oxide purification apparatus according to the present invention, the reaction temperature at the time of reductive denitration is preferably within a range of 150 ° C. to 500 ° C., and the ammonia reduction catalyst efficiently converts ammonia. It is particularly preferably in the range of 185 ° C. to 500 ° C. in terms of good adsorption, and most preferably in the range of 220 ° C. to 500 ° C. in terms of efficiently purifying nitrogen oxides. In addition, when adding urea and producing | generating ammonia, it is preferable that the reaction temperature at the time of reductive denitration exists in the range of 170 to 250 degreeC at the point which can produce | generate ammonia efficiently.
さらに、本発明に係る窒素酸化物浄化方法又は窒素酸化物浄化装置において、窒素酸化物浄化装置に導入する窒素酸化物の空間速度は、５，０００／ｈ〜２００，０００／ｈの範囲内であることが好ましく、１０，０００／ｈ〜５０，０００／ｈの範囲内であることが特に好ましい。 Furthermore, in the nitrogen oxide purification method or the nitrogen oxide purification device according to the present invention, the space velocity of the nitrogen oxide introduced into the nitrogen oxide purification device is within the range of 5,000 / h to 200,000 / h. It is preferable that it is within a range of 10,000 / h to 50,000 / h.
以下に本発明を実施例によって具体的に説明する。なお、これらの実施例は本発明を説明するためのものであって、本発明の範囲を限定するものではない。 Hereinafter, the present invention will be specifically described by way of examples. These examples are for explaining the present invention, and do not limit the scope of the present invention.
［参考例１］
＜Ce-Ti-SO4-Zr系触媒の製造＞
１００ｇのZrの塩（硫酸ジルコニウム）、５０ｇのTiの塩（塩化チタン）、及び５０ｇのCeの塩（硝酸セリウム）を１Ｌの水に溶解した混合水溶液を調製後、アルカリ溶液（アンモニア水）を加え中和し濾取した。その後、４００℃以上で焼成し粉砕することにより、粉末を得た。その後、この粉末がCe-Ti-SO4-Zr系触媒であるかどうかを確認した（図１参照）。
[Reference Example 1]
<Manufacture of Ce-Ti-SO 4 -Zr catalyst>
After preparing a mixed aqueous solution in which 100 g of Zr salt (zirconium sulfate), 50 g of Ti salt (titanium chloride), and 50 g of Ce salt (cerium nitrate) were dissolved in 1 L of water, an alkaline solution (ammonia water) was added. The mixture was neutralized and collected by filtration. Then, powder was obtained by baking at 400 degreeC or more and grind | pulverizing. Thereafter, it was confirmed whether this powder was a Ce—Ti—SO 4 —Zr catalyst (see FIG. 1).
［参考例２］
＜Fe-Si-Al系触媒の製造＞
シリカ−アルミナからなる多孔質酸化物（モル組成比＝４０／１）１０００ｇに、硝酸鉄水溶液（５００Ｌの水に１０００ｇの硝酸鉄を溶解）を攪拌しながら徐々に滴下した。得られたパウダーを１２０℃で乾燥後、４５０℃で２時間焼成し、粉末を得た。その後、この粉末がFe-Si-Al系触媒であるかどうかを確認した（図２参照）。
[Reference Example 2]
<Manufacture of Fe-Si-Al catalyst>
An aqueous iron nitrate solution (1000 g of iron nitrate dissolved in 500 L of water) was gradually added dropwise to 1000 g of a porous oxide composed of silica-alumina (molar composition ratio = 40/1) with stirring. The obtained powder was dried at 120 ° C. and then calcined at 450 ° C. for 2 hours to obtain a powder. Then, it was confirmed whether this powder was a Fe-Si-Al type catalyst (refer FIG. 2).
［実施例３］
＜Ce-W-Zr系触媒の製造＞
１００ｇのZrの塩（硫酸ジルコニウム）、及び５０ｇのCeの塩（硝酸セリウム）を１Ｌの水に溶解した混合水溶液を調製し、アルカリ溶液（アンモニア水）を加え中和し濾取した。その後、１５ｇのタングステン酸アンモニウムを含浸し、４００℃以上で焼成し粉砕することにより、粉末を得た。その後、この粉末がCe-Ti-SO4-Zr系触媒であるかどうかを確認した（図３参照）。
[Example 3]
<Manufacture of Ce-W-Zr catalyst>
A mixed aqueous solution in which 100 g of Zr salt (zirconium sulfate) and 50 g of Ce salt (cerium nitrate) were dissolved in 1 L of water was prepared, neutralized by adding an alkaline solution (aqueous ammonia) and collected by filtration. Thereafter, 15 g of ammonium tungstate was impregnated, fired at 400 ° C. or higher and pulverized to obtain a powder. Thereafter, it was confirmed whether this powder was a Ce—Ti—SO 4 —Zr catalyst (see FIG. 3).
＜尿素の熱分解反応テスト＞
従来のV2O5−TiO2系触媒雰囲気下で尿素（還元脱硝剤）を熱分解（加水分解）させると、アンモニア以外に副生成物を生成することが知られている。そこで、尿素の熱分解において本発明に係る窒素酸化物浄化触媒を用いると副生成物が生成されるかどうかを調べてみた。
参考例１により得られたCe-Ti-SO4-Zr系触媒粉末０．１ｇを尿素水溶液（２．５Wt％）０．２ｍｌに含浸後、乾燥したものを用意し、ＴＰＤ（昇温脱離法：Temperature Programmed Desorption）−Ｍａｓｓにより、昇温時に熱分解で生じるガス成分を測定した。なお、昇温条件は＋１０℃／分とした。また、ＴＰＤ−Ｍａｓｓ分析は大気条件下で１００℃〜３００℃の範囲で行った。
その結果を図４に示す。図４に示すように、従来のV2O5−TiO2系触媒は、１５０℃〜２５０℃の反応温度条件下において、尿素を熱分解させてアンモニア（△）を生成させるとともに、副生成物（▲）を生成した。しかしながら、Ce-Ti-SO4-Zr系触媒は、どの反応温度条件下においても、副生成物（●）を生成すること無しにアンモニア（○）のみを生成することがわかった。このことから、アンモニア還元触媒は、触媒活性性能の向上に有用であることが明らかとなった。
<Thermal decomposition reaction test of urea>
It is known that when urea (reductive denitration agent) is thermally decomposed (hydrolyzed) in a conventional V 2 O 5 —TiO 2 catalyst atmosphere, a by-product is generated in addition to ammonia. Therefore, it was examined whether or not a by-product is produced when the nitrogen oxide purification catalyst according to the present invention is used in the thermal decomposition of urea.
After impregnating 0.1 ml of Ce-Ti-SO 4 -Zr-based catalyst powder obtained in Reference Example 1 with 0.2 ml of urea aqueous solution (2.5 Wt%), prepare a dried one, and TPD (thermal desorption) Method: Temperature Programmed Desorption) -Mass was used to measure gas components generated by thermal decomposition at elevated temperature. The temperature raising condition was + 10 ° C./min. Moreover, the TPD-Mass analysis was performed in the range of 100 ° C. to 300 ° C. under atmospheric conditions.
The result is shown in FIG. As shown in FIG. 4, the conventional V 2 O 5 —TiO 2 -based catalyst generates ammonia (Δ) by thermally decomposing urea under reaction temperature conditions of 150 ° C. to 250 ° C., and a by-product. (▲) was generated. However, it was found that the Ce—Ti—SO 4 —Zr catalyst produced only ammonia (◯) without producing a by-product (●) under any reaction temperature conditions. From this, it became clear that the ammonia reduction catalyst is useful for improving the catalytic activity performance.
［参考例５］
＜脱硝反応テスト１＞
参考例１により得られたCe-Ti-SO4-Zr系触媒について、脱硝反応テストを以下の条件により行った。直径２５ｍｍφ、長さ５０ｍｍのハニカム担体に触媒担持し、反応ガスとして、Ｏ２が１０％、ＮＯとＮＯ２はそれぞれ１５０ppm、Ｈ２Ｏは５％、残りは窒素からなるガスを用い、空間速度（ＳＶ）が５００００／ｈの条件で導入した。触媒入口温度は、１５０℃〜４００℃の範囲で行った。また、比較対照として、V2O5−TiO2系触媒を用いて同様の実験を行った。それらの結果を図５に示す。
図５に示すように、Ce-Ti-SO4-Zr系触媒（○）は、V2O5−TiO2系触媒（●）に比べて高い効率で窒素酸化物を浄化できることがわかった。
[Reference Example 5]
<Denitration test 1>
The Ce—Ti—SO 4 —Zr catalyst obtained in Reference Example 1 was subjected to a denitration reaction test under the following conditions. The catalyst is supported on a honeycomb carrier having a diameter of 25 mmφ and a length of 50 mm, and the reaction velocity is 10% O 2 , NO and NO 2 are each 150 ppm, H 2 O is 5%, and the rest is nitrogen. (SV) was introduced under the condition of 50000 / h. The catalyst inlet temperature was in the range of 150 ° C to 400 ° C. As a comparative control, a similar experiment was performed using a V 2 O 5 —TiO 2 catalyst. The results are shown in FIG.
As shown in FIG. 5, it was found that the Ce—Ti—SO 4 —Zr-based catalyst (◯) can purify nitrogen oxides with higher efficiency than the V 2 O 5 —TiO 2 -based catalyst (●).
［参考例６］
＜脱硝反応テスト２＞
ＳＣＲ入口温度に対する窒素酸化物の浄化率を調べるために、φ７．５”×７”（５Ｌ）のＳＣＲ触媒サイズのCe-Ti-SO4-Zr系触媒を５Ｌ−ＮＡエンジンの排気マフラーに装着し、ＳＣＲ触媒前段部にPt系酸化触媒（Pt−アルミナ触媒；東京濾器株式会社製）を装着して実機定常評価試験を行った。その結果を図６に示す。
図６に示すように、Ce-Ti-SO4-Zr系触媒はＳＣＲ入口温度がおよそ２２０℃以上において８０％以上の窒素酸化物を浄化できることがわかった。
[Reference Example 6]
<
In order to investigate the purification rate of nitrogen oxides relative to the SCR inlet temperature, a Ce-Ti-SO 4 -Zr catalyst with a SCR catalyst size of φ7.5 ”× 7” (5L) is installed in the exhaust muffler of a 5L-NA engine. Then, a Pt-based oxidation catalyst (Pt-alumina catalyst; manufactured by Tokyo Filter Co., Ltd.) was attached to the front part of the SCR catalyst, and an actual machine steady state evaluation test was performed. The result is shown in FIG.
As shown in FIG. 6, it was found that the Ce—Ti—SO 4 —Zr-based catalyst can purify 80% or more of nitrogen oxides at an SCR inlet temperature of about 220 ° C. or more.
［実施例７］
＜脱硝反応テスト５＞
実施例３により得られたCe-W-Zr系触媒について、参考例５に記載の方法と同様に脱硝反応テストを行った。なお、触媒入口温度は１５０℃〜４００℃の範囲で触媒評価をした。それらの結果を図７に示す。
図７に示すように、Ce-W-Zr系触媒（○）は、２５０℃〜４００℃の反応温度でV2O5−TiO2系触媒（●）より高い効率で窒素酸化物を浄化できることがわかった。
[Example 7]
<
The Ce—W—Zr-based catalyst obtained in Example 3 was subjected to a denitration reaction test in the same manner as described in Reference Example 5. The catalyst inlet temperature was in the range of 150 ° C to 400 ° C. The results are shown in FIG.
As shown in FIG. 7, the Ce—W—Zr catalyst (◯) can purify nitrogen oxides at a reaction temperature of 250 ° C. to 400 ° C. with higher efficiency than the V 2 O 5 —TiO 2 catalyst (●). I understood.
［参考例８］
＜アンモニア吸着テスト＞
参考例２により得られたFe-Si-Al系触媒及び比較品（V2O5−TiO2系触媒）を用いたＴＰＤ−Ｍａｓｓ分析により、アンモニア昇温脱離スペクトルを測定した。なお、昇温速度は＋１０℃／分とした。また、ＴＰＤ−Ｍａｓｓ分析はヘリウム雰囲気下で１００℃〜５００℃の範囲で行った。その結果を図８に示す。
図８に示すように、Fe-Si-Al系触媒（○）は、比較品（●）に比べ、低温から高温においてアンモニアを保持できることがわかった。このことから、Fe-Si-Al系触媒は触媒活性性能向上に寄与するものと考えられる。
[Reference Example 8]
<Ammonia adsorption test>
An ammonia temperature-programmed desorption spectrum was measured by TPD-Mass analysis using the Fe—Si—Al catalyst obtained in Reference Example 2 and a comparative product (V 2 O 5 —TiO 2 catalyst). The temperature rising rate was + 10 ° C./min. TPD-Mass analysis was performed in a range of 100 ° C. to 500 ° C. in a helium atmosphere. The result is shown in FIG.
As shown in FIG. 8, it was found that the Fe—Si—Al-based catalyst (◯) can hold ammonia from a low temperature to a high temperature as compared with the comparative product (●). From this, it is considered that the Fe—Si—Al catalyst contributes to the improvement of the catalytic activity performance.
［参考例９］
＜脱硝反応テスト３＞
参考例２により得られたFe-Si-Al系触媒について、参考例５に記載の方法と同様に脱硝反応テストを行った。なお、触媒入口温度は１５０℃〜４００℃の範囲で触媒評価をした。それらの結果を図９に示す。
図９に示すように、Fe-Si-Al系触媒（○）は、V2O5−TiO2系触媒（●）に比べ窒素酸化物を高い効率で浄化できることがわかった。
また、参考例８及び参考例９の結果から、アンモニアの吸着性が高い触媒は、脱硝反応を促進し、窒素酸化物の浄化効率を高めているものと考えられる。従って、窒素酸化物の浄化効率が高いCe-Ti-SO4-Zr系触媒はアンモニアの吸着性が優れているものと考えられる。
[Reference Example 9]
<
The Fe—Si—Al catalyst obtained in Reference Example 2 was subjected to a denitration reaction test in the same manner as described in Reference Example 5. The catalyst inlet temperature was in the range of 150 ° C to 400 ° C. The results are shown in FIG.
As shown in FIG. 9, it was found that the Fe—Si—Al-based catalyst (◯) can purify nitrogen oxides with higher efficiency than the V 2 O 5 —TiO 2 -based catalyst (●).
Further, from the results of Reference Example 8 and Reference Example 9, it is considered that the catalyst having a high ammonia adsorptivity promotes the denitration reaction and increases the purification efficiency of nitrogen oxides. Therefore, it is considered that the Ce—Ti—SO 4 —Zr-based catalyst having high nitrogen oxide purification efficiency is excellent in ammonia adsorption.
［参考例１０］
＜脱硝反応テスト６＞
次に、Ce-Ti-SO4-Zr系触媒とFe-Si-Al系触媒との混合触媒が、窒素酸化物の浄化効率に与える影響を調べるため、φ７．５”×７”（５Ｌ）のＳＣＲ触媒サイズのCe-Ti-SO4-Zr系触媒及びFe-Si-Al系触媒の混合触媒（材料担持比率（Ce-Ti-SO4-Zr系触媒／Fe-Si-Al系触媒）は１／２）を用いて参考例６に記載の方法に準じて実機定常評価試験を行った。その結果を図１０に示す。
図１０に示すように、ＳＣＲ温度が２５０℃以上において混合触媒（△）は、Ce-Ti-SO4-Zr系触媒（◆）やFe-Si-Al系触媒（■）を単品で用いた場合に比べて、窒素酸化物をより効率よく浄化できることがわかった。また、以上のことから、Fe-Si-Al系触媒の上にCe-Ti-SO4-Zr系触媒を担持することにより、シリカ−アルミナ材の高温排ガスアタックを抑制することができ、耐熱性が改善できるものと考えられる。
[Reference Example 10]
<Denitration test 6>
Next, in order to investigate the effect of the mixed catalyst of Ce-Ti-SO 4 -Zr catalyst and Fe-Si-Al catalyst on the purification efficiency of nitrogen oxides, φ7.5 "x 7" (5L) Of SCR catalyst size of Ce-Ti-SO 4 -Zr catalyst and Fe-Si-Al catalyst (material loading ratio (Ce-Ti-SO 4 -Zr catalyst / Fe-Si-Al catalyst)) Was subjected to a real machine steady state evaluation test according to the method described in Reference Example 6. The result is shown in FIG.
As shown in FIG. 10, Ce-Ti-SO 4 -Zr-based catalyst (♦) and Fe-Si-Al-based catalyst (■) were used individually as the mixed catalyst (△) when the SCR temperature was 250 ° C or higher. It was found that nitrogen oxides can be purified more efficiently than in the case. From the above, by supporting the Ce-Ti-SO 4 -Zr catalyst on the Fe-Si-Al catalyst, high-temperature exhaust gas attack of the silica-alumina material can be suppressed, and the heat resistance Can be improved.
Claims (7)
シリカ、アルミナ、チタニア、ジルコニア、及び酸化タングステンから選ばれる１又は２以上の酸化物と、希土類金属又は遷移金属と、を有効成分として含有する第二の複合体と、を有し、前記第一の複合体と前記第二の複合体とは活性種成分が異なることを特徴とする窒素酸化物浄化触媒。 A first composite containing at least a tungsten oxide-zirconia composite oxide and cerium as active ingredients;
A second composite containing one or more oxides selected from silica, alumina, titania, zirconia, and tungsten oxide, and a rare earth metal or a transition metal as active ingredients, A nitrogen oxide purifying catalyst characterized in that the active complex component is different between the composite of the above and the second composite.
前記第一の複合体は前記第二の複合体に担持されていることを特徴とする請求項３又は４に記載の窒素酸化物浄化触媒。 The second composite is supported on a carrier substrate;
The nitrogen oxide purification catalyst according to claim 3 or 4, wherein the first complex is supported on the second complex.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010506724A (en) * | 2006-10-19 | 2010-03-04 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Ce-Zr-R-O catalyst, article containing Ce-Zr-R-O catalyst, and method for producing and using the Ce-Zr-R-O catalyst |
| WO2011118777A1 (en) | 2010-03-26 | 2011-09-29 | 株式会社 キャタラー | Exhaust gas purification system |
| CN105728026A (en) * | 2016-02-02 | 2016-07-06 | 无锡威孚环保催化剂有限公司 | Diesel vehicle platinum-based oxidation catalyst and preparation method thereof |
| CN105797767A (en) * | 2016-03-14 | 2016-07-27 | 无锡威孚环保催化剂有限公司 | Diesel vehicle oxidized form catalyst having low temperature activity and preparation method thereof |
| CN109513438A (en) * | 2018-11-21 | 2019-03-26 | 南京工业大学 | Environment-friendly high-temperature denitration catalyst and preparation method thereof |
| CN111974399A (en) * | 2020-08-18 | 2020-11-24 | 山东大学 | Red mud-based SCR denitration catalyst and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010506724A (en) * | 2006-10-19 | 2010-03-04 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Ce-Zr-R-O catalyst, article containing Ce-Zr-R-O catalyst, and method for producing and using the Ce-Zr-R-O catalyst |
| WO2011118777A1 (en) | 2010-03-26 | 2011-09-29 | 株式会社 キャタラー | Exhaust gas purification system |
| US8679412B2 (en) | 2010-03-26 | 2014-03-25 | Cataler Corporation | Exhaust gas-purifying system |
| CN105728026A (en) * | 2016-02-02 | 2016-07-06 | 无锡威孚环保催化剂有限公司 | Diesel vehicle platinum-based oxidation catalyst and preparation method thereof |
| CN105728026B (en) * | 2016-02-02 | 2019-07-05 | 无锡威孚环保催化剂有限公司 | Diesel vehicle platinum base oxidative catalyst and preparation method thereof |
| CN105797767A (en) * | 2016-03-14 | 2016-07-27 | 无锡威孚环保催化剂有限公司 | Diesel vehicle oxidized form catalyst having low temperature activity and preparation method thereof |
| CN105797767B (en) * | 2016-03-14 | 2018-05-29 | 无锡威孚环保催化剂有限公司 | A kind of diesel vehicle oxidation catalyst with low temperature active and preparation method thereof |
| CN109513438A (en) * | 2018-11-21 | 2019-03-26 | 南京工业大学 | Environment-friendly high-temperature denitration catalyst and preparation method thereof |
| CN109513438B (en) * | 2018-11-21 | 2022-07-08 | 南京工业大学 | Environment-friendly high-temperature denitration catalyst and preparation method thereof |
| CN111974399A (en) * | 2020-08-18 | 2020-11-24 | 山东大学 | Red mud-based SCR denitration catalyst and preparation method and application thereof |
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