JPS63302948A - Catalyst for reducing oxide of nitrogen - Google Patents
Catalyst for reducing oxide of nitrogenInfo
- Publication number
- JPS63302948A JPS63302948A JP62136231A JP13623187A JPS63302948A JP S63302948 A JPS63302948 A JP S63302948A JP 62136231 A JP62136231 A JP 62136231A JP 13623187 A JP13623187 A JP 13623187A JP S63302948 A JPS63302948 A JP S63302948A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alumina
- nitrogen
- oxide
- aqueous solution
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000002803 fossil fuel Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 abstract 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 21
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+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 Chemical compound [V+5].[V+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 LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、排ガス中の窒素酸化物の還元用触媒に係わ
り、特には窒素酸化物をアンモニアにより還元する際に
用いられる窒素酸化物還元触媒に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a catalyst for reducing nitrogen oxides in exhaust gas, and particularly to a nitrogen oxide reducing catalyst used when reducing nitrogen oxides with ammonia. Regarding.
各種排ガス中の有害な窒素酸化物を触媒の存在下にアン
モニアと反応させて無害の窒素に還元することは従来か
ら行われている。その触媒としてはアルミナを担体とし
、これに銅、バナジウム、鉄、マンガン、ニッケル、ク
ロム、コバルトのうちの少なくともＩＦｉを担持させた
ものが用いられている。従来、この種の触媒の担体とし
て用いられているアルミナはγあるいはδ型の結晶構造
を有するものである。BACKGROUND ART Conventionally, harmful nitrogen oxides in various exhaust gases are reduced to harmless nitrogen by reacting with ammonia in the presence of a catalyst. The catalyst used is an alumina carrier on which at least IFi selected from copper, vanadium, iron, manganese, nickel, chromium, and cobalt is supported. Alumina conventionally used as a support for this type of catalyst has a γ- or δ-type crystal structure.
ところで、重油、軽油、原油等の鉱油類あるいは石炭等
の化石燃料を燃焼した後の排ガス中には、窒素酸化物の
ほかに硫黄酸化物も含まれている。Incidentally, exhaust gas after burning mineral oils such as heavy oil, light oil, and crude oil, or fossil fuels such as coal, contains sulfur oxides in addition to nitrogen oxides.
しかしながら、窒素酸化物還元触媒の担体として従来よ
り用いられているγ−あるいはδ−アルミナは、硫黄酸
化物と反応しやすいため硫黄酸化物をも含む排ガスと長
時間接触させると硫黄酸化物とめ反応により劣化しやす
く、これに金属を担持させた触媒は触媒活性が低下して
しまう。However, γ- or δ-alumina, which has been conventionally used as a support for nitrogen oxide reduction catalysts, easily reacts with sulfur oxides, so if it comes into contact with exhaust gas that also contains sulfur oxides for a long time, it will cause a reaction to stop sulfur oxides. The catalytic activity of catalysts with metals supported on them is likely to deteriorate.
したがって、この発明の目的は硫黄酸化物の共存下にお
いても排ガス中の窒素酸化物のアンモニアによる還元反
応に対して長時間にわたって効率よく触媒作用を発揮で
きる窒素酸化物還元触媒を提供することにある。Therefore, an object of the present invention is to provide a nitrogen oxide reduction catalyst that can efficiently exert a catalytic action over a long period of time on the reduction reaction of nitrogen oxides in exhaust gas with ammonia even in the presence of sulfur oxides. .
この発明では硫黄酸化物に反応しやすい従来のγ−ある
いはδ−アルミナに替えて、安定なθ、α型のいずれか
あるいは両者の結晶構造を有するアルミナを担体とし、
銅、バナジウム、鉄、マンガン、ニッケル、クロム、コ
バルトのうち少なくとも１種を担持させている。この結
晶構造の決定はＸ線回折によるものである。In this invention, instead of conventional γ- or δ-alumina that easily reacts with sulfur oxides, alumina having a stable θ-type, α-type, or both crystal structures is used as a carrier,
At least one of copper, vanadium, iron, manganese, nickel, chromium, and cobalt is supported. This crystal structure was determined by X-ray diffraction.
この発明の触媒の担体として用いるθ型、α型の結晶構
造を有するアルミナ（θ−アルミナ、α−アルミナ）は
、γ−アルミナまたはδ−アルミナを熱処理することに
よって得られる。この熱処理は、通常、９００°Ｃない
し１２００℃の温度で、１時間ないし５時間行う。Alumina having a θ-type or α-type crystal structure (θ-alumina, α-alumina) used as a support for the catalyst of the present invention can be obtained by heat-treating γ-alumina or δ-alumina. This heat treatment is usually carried out at a temperature of 900°C to 1200°C for 1 to 5 hours.
上記θ−アルミナおよび（または）α−アルミナに担持
される金属は、銅、バナジウム、鉄、マンガン、ニッケ
ル、クロムおよびコバルトよりなる群の中から選ばれる
少なくとも一種の金属である。これら金属をアルミナに
担持させるには、従来と同様、当該金属の塩（例えば、
硝酸塩、シュウ酸塩等）の水溶液にアルミナを浸漬し、
乾燥後２００℃ないし７００℃で焼成する。金属の担持
量はアルミナ担体の０．１重量％ないし１０重量％相当
息である。The metal supported on the θ-alumina and/or α-alumina is at least one metal selected from the group consisting of copper, vanadium, iron, manganese, nickel, chromium, and cobalt. In order to support these metals on alumina, as in the past, salts of the metals (e.g.
Alumina is immersed in an aqueous solution of nitrates, oxalates, etc.
After drying, it is fired at 200°C to 700°C. The amount of metal supported is 0.1% to 10% by weight of the alumina carrier.
この発明の触媒を用いて窒素酸化物を還元するに際し、
窒素酸化物を硫黄酸化物とともに含む排ガス（例えば、
重油、軽油、原油等の鉱油類あるいは石炭等の化石燃料
の燃焼排ガス）に還元剤としてアンモニアを添加する。When reducing nitrogen oxides using the catalyst of this invention,
Exhaust gas containing nitrogen oxides together with sulfur oxides (e.g.
Ammonia is added as a reducing agent to mineral oils such as heavy oil, light oil, and crude oil, or combustion exhaust gas from fossil fuels such as coal.
このガスをこの発明の触媒を充填したカラムに２００℃
ないし７００°Ｃの温度で通す。これにより窒素酸化物
は窒素に還元される。This gas was transferred to a column packed with the catalyst of this invention at 200°C.
Pass at a temperature of 700°C to 700°C. This reduces nitrogen oxides to nitrogen.
〈実施例１〉
γ型の結晶構造を有する粒状アルミナ担体を電気炉に入
れ９００°Ｃで３時間焼成した。生成物の結晶構造はＸ
線回折法によりθ型であることが確められた。該担体を
硝酸銅水溶液に浸し、液切り後乾燥焼成して触媒を得た
（これを触媒Ａとする）。触媒Ａの銅担持量は２．２重
量％であった。<Example 1> A granular alumina support having a γ-type crystal structure was placed in an electric furnace and fired at 900°C for 3 hours. The crystal structure of the product is
It was confirmed by line diffraction that it was of the θ type. The carrier was immersed in an aqueous copper nitrate solution, drained, and then dried and fired to obtain a catalyst (this is referred to as catalyst A). The amount of copper supported on Catalyst A was 2.2% by weight.
耐久性を評価するために上記の方法で調製した触媒Ａ３
０ｃｃを内径３０ｍ＋ｎの反応管に充填し、ボイラー排
気ガスに近似した下記組成の合成ガスを連続的に通し、
Ｎｏ還元率を定期的に測定した。Catalyst A3 prepared by the above method to evaluate durability
A reaction tube with an inner diameter of 30 m + n is filled with 0 cc, and a synthesis gas having the following composition, which is similar to boiler exhaust gas, is continuously passed through.
The No reduction rate was measured periodically.
Ｎｏ ： ２３００ｐｐｍ ＳＯ２： ７５０ｐｐ
ａ＋ＮＨ３： ３０００ｐｐｍ ０２ ： ５％ｃ
ｏ２ ：１２．３％ Ｈ２Ｏ：１Ｂ％Ｎ２ ：残部
入口ガス温度：４００℃空間速度：８００ｈｒ’
結果を第１図に示す。No.: 2300ppm SO2: 750ppm
a+NH3: 3000ppm 02: 5%c
o2: 12.3% H2O: 1B% N2: remainder
Inlet gas temperature: 400° C. Space velocity: 800 hr' The results are shown in FIG.
〈実施例２〉
実施例１と同様のγ−アルミナを電気炉に入れ１０５０
℃で３時間焼成した。生成物の結晶構造はＸ線回折法に
よりθおよびα型であることが確められた。該担体を硝
酸銅水溶液に浸し、液切り後乾燥焼成して触媒を得た（
これを触媒Ｂとする）。触媒Ｂの銅担持量は２，１重量
％であった。<Example 2> The same γ-alumina as in Example 1 was placed in an electric furnace and heated to 1050
It was baked at ℃ for 3 hours. The crystal structure of the product was confirmed to be θ and α types by X-ray diffraction. The carrier was immersed in a copper nitrate aqueous solution, drained, and then dried and fired to obtain a catalyst (
This will be referred to as catalyst B). The amount of copper supported on catalyst B was 2.1% by weight.
触媒Ｂを用いて実施例１と同一の条件でＮｏ還元率をＡ
ｌ１１定した。結果を第１図に示す。Using catalyst B, the No reduction rate was reduced to A under the same conditions as in Example 1.
l11 was determined. The results are shown in Figure 1.
〈実施例３〉
実施例１と同様のγ−アルミナを電気炉に入れ１１２０
℃で３時間焼成した。生成物の結晶構造はＸ線回折法に
よりα型であることが確められた。<Example 3> The same γ-alumina as in Example 1 was placed in an electric furnace at 1120
It was baked at ℃ for 3 hours. The crystal structure of the product was confirmed to be α type by X-ray diffraction method.
該担体を硝酸銅水溶液に浸し、液切り後乾燥焼成して触
媒を得た（これを触媒Ｃとする）。触媒Ｃの銅担持量は
２．０重量％であった。The carrier was immersed in an aqueous copper nitrate solution, drained, and then dried and fired to obtain a catalyst (this will be referred to as Catalyst C). The amount of copper supported on Catalyst C was 2.0% by weight.
触媒Ｃを用いて実施例１と同一の条件でＮｏ還元率を測
定し結果を第１図に示す。The No reduction rate was measured using Catalyst C under the same conditions as in Example 1, and the results are shown in FIG.
〈実施例４〉
実施例２と同様にγ−アルミナを電気炉に入れ１０５０
°Ｃで３時間焼成することによって得られたθおよびα
型の結晶構造を有するアルミナを、シュウ酸バナジウム
水溶液に浸し、液切り後乾燥焼成して触媒を得た（これ
を触媒りとする）。触媒りのバナジウム担持量は２．２
重量％であった。<Example 4> As in Example 2, γ-alumina was placed in an electric furnace and heated to 1050
θ and α obtained by calcination for 3 hours at °C
Alumina having a type crystal structure was immersed in a vanadium oxalate aqueous solution, the liquid was drained, and then dried and fired to obtain a catalyst (this was used as a catalyst). The amount of vanadium supported on the catalyst is 2.2
% by weight.
触媒りに、実施例１で用いたものと同一の組成および条
件の合成ガスを８００時間連続して通した後、Ｎｏ還元
率を測定した。結果を下記表１に示す。Synthesis gas having the same composition and conditions as those used in Example 1 was continuously passed through the catalyst for 800 hours, and then the No reduction rate was measured. The results are shown in Table 1 below.
〈実施例５〉
シュウ酸バナジウム水溶液を硝酸第２鉄水溶液に替えた
ことを除き、実施例４と同様にして触媒を得た（これを
触媒Ｅとする）。触媒Ｅの鉄担持量は２．２重量％であ
った。<Example 5> A catalyst was obtained in the same manner as in Example 4, except that the vanadium oxalate aqueous solution was replaced with a ferric nitrate aqueous solution (this was referred to as catalyst E). The amount of iron supported on Catalyst E was 2.2% by weight.
さらに、触媒Ｅを用いて実施例４と同一の条件でＮｏ還
元率を測定した。結果を表１に示す。Furthermore, the No reduction rate was measured using Catalyst E under the same conditions as in Example 4. The results are shown in Table 1.
〈実施例６〉
シュウ酸バナジウム水溶液を硝酸マンガン水溶液に替え
たことを除き、実施例４と同様にして触媒を得た（これ
を触媒Ｆとする）。触媒Ｆのマンガン担持量は２．２重
量９６であった。<Example 6> A catalyst was obtained in the same manner as in Example 4, except that the vanadium oxalate aqueous solution was replaced with a manganese nitrate aqueous solution (this was referred to as catalyst F). The amount of manganese supported on Catalyst F was 2.2 weight 96.
さらに、触媒Ｆを用いて実施例４と同一の条件でＮｏ還
元率を測定した。結果を表１に示す。Furthermore, the No reduction rate was measured using Catalyst F under the same conditions as in Example 4. The results are shown in Table 1.
〈実施例７〉
シュウ酸バナジウム水溶液を硝酸ニッケル水溶液に替え
たことを除き、実施例４と同様にして触媒を得た（これ
を触媒Ｇとする）。触媒Ｇのニッケル担持量は２．２重
量％であった。<Example 7> A catalyst was obtained in the same manner as in Example 4, except that the vanadium oxalate aqueous solution was replaced with a nickel nitrate aqueous solution (this is referred to as catalyst G). The amount of nickel supported on Catalyst G was 2.2% by weight.
さらに、触媒Ｇを用いて実施例４と同一の条件でＮｏ還
元率を測定した。結果を表１に示す。Furthermore, the No reduction rate was measured using Catalyst G under the same conditions as in Example 4. The results are shown in Table 1.
〈実施例８〉
シュウ酸バナジウム水溶液を硝酸クロム水溶液に替えた
ことを除き、実施例４と同様にして触媒を得た（これを
触媒Ｈとする）。触媒Ｈのクロム担持量は２．２重量％
であった。<Example 8> A catalyst was obtained in the same manner as in Example 4, except that the vanadium oxalate aqueous solution was replaced with a chromium nitrate aqueous solution (this was referred to as catalyst H). The amount of chromium supported on catalyst H is 2.2% by weight.
Met.
さらに、触媒Ｈを用いて実施例４と同一の条件でＮｏ還
元率を測定した。結果を表１に示す。Furthermore, the No reduction rate was measured using Catalyst H under the same conditions as in Example 4. The results are shown in Table 1.
〈実施例９〉
シュウ酸バナジウム水溶液を硝酸コバルト水溶液に替え
たことを除き、実施例４と同様にして触媒を得た（これ
を触媒Ｉとする）。触媒Ｉのコバルト担持量は２，２重
量％であった。<Example 9> A catalyst was obtained in the same manner as in Example 4, except that the vanadium oxalate aqueous solution was replaced with a cobalt nitrate aqueous solution (this is referred to as catalyst I). The amount of cobalt supported in Catalyst I was 2.2% by weight.
さらに、触媒Ｉを用いて実施例４と同一の条件でＮｏ還
元率を測定した。結果を表１に示す。Furthermore, the No reduction rate was measured using Catalyst I under the same conditions as in Example 4. The results are shown in Table 1.
〈比較例１〉
γ型の結晶構造を有するアルミナ担体を硝酸銅水溶液に
浸し、液切り後乾燥焼成して触媒を得た（これを触媒Ａ
′とする）。触媒へ゛の銅担持量は２．２重量％であっ
た。<Comparative Example 1> An alumina support having a γ-type crystal structure was immersed in a copper nitrate aqueous solution, the liquid was drained off, and then dried and fired to obtain a catalyst (this was used as catalyst A).
’). The amount of copper supported on the catalyst was 2.2% by weight.
触媒Ａ′を用いて、実施例１と同一の条件でＮｏ還元率
の経時変化を測定した。結果を第１図に示す。Using catalyst A', the change in No reduction rate over time was measured under the same conditions as in Example 1. The results are shown in Figure 1.
〈比較例２〉
γ型の結晶構造を有するアルミナ担体をシュウ酸バナジ
ウム水溶液に浸し、液切り後乾燥焼成して触媒を得た（
これを触媒Ｄ′とする）。触媒Ｄ′のバナジウム担持量
は２．２重量％であった。<Comparative Example 2> An alumina support having a γ-type crystal structure was immersed in a vanadium oxalate aqueous solution, the liquid was drained off, and then dried and calcined to obtain a catalyst (
This will be referred to as catalyst D'). The amount of vanadium supported on catalyst D' was 2.2% by weight.
実施例４と同様に、触媒Ｄ′に実施例１と同一の組成お
よび条件の合成ガスを８００時間連続して通した後Ｎｏ
還元率を測定した。結果を表１に示す。Similarly to Example 4, after continuously passing synthesis gas having the same composition and conditions as in Example 1 through catalyst D' for 800 hours, No.
The reduction rate was measured. The results are shown in Table 1.
く比較例３〉
シュウ酸バナジウム水溶液を硝酸第２鉄水溶液に替えた
ことを除き、比較例２と同様にして触媒を得た（これを
触媒Ｅ゛とする）。触媒Ｅ′の鉄担持二は２．２重量％
であった。Comparative Example 3 A catalyst was obtained in the same manner as in Comparative Example 2, except that the vanadium oxalate aqueous solution was replaced with a ferric nitrate aqueous solution (this was referred to as catalyst E'). The amount of iron supported on catalyst E' is 2.2% by weight.
Met.
さらに、触媒Ｅ゛を用いて実施例４と同一の条件でＮｏ
還元率を１（ＩＩＩ定した。結果を表１に示す。Furthermore, using catalyst E'' and under the same conditions as in Example 4, No.
The reduction rate was determined to be 1 (III). The results are shown in Table 1.
〈比較例４〉
シュウ酸バナジウム水溶液を硝酸マンガン水溶液に替え
たことを除き、比較例２と同様にして触媒を得た（これ
を触媒Ｆ′とする）。触媒Ｆ゛のマンガン担持量は２．
２重量％であった。<Comparative Example 4> A catalyst was obtained in the same manner as in Comparative Example 2, except that the vanadium oxalate aqueous solution was replaced with a manganese nitrate aqueous solution (this was referred to as catalyst F'). The amount of manganese supported on catalyst F' is 2.
It was 2% by weight.
さらに、触媒Ｆ゛を用いて実施例４と同一の条件でＮｏ
還元率を測定した。結果を表１に示す。Furthermore, using catalyst F'' and under the same conditions as in Example 4, No.
The reduction rate was measured. The results are shown in Table 1.
〈比較例５〉
シュウ酸バナジウム水溶液を硝酸ニッケル水溶液に替え
たことを除き、比較例２と同様にして触媒を得た（これ
を触媒Ｇ′とする）。触媒Ｇ″のニッケル担持量は２．
２重量％であった。<Comparative Example 5> A catalyst was obtained in the same manner as in Comparative Example 2, except that the vanadium oxalate aqueous solution was replaced with a nickel nitrate aqueous solution (this was referred to as catalyst G'). The amount of nickel supported on catalyst G″ is 2.
It was 2% by weight.
さらに、触媒Ｇ′を用いて実施例４と同一の条件でＮｏ
還元率をｄｌｌ定した。結果を表１に示す。Further, using catalyst G′ and under the same conditions as in Example 4, No.
The reduction rate was determined. The results are shown in Table 1.
く比較例６〉
シュウ酸バナジウム水溶液を硝酸クロム水溶液に替えた
ことを除き、比較例２と同様にして触媒を得た（これを
触媒Ｈ′とする）。触媒Ｈ′のクロム担持量は２．２重
量％であった。Comparative Example 6 A catalyst was obtained in the same manner as in Comparative Example 2, except that the vanadium oxalate aqueous solution was replaced with a chromium nitrate aqueous solution (this was referred to as catalyst H'). The amount of chromium supported on catalyst H' was 2.2% by weight.
さらに、触媒Ｈ゛を用いて実施例４と同一の条件でＮｏ
還元率を測定した。結果を表１に示す。Furthermore, using catalyst H, No.
The reduction rate was measured. The results are shown in Table 1.
く比較例７〉
シュウ酸バナジウム水溶液を硝酸コバルト水溶液に替え
たことを除き、比較例２と同様にして触媒を得た（これ
を触媒■゛とする）。触媒！゛のコバルト担持量は２．
２重量％であった。Comparative Example 7 A catalyst was obtained in the same manner as in Comparative Example 2, except that the vanadium oxalate aqueous solution was replaced with a cobalt nitrate aqueous solution (this will be referred to as catalyst ①). catalyst! The amount of cobalt supported is 2.
It was 2% by weight.
さらに、触媒Ｉ′を用いて実施例４と同一の条件でＮｏ
還元率を測定した。結果を表１に示す。Further, using catalyst I′ and under the same conditions as in Example 4, No.
The reduction rate was measured. The results are shown in Table 1.
表 １
第１図および表１に示す結果から明らかなように、本発
明の触媒は硫黄酸化物を含むガスを長時間流した後でも
Ｎｏ還元率にほとんど変化はなく、従来の触媒に見られ
た触媒活性の大きな低下は認められなかった。Table 1 As is clear from the results shown in Figure 1 and Table 1, the catalyst of the present invention shows almost no change in the No reduction rate even after flowing gas containing sulfur oxides for a long time, which is different from that seen in conventional catalysts. No significant decrease in catalyst activity was observed.
以上述べたように、この発明の触媒は硫黄酸化物の共存
下においても担体の劣化による触媒活性の低下はみられ
ず、排ガス中の窒素酸化物のアンモニアによる還元反応
に対して長時間にわたって効率よく触媒作用を発揮する
。As mentioned above, the catalyst of this invention does not show any decrease in catalytic activity due to deterioration of the carrier even in the coexistence of sulfur oxides, and is highly efficient over a long period of time in the reduction reaction of nitrogen oxides in exhaust gas with ammonia. It has a good catalytic effect.
Claims (1)
ニアを添加し、このガスを触媒に接触させ、該ガス中の
窒素酸化物を窒素に還元する反応に用いる触媒であって
、θ、α型のいずれかあるいは両者の結晶構造を有する
アルミナを担体とし、これに銅、バナジウム、鉄、マン
ガン、ニッケル、クロムおよびコバルトのうちの少なく
とも１種を担持させたことを特徴とする窒素酸化物還元
触媒。A catalyst used in a reaction in which ammonia is added to a gas containing nitrogen oxides and sulfur oxides, the gas is brought into contact with a catalyst, and the nitrogen oxides in the gas are reduced to nitrogen. A nitrogen oxide reduction catalyst characterized in that alumina having one or both of the crystal structures is used as a carrier, and at least one of copper, vanadium, iron, manganese, nickel, chromium and cobalt is supported on the carrier. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62136231A JPS63302948A (en) | 1987-05-30 | 1987-05-30 | Catalyst for reducing oxide of nitrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62136231A JPS63302948A (en) | 1987-05-30 | 1987-05-30 | Catalyst for reducing oxide of nitrogen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63302948A true JPS63302948A (en) | 1988-12-09 |
Family
ID=15170352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62136231A Pending JPS63302948A (en) | 1987-05-30 | 1987-05-30 | Catalyst for reducing oxide of nitrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63302948A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041407A (en) * | 1989-12-14 | 1991-08-20 | Allied-Signal Inc. | High-temperature three-way catalyst for treating automotive exhaust gases |
| KR20000039143A (en) * | 1998-12-11 | 2000-07-05 | 이구택 | Method for simultaneously eliminating nitrogen oxides and dioxin compound |
-
1987
- 1987-05-30 JP JP62136231A patent/JPS63302948A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041407A (en) * | 1989-12-14 | 1991-08-20 | Allied-Signal Inc. | High-temperature three-way catalyst for treating automotive exhaust gases |
| KR20000039143A (en) * | 1998-12-11 | 2000-07-05 | 이구택 | Method for simultaneously eliminating nitrogen oxides and dioxin compound |
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