JPH04284848A - Catalyst for reducing and removing nitrogen oxide and its preparation - Google Patents
Catalyst for reducing and removing nitrogen oxide and its preparationInfo
- Publication number
- JPH04284848A JPH04284848A JP3073975A JP7397591A JPH04284848A JP H04284848 A JPH04284848 A JP H04284848A JP 3073975 A JP3073975 A JP 3073975A JP 7397591 A JP7397591 A JP 7397591A JP H04284848 A JPH04284848 A JP H04284848A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alumina
- nitrogen oxides
- nitrogen oxide
- exhaust gas
- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 16
- 239000011701 zinc Substances 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ボイラー、自動車エン
ジン等から排出される窒素酸化物を含有する排ガスを処
理するための触媒、及び、その使用方法に関し、更に詳
細には、活性の非常に優れた窒素酸化物除去用触媒、及
び、その使用方法に関する。[Field of Industrial Application] The present invention relates to a catalyst for treating exhaust gas containing nitrogen oxides emitted from boilers, automobile engines, etc., and a method of using the same. This invention relates to an excellent catalyst for removing nitrogen oxides and a method for using the same.
【０００２】0002
【従来の技術】ボイラー、自動車エンジン等から排出さ
れる排ガス中の窒素酸化物を除去する方法として、触媒
の存在下にアンモニアで処理する選択的接触還元法、及
び、排ガスを触媒に通し、未燃焼の一酸化炭素及び炭化
水素により還元する非選択的接触還元法等が実用化され
ている。更には、例えば、特開昭６０−１２５、２５０
号公報には、還元剤非共存下で窒素酸化物を直接接触分
解できる触媒として銅イオン交換したゼオライトを用い
る方法が提案されている。[Prior Art] As a method for removing nitrogen oxides from exhaust gas emitted from boilers, automobile engines, etc., there is a selective catalytic reduction method in which the exhaust gas is treated with ammonia in the presence of a catalyst, and a selective catalytic reduction method in which exhaust gas is passed through a catalyst to remove nitrogen oxides. Non-selective catalytic reduction methods that reduce carbon monoxide and hydrocarbons by combustion have been put into practical use. Furthermore, for example, JP-A-60-125, 250
The publication proposes a method using copper ion-exchanged zeolite as a catalyst that can directly catalytically decompose nitrogen oxides in the absence of a reducing agent.
【０００３】また、酸素過剰下でも、未燃焼の一酸化炭
素、炭化水素等の還元成分により窒素酸化物を選択的に
還元できる触媒として、Ｃｕ等の卑金属をゼオライト等
に含有させた触媒が提案されている（特開昭６３−１０
０，９１９号公報等）。しかしながら、これらの提案さ
れている触媒といえども、活性が十分とはいえず、また
、自動車の高速運転時等で必要とされる高温での活性が
不十分であることから、未だ実用化されるに至っていな
い。[0003] In addition, a catalyst in which base metals such as Cu are contained in zeolite has been proposed as a catalyst that can selectively reduce nitrogen oxides using reducing components such as unburned carbon monoxide and hydrocarbons even in the presence of excess oxygen. (Unexamined Japanese Patent Publication No. 1983-10)
0,919, etc.). However, even with these proposed catalysts, the activity is not sufficient, and the activity at high temperatures required for high-speed driving of automobiles is insufficient, so they have not yet been put into practical use. This has not yet been achieved.
【０００４】0004
【発明が解決しようとする課題】本発明の目的は、アン
モニア等の還元剤を添加することなく、ボイラー、自動
車エンジン等、特にディーゼルエンジン等の内燃機関か
ら排出される排ガスを、効率良く浄化し、特に高温でも
活性の高い窒素酸化物除去用触媒を提供するものである
。[Problems to be Solved by the Invention] An object of the present invention is to efficiently purify exhaust gas emitted from internal combustion engines such as boilers and automobile engines, especially diesel engines, without adding reducing agents such as ammonia. The present invention provides a catalyst for removing nitrogen oxides that is highly active even at high temperatures.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記課題に
ついて鋭意検討した結果、本発明を完成するに至った。
即ち、本発明は、窒素酸化物及び炭化水素及び酸素を含
有する燃焼排ガスから窒素酸化物を除去する触媒であっ
て、アルミナあるいはシリカアルミナにＣｕ，Ｃｏ，Ｆ
ｅ，Ｃｒ，Ｚｎ，Ｎｉ及びＶの中から選ばれた少くとも
一種を含有させたことを特徴とする窒素酸化物除去用触
媒及びその使用方法を提供するものである。[Means for Solving the Problems] The present inventor has completed the present invention as a result of intensive study on the above-mentioned problems. That is, the present invention provides a catalyst for removing nitrogen oxides from combustion exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen, and which comprises alumina or silica alumina containing Cu, Co, and F.
The present invention provides a catalyst for removing nitrogen oxides, characterized in that it contains at least one selected from among e, Cr, Zn, Ni, and V, and a method for using the same.
【０００６】以下、本発明をより詳細に説明する。アル
ミナ、シリカアルミナは数多くの種類が知られているが
、本発明において用いられるアルミナ、シリカアルミナ
はいずれの種類でも良い。その表面積に限定はないが、
その表面積の大きいアルミナあるいはシリカアルミナが
好ましい。好ましくは、表面積が１００ｍ２／ｇ以上で
ある。表面積が１００ｍ２／ｇ未満であると、Ｃｕ，Ｃ
ｏ，Ｆｅ，Ｃｒ，Ｚｎ，ＮｉあるいはＶが担持され難く
不均一な担持となる場合があり、触媒性能が不充分とな
る恐れがある。The present invention will be explained in more detail below. Although many types of alumina and silica-alumina are known, any type of alumina and silica-alumina may be used in the present invention. There is no limit to its surface area, but
Alumina or silica alumina is preferred because of its large surface area. Preferably, the surface area is 100 m2/g or more. If the surface area is less than 100 m2/g, Cu, C
o, Fe, Cr, Zn, Ni, or V may be difficult to support and may be supported unevenly, which may result in insufficient catalytic performance.
【０００７】本発明の窒素酸化物還元除去用触媒は、Ｃ
ｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎｉ及びＶの中から選ば
れた少くとも一種を含有することが必須である。Ｃｕ，
Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，ＮｉあるいはＶの含有量は特
に限定されないが、０．１〜４重量％含有することが好
ましい。Ｃｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎｉあるいは
Ｖが０．１重量％未満であると十分な活性が得られない
場合があり、また、４重量％を越えるとＣｕ，Ｃｏ，Ｆ
ｅ，Ｃｒ，Ｚｎ，ＮｉあるいはＶの担持状態が不均一と
なり性能が悪くなる恐れがある。The catalyst for reducing and removing nitrogen oxides of the present invention has C
It is essential to contain at least one selected from u, Co, Fe, Cr, Zn, Ni and V. Cu,
The content of Co, Fe, Cr, Zn, Ni, or V is not particularly limited, but it is preferably contained in an amount of 0.1 to 4% by weight. If Cu, Co, Fe, Cr, Zn, Ni or V is less than 0.1% by weight, sufficient activity may not be obtained, and if it exceeds 4% by weight, Cu, Co, F
There is a risk that the supported state of e, Cr, Zn, Ni, or V may be uneven, resulting in poor performance.
【０００８】本発明の窒素酸化物除去用触媒は、アルミ
ナあるいはシリカアルミナにＣｕ，Ｃｏ，Ｆｅ，Ｃｒ，
Ｚｎ，Ｎｉ及びＶの中から選ばれた少くとも一種を含有
させて製造される。Ｃｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎ
ｉあるいはＶの導入方法は特に限定されることはなく、
含浸担持、蒸発乾固等の方法により含有されるが、特に
含浸担持する方法が好ましい。The catalyst for removing nitrogen oxides of the present invention includes alumina or silica alumina containing Cu, Co, Fe, Cr,
It is manufactured by containing at least one selected from Zn, Ni and V. Cu, Co, Fe, Cr, Zn, N
The method of introducing i or V is not particularly limited,
It can be contained by methods such as impregnating and supporting, evaporation to dryness, etc., and particularly preferred is an impregnating and supporting method.
【０００９】Ｃｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎｉある
いはＶの含浸担持は通常の方法で良く、例えば、原料ア
ルミナあるいはシリカアルミナにＣｕ，Ｃｏ，Ｆｅ，Ｃ
ｒ，Ｚｎ，Ｎｉ及びＶの中から選ばれた少くとも一種の
原料化合物を含む水溶液を含浸させ、乾燥する手法が採
られる。Ｃｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎｉあるいは
Ｖの原料化合物としては特に限定されないが、Ｃｕ，Ｃ
ｏ，Ｆｅ，Ｃｒ，Ｚｎ，ＮｉあるいはＶの塩化物、硝酸
塩、硫酸塩、酢酸塩等の中性塩が好ましく用いられる。
これらの化合物は２種以上を用いてもよい。[0009] Cu, Co, Fe, Cr, Zn, Ni, or V may be impregnated and supported by a conventional method. For example, Cu, Co, Fe,
A method is adopted in which the material is impregnated with an aqueous solution containing at least one raw material compound selected from r, Zn, Ni, and V, and then dried. The raw material compounds for Cu, Co, Fe, Cr, Zn, Ni or V are not particularly limited, but Cu, C
Neutral salts such as chlorides, nitrates, sulfates, and acetates of O, Fe, Cr, Zn, Ni, or V are preferably used. Two or more types of these compounds may be used.
【００１０】本発明の窒素酸化物還元除去用触媒は、円
柱状、球状、ハニカム状等に成形して使用することもで
きる。また、予めアルミナあるいはシリカアルミナを成
形し、その成形体にＣｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎ
ｉあるいはＶを含有させることもできる。本発明の窒素
酸化物還元除去方法においては、窒素酸化物、炭化水素
及び酸素を含有する燃焼排ガスを、Ｃｕ，Ｃｏ，Ｆｅ，
Ｃｒ，Ｚｎ，ＮｉあるいはＶを含有させたアルミナある
いはシリカアルミナに接触させることが必須である。窒
素酸化物とは、ＮＯ，ＮＯ２ ，Ｎ２ Ｏ，Ｎ２ Ｏ２
等である。また、炭化水素の種類は特に限定されない
が、炭素数６以下の炭化水素の含有量が多い燃焼排ガス
において本発明方法の効果は顕著に現れる。The catalyst for reducing and removing nitrogen oxides of the present invention can also be used after being formed into a cylindrical, spherical, or honeycomb shape. In addition, alumina or silica alumina is molded in advance, and the molded body is coated with Cu, Co, Fe, Cr, Zn, N.
It is also possible to contain i or V. In the nitrogen oxide reduction and removal method of the present invention, combustion exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen is
It is essential to contact alumina or silica alumina containing Cr, Zn, Ni or V. Nitrogen oxides are NO, NO2, N2 O, N2 O2
etc. Although the type of hydrocarbon is not particularly limited, the effect of the method of the present invention is noticeable in combustion exhaust gas containing a large amount of hydrocarbons having 6 or less carbon atoms.
【００１１】被処理対象である燃焼排ガス中のこれらの
成分ガスの濃度は特に制限されないが、通常、窒素酸化
物が１０〜１００００ｐｐｍ 、炭化水素が１０〜１０
０００ｐｐｍ 、また、酸素は、０．１〜１５％である
。特に、排ガス中に含まれる炭化水素等の還元成分を完
全に酸化するのに必要な酸素量よりも過剰な酸素が含ま
れている場合においても、窒素酸化物を効率良く除去で
きる。また、排ガス中に炭化水素を更に添加して窒素酸
化物を還元除去することもできる。還元除去する際の、
排ガスの空間速度及び温度は特に限定されないが、空間
速度（体積基準）１０００〜５０００００ｈｒ−１、温
度１００℃〜７００℃が好ましい。[0011] The concentrations of these component gases in the combustion exhaust gas to be treated are not particularly limited, but usually 10 to 10,000 ppm for nitrogen oxides and 10 to 10 ppm for hydrocarbons.
000 ppm, and oxygen is 0.1-15%. In particular, nitrogen oxides can be efficiently removed even when exhaust gas contains oxygen in excess of the amount of oxygen required to completely oxidize reducing components such as hydrocarbons contained in the exhaust gas. Further, nitrogen oxides can be reduced and removed by further adding hydrocarbons to the exhaust gas. When reducing and removing,
The space velocity and temperature of the exhaust gas are not particularly limited, but preferably the space velocity (volume basis) is 1000 to 500000 hr-1 and the temperature is 100°C to 700°C.
【００１２】0012
【発明の効果】本発明の窒素酸化物還元除去用触媒は、
燃焼排ガスから窒素酸化物を効率良く除去することがで
きる。[Effect of the invention] The catalyst for reducing and removing nitrogen oxides of the present invention is
Nitrogen oxides can be efficiently removed from combustion exhaust gas.
【００１３】[0013]
【実施例】以下、実施例について本発明を更に詳細に説
明する。しかし、本発明はこれら実施例のみに限定され
るものではない。
実施例１
アルミナ（表面積１７４ｍ２ ／ｇ）１０ｇに、銅の担
持量が０．２重量％になるように硝酸銅水溶液を含浸さ
せた後１１０℃にて乾燥させ触媒１を調製した。
実施例２
実施例１で用いたアルミナ１０ｇに、コバルトの担持量
が０．２重量％になるように硝酸コバルト水溶液を含浸
させた後１１０℃にて乾燥させ触媒２を調製した。
実施例３
実施例１で用いたアルミナ１０ｇに、鉄の担持量が０．
２重量％になるように硝酸鉄水溶液を含浸させた後１１
０℃にて乾燥させ触媒３を調製した。[Examples] The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to these examples. Example 1 Catalyst 1 was prepared by impregnating 10 g of alumina (surface area: 174 m 2 /g) with an aqueous copper nitrate solution so that the amount of copper supported was 0.2% by weight, and then drying at 110°C. Example 2 Catalyst 2 was prepared by impregnating 10 g of alumina used in Example 1 with an aqueous cobalt nitrate solution so that the amount of cobalt supported was 0.2% by weight, and then drying at 110°C. Example 3 The amount of iron supported on 10 g of alumina used in Example 1 was 0.
After impregnation with iron nitrate aqueous solution to a concentration of 2% by weight11
Catalyst 3 was prepared by drying at 0°C.
【００１４】実施例４
実施例１で用いたアルミナ１０ｇに、クロムの担持量が
０．２重量％になるように硝酸クロム水溶液を含浸させ
た後１１０℃にて乾燥させ触媒４を調製した。
実施例５
実施例１で用いたアルミナ１０ｇに、亜鉛の担持量が０
．２重量％になるように硝酸亜鉛水溶液を含浸させた後
１１０℃にて乾燥させ触媒５を調製した。
実施例６
実施例１で用いたアルミナ１０ｇに、ニッケルの担持量
が０．２重量％になるように硝酸ニッケル水溶液を含浸
させた後１１０℃にて乾燥させ触媒６を調製した。Example 4 Catalyst 4 was prepared by impregnating 10 g of the alumina used in Example 1 with an aqueous chromium nitrate solution so that the amount of chromium supported was 0.2% by weight, and then drying at 110°C. Example 5 The amount of zinc supported on 10 g of alumina used in Example 1 was 0.
．． Catalyst 5 was prepared by impregnating an aqueous zinc nitrate solution to a concentration of 2% by weight and drying at 110°C. Example 6 10 g of alumina used in Example 1 was impregnated with an aqueous nickel nitrate solution so that the amount of nickel supported was 0.2% by weight, and then dried at 110° C. to prepare catalyst 6.
【００１５】実施例７
実施例１で用いたアルミナ１０ｇに、バナジウムの担持
量が０．２重量％になるように硝酸バナジウム水溶液を
含浸させた後１１０℃にて乾燥させ触媒７を調製した。
実施例８
実施例１で用いたアルミナ１０ｇに、銅の担持量が５重
量％になるように硝酸銅水溶液を含浸させた後１１０℃
にて乾燥させ触媒８を調製した。
実施例９
アルミナ（表面積３０ｍ２／ｇ）１０ｇに、銅の担持量
が０．２重量％になるように硝酸銅水溶液を含浸させた
後１１０℃にて乾燥させ触媒９を調製した。Example 7 Catalyst 7 was prepared by impregnating 10 g of the alumina used in Example 1 with an aqueous vanadium nitrate solution so that the amount of vanadium supported was 0.2% by weight, and then drying at 110°C. Example 8 10 g of the alumina used in Example 1 was impregnated with an aqueous copper nitrate solution so that the amount of copper supported was 5% by weight, and then heated at 110°C.
The catalyst 8 was prepared by drying. Example 9 Catalyst 9 was prepared by impregnating 10 g of alumina (surface area: 30 m2/g) with an aqueous copper nitrate solution so that the amount of copper supported was 0.2% by weight, and then drying at 110°C.
【００１６】実施例１０
シリカアルミナ（表面積４１０ｍ２／ｇ） １０ｇに、
銅の担持量が３．３重量％になるように硝酸銅水溶液を
含浸させた後１１０℃にて乾燥させ触媒１０を調製した
。
実施例１１
実施例１〜１０で得られた触媒１〜１０を用いて活性試
験を行った。各触媒をプレス成形した後粉砕して１２〜
２０メッシュに整粒し、その０．５ｇを流通式反応装置
に装着した。Ｈｅガスの流通下、徐々に昇温した後５０
０℃５時間の前処理を行った。冷却後、ＮＯ：１０００
ｐｐｍ ，Ｃ２ Ｈ４ ：２５０ｐｐｍ、Ｏ２ ：２％
を含有するＨｅガスを１５０ｃｃ／ｍｉｎの速度で流し
、各温度での定常浄化活性を測定した。定常浄化活性は
、各温度で２時間保持した後のＮＯの窒素への転化率と
して評価した。
窒素への転化率は
Ｎ２ への転化率＝２×（Ｎ２ ）ｏｕｔ／（ＮＯ）ｉ
ｎ（Ｎ２ ）ｏｕｔ：触媒層出口におけるＮ２ 濃度（
ＮＯ）ｉｎ ：触媒層入口におけるＮＯ濃度で示され
る。得られた結果を表１に示す。Example 10 10 g of silica alumina (surface area 410 m2/g),
Catalyst 10 was prepared by impregnating an aqueous copper nitrate solution so that the amount of copper supported was 3.3% by weight and then drying at 110°C. Example 11 An activity test was conducted using catalysts 1 to 10 obtained in Examples 1 to 10. After press-molding each catalyst, crush it and
The particles were sized to 20 mesh, and 0.5 g of the particles was placed in a flow reactor. After gradually increasing the temperature under He gas flow, 50
Pretreatment was performed at 0°C for 5 hours. After cooling, NO: 1000
ppm, C2 H4: 250 ppm, O2: 2%
He gas containing was flowed at a rate of 150 cc/min, and steady purification activity was measured at each temperature. Steady-state purification activity was evaluated as the conversion rate of NO to nitrogen after holding at each temperature for 2 hours. The conversion rate to nitrogen is the conversion rate to N2 = 2 x (N2) out/(NO)i
n(N2)out: N2 concentration at the catalyst layer outlet (
NO)in: Indicates the NO concentration at the inlet of the catalyst layer. The results obtained are shown in Table 1.
【００１７】[0017]
【表１】
比較例１
実施例１１と同様の方法で、実施例１で用いたアルミナ
について活性試験を行った。得られた結果を表２に示す
。[Table 1] Comparative Example 1 An activity test was conducted on the alumina used in Example 1 in the same manner as in Example 11. The results obtained are shown in Table 2.
【００１８】[0018]
【表２】
実施例及び比較例より明らかなように、本発明の窒素酸
化物還元除去用触媒、及び、本発明の方法によれば、燃
焼排ガスから窒素酸化物を効率良く還元除去することが
できる。[Table 2] As is clear from the Examples and Comparative Examples, according to the catalyst for reducing and removing nitrogen oxides of the present invention and the method of the present invention, nitrogen oxides can be efficiently reduced and removed from combustion exhaust gas. can.
Claims (4)
有する燃焼排ガスから窒素酸化物を除去する触媒であっ
て、アルミナあるいはシリカアルミナにＣｕ，Ｃｏ，Ｆ
ｅ，Ｃｒ，Ｚｎ，Ｎｉ及びＶの中から選ばれた少くとも
一種を含有させたことを特徴とする窒素酸化物還元除去
用触媒。Claim 1: A catalyst for removing nitrogen oxides from combustion exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen, the catalyst comprising alumina or silica alumina containing Cu, Co, and F.
1. A catalyst for reducing and removing nitrogen oxides, characterized in that it contains at least one selected from e, Cr, Zn, Ni and V.
及びＶの中から選ばれた少くとも一種を０．１〜４重量
％含有することを特徴とする請求項１記載の窒素酸化物
還元除去用触媒。[Claim 2] Cu, Co, Fe, Cr, Zn, Ni
The catalyst for reducing and removing nitrogen oxides according to claim 1, characterized in that it contains 0.1 to 4% by weight of at least one selected from the group consisting of V and V.
有する燃焼排ガスを、Ｃｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，
Ｎｉ及びＶの中から選ばれた少くとも一種を含有させた
アルミナあるいはシリカアルミナに接触させることを特
徴とする窒素酸化物還元除去方法。3. Combustion exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen is treated with Cu, Co, Fe, Cr, Zn,
A method for reducing and removing nitrogen oxides, which comprises contacting with alumina or silica alumina containing at least one selected from Ni and V.
ｕ，Ｃｏ，Ｆｅ，Ｃｒ，Ｚｎ，Ｎｉ及びＶの中から選ば
れた少くとも一種を０．１〜４重量％含有することを特
徴とする請求項３記載の窒素酸化物還元除去方法。Claim 4: Alumina or silica alumina is C
4. The method for reducing and removing nitrogen oxides according to claim 3, further comprising 0.1 to 4% by weight of at least one selected from u, Co, Fe, Cr, Zn, Ni, and V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3073975A JPH04284848A (en) | 1991-03-13 | 1991-03-13 | Catalyst for reducing and removing nitrogen oxide and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3073975A JPH04284848A (en) | 1991-03-13 | 1991-03-13 | Catalyst for reducing and removing nitrogen oxide and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04284848A true JPH04284848A (en) | 1992-10-09 |
Family
ID=13533607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3073975A Pending JPH04284848A (en) | 1991-03-13 | 1991-03-13 | Catalyst for reducing and removing nitrogen oxide and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04284848A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000039143A (en) * | 1998-12-11 | 2000-07-05 | 이구택 | Method for simultaneously eliminating nitrogen oxides and dioxin compound |
-
1991
- 1991-03-13 JP JP3073975A patent/JPH04284848A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000039143A (en) * | 1998-12-11 | 2000-07-05 | 이구택 | Method for simultaneously eliminating nitrogen oxides and dioxin compound |
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