JP2000126591A - Denitrification catalyst - Google Patents
Denitrification catalystInfo
- Publication number
- JP2000126591A JP2000126591A JP11124794A JP12479499A JP2000126591A JP 2000126591 A JP2000126591 A JP 2000126591A JP 11124794 A JP11124794 A JP 11124794A JP 12479499 A JP12479499 A JP 12479499A JP 2000126591 A JP2000126591 A JP 2000126591A
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- Japan
- Prior art keywords
- denitration
- catalyst
- catalyst component
- metal
- carrier
- Prior art date
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、脱硝触媒に係り、
特に、五酸化バナジウムを主成分とし、二酸化硫黄の転
化率が低い脱硝触媒に関するものである。[0001] The present invention relates to a denitration catalyst,
In particular, the present invention relates to a denitration catalyst containing vanadium pentoxide as a main component and having a low conversion of sulfur dioxide.
【０００２】[0002]
【従来の技術】火力発電所などにおけるボイラ１の排ガ
スＧに対しては、図７に示すように、脱硝装置２を用い
て脱硝した後、排ガスＧ中の燃焼灰などを集塵器（例え
ば、バグフィルタなど）３で除去し、その後、脱硫装置
４を用いて脱硫し、煙突５から排出を行っている。2. Description of the Related Art As shown in FIG. 7, exhaust gas G from a boiler 1 in a thermal power plant or the like is denitrified using a denitration apparatus 2, and then the combustion ash and the like in the exhaust gas G are collected into a dust collector (for example, a dust collector). , A bag filter, etc.) 3, then desulfurize using a desulfurizer 4, and discharge from a chimney 5.
【０００３】脱硝装置２は、ケーシング（図示せず）内
に、図８に示すように、酸化チタンや酸化タングステン
などからなるハニカム構造の担体１１に、五酸化バナジ
ウム（以下、Ｖ2 Ｏ5 と呼ぶ）を主成分とする触媒成分
を担持させてなる脱硝触媒１２が多数個設けられてな
り、脱硝反応の副反応において、二酸化硫黄（以下、Ｓ
Ｏ2 と呼ぶ）を酸化し、三酸化硫黄（以下、ＳＯ3 と呼
ぶ）に転化させる。ここで、担体１１に対するＶ2 Ｏ5
の重量比は、通常で１〜２％、最大でも５〜６％程度で
ある。As shown in FIG. 8, a denitration apparatus 2 includes a carrier 11 having a honeycomb structure made of titanium oxide or tungsten oxide and a vanadium pentoxide (hereinafter, referred to as V 2 O 5 ) in a casing (not shown). ) Is provided with a large number of denitration catalysts 12 each carrying a catalyst component whose main component is sulfur dioxide (hereinafter referred to as S2) in a side reaction of the denitration reaction.
O 2 hereinafter) to oxidize the sulfur trioxide (hereinafter, it is converted to be called SO 3). Here, V 2 O 5 with respect to carrier 11
Is usually about 1 to 2%, and at most about 5 to 6%.
【０００４】ＳＯ2 が転化されてなるＳＯ3 は、乾式の
脱硫装置４では捕捉（脱硫）することができず、煙突５
から排出される際に紫色の煙に見えるため、環境・住民
対策上好ましくない。また、ＳＯ3 は、脱硝反応（還元
反応）の際に用いられるアンモニアガスＡと反応して固
体の硫酸アンモニウム（ＮＨ4 ＳＯ3 ；硫安）及び酸性
硫安を生成し、この硫安が煙道を閉塞させるおそれがあ
る。[0004] SO 3 which SO 2 is formed by conversion can not be captured (desulfurization) in dry desulfurizer 4, the chimney 5
This is not preferable in terms of environmental and inhabitant measures because it looks like purple smoke when discharged from the city. In addition, SO 3 reacts with ammonia gas A used in the denitration reaction (reduction reaction) to generate solid ammonium sulfate (NH 4 SO 3 ; ammonium sulfate) and acidic ammonium sulfate, and this ammonium sulfate blocks the flue. There is a risk.
【０００５】よって、脱硝触媒１２においては、ＳＯ3
への転化率を下げる方法が採られているのが現状であ
る。ＳＯ3 への転化率を下げる従来の方法は、担体１１
に対するＶ2 Ｏ5 の重量比を小さくする又は担体１１に
触媒成分と金属（例えば、Ａｌ、Ｓｃ、Ｍｇ、Ｚｎ）か
らなる第２触媒成分とを担持させることで対応してい
た。Therefore, in the denitration catalyst 12, SO 3
At present, there is a method to reduce the conversion rate to wastewater. Conventional methods of reducing the conversion to SO 3 include the support 11
Catalyst component and a metal (e.g., Al, Sc, Mg, Zn ) or carrier 11 to reduce the weight ratio of V 2 O 5 with respect corresponded by supporting the second catalyst component comprising.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、この方
法では以下に挙げるような問題があった。However, this method has the following problems.
【０００７】 担体１１に対するＶ2 Ｏ5 の重量比を
小さくしても、オリマルジョン等のようなＶ分を多く含
有した燃料を燃焼させると、燃焼灰中にＶ2 Ｏ5 が析出
し、その結果、脱硝触媒１２におけるＶ2 Ｏ5 の重量比
が再び大きくなるため、ＳＯ3への転化率が上昇する。[0007] Even when the weight ratio of V 2 O 5 to the carrier 11 is reduced, when a fuel containing a large amount of V such as orimulsion is burned, V 2 O 5 is precipitated in the combustion ash, and as a result, Since the weight ratio of V 2 O 5 in the denitration catalyst 12 increases again, the conversion to SO 3 increases.
【０００８】 担体１１に対するＶ2 Ｏ5 の重量比を
小さくすると、脱硝反応（ＮＯX をＮ2 に還元）におけ
るＮ2 への転化率が低くなってしまう。[0008] Reducing the weight ratio of V 2 O 5 with respect to the carrier 11, conversion to N 2 in the denitration reaction (reducing the NO X to N 2) is lowered.
【０００９】 第２触媒成分を担持させることでＳＯ
3 への転化率は下げることができるが、触媒成分の良好
な脱硝性能を阻害し、脱硝反応におけるＮ2 への転化率
が著しく低くなってしまう。By supporting the second catalyst component, SO 2
Although the conversion to 3 can be reduced, the favorable denitration performance of the catalyst component is impaired, and the conversion to N 2 in the denitration reaction becomes extremely low.
【００１０】そこで本発明は、上記課題を解決し、Ｎ2
への転化率が高く、かつ、ＳＯ3 への転化率が低い脱硝
触媒を提供することにある。Therefore, the present invention solves the above-mentioned problems and provides N 2
Conversion to high, and is that the conversion to SO 3 to provide a low denitration catalyst.
【００１１】[0011]
【課題を解決するための手段】上記課題を解決するため
に請求項１の発明は、担体に五酸化バナジウムを主成分
とする触媒成分を担持させた脱硝触媒において、上記担
体に、上記触媒成分と第一イオン化ポテンシャルがＶよ
りも大きい金属及びその酸化物からなる第２触媒成分と
を担持させたものである。In order to solve the above-mentioned problems, the present invention is directed to a denitration catalyst comprising a carrier having a catalyst component containing vanadium pentoxide as a main component. And a metal having a first ionization potential greater than V and a second catalyst component composed of an oxide thereof.
【００１２】請求項２の発明は、上記担体に、重量比で
１〜３％の上記五酸化バナジウム、および重量比で１〜
３％の上記金属及びその酸化物を担持させた請求項１記
載の脱硝触媒である。The invention of claim 2 is characterized in that the carrier is provided with 1 to 3% by weight of the vanadium pentoxide,
The denitration catalyst according to claim 1, wherein 3% of the metal and its oxide are supported.
【００１３】請求項３の発明は、上記金属が、Ｃｒ、Ｚ
ｒ、Ｎｂ、Ａｃ、Ｈｆ、Ｍｏ、Ｔｅ、Ｂｉ、Ｓｎ、Ｒ
ｕ、Ｐｂ、Ｍｎの中から選択される少なくとも一つであ
る請求項１記載の脱硝触媒である。According to a third aspect of the present invention, the metal is Cr, Z
r, Nb, Ac, Hf, Mo, Te, Bi, Sn, R
The denitration catalyst according to claim 1, which is at least one selected from u, Pb, and Mn.
【００１４】以上の構成によれば、脱硝率を下げること
なく、かつ、担体に対するＶ2 Ｏ5の重量比を小さくす
ることなく、ＳＯ3 への転化率を下げることができ、ま
た、Ｖ分を多く含有した燃料を燃焼させても、ＳＯ3 へ
の転化率が上昇することはない。According to the above configuration, the conversion rate to SO 3 can be reduced without lowering the denitration rate and without reducing the weight ratio of V 2 O 5 to the carrier. Even if a fuel containing a large amount of is burned, the conversion rate to SO 3 does not increase.
【００１５】[0015]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００１６】先ず、本発明者らは、Ｖ2 Ｏ5 触媒の量子
化学的検討を行った。First, the present inventors conducted a quantum chemical study on a V 2 O 5 catalyst.
【００１７】Ｖ2 Ｏ5 の結晶構造モデル図を図４に示
す。FIG. 4 shows a model of the crystal structure of V 2 O 5 .
【００１８】図４に示すように、Ｖ原子と結合するＯ原
子は、１個のＶ原子と二重結合した１配位格子酸素（Ｏ
1 ）、２個のＶ原子と結合した２配位格子酸素
（Ｏ2 ）、および同じく２個のＶ原子と結合した２配位
格子酸素（Ｏ3 ）というように、配位の異なる３つに分
類される。As shown in FIG. 4, an O atom bonded to a V atom is a one-coordinate lattice oxygen (O) double-bonded to one V atom.
1 ) three coordination lattice oxygen (O 2 ) bonded to two V atoms and two coordination lattice oxygen (O 3 ) also bonded to two V atoms are categorized.
【００１９】Ｖ2 Ｏ5 の各Ｏ原子におけるエネルギーと
ピーク強度との関係を図５に示す。FIG. 5 shows the relationship between the energy and the peak intensity of each O atom of V 2 O 5 .
【００２０】図５に示すように、各Ｏ原子において、２
配位格子酸素（Ｏ3 ）のエネルギーが一番低く、チャー
ジ（マイナスの電荷）をたくさん帯びていることが伺え
る。As shown in FIG. 5, for each O atom, 2
It can be seen that the energy of coordination lattice oxygen (O 3 ) is the lowest, and that it has a lot of charge (negative charge).
【００２１】すなわち、脱硝反応初期のＨ2 Ｏ（又は
Ｈ）は、図５に示すように、エネルギーが最も高い１配
位格子酸素（Ｏ1 ）に吸着され、１配位格子酸素
（Ｏ1 ）のエネルギーレベルが作用することが伺える。
また、ＳＯ2 の吸着は、チャージの大きさがその反応性
を決定するため、図５に示すように、チャージが最も大
きい２配位格子酸素（Ｏ3 ）に吸着されることが伺え
る。[0021] That is, the denitration reaction initial H 2 O (or H), as shown in FIG. 5, is attracted to the energy is the highest 1 coordination lattice oxygen (O 1), 1 coordination lattice oxygen (O 1 It can be seen that the energy level of ()) works.
In addition, since the magnitude of the charge determines the reactivity of the adsorption of SO 2 , the charge is adsorbed to the two-coordinate lattice oxygen (O 3 ) having the largest charge as shown in FIG.
【００２２】脱硝反応におけるＳＯ2 の吸着量とＳＯ3
への転化率との関係を図６に示す。The adsorption amount of SO 2 and SO 3 in the denitration reaction
FIG. 6 shows the relationship with the conversion rate to the temperature.
【００２３】ここで、図６に示すように、脱硝反応にお
けるＳＯ2 の吸着量が増加するにつれてＳＯ3 への転化
率も増加する。このため、２配位格子酸素（Ｏ3 ）によ
るＳＯ2 の吸着を防ぐことが必要となってくる。Here, as shown in FIG. 6, the conversion to SO 3 increases as the amount of SO 2 adsorbed in the denitration reaction increases. Therefore, it is necessary to prevent the adsorption of SO 2 by the two-coordinate lattice oxygen (O 3 ).
【００２４】よって、本発明者らは、２配位格子酸素
（Ｏ3 ）によるＳＯ2 の吸着を減らすべく、すなわち、
２配位格子酸素（Ｏ3 ）のチャージを低下させるべく、
担体に、Ｖ2 Ｏ5 と共に、Ｖよりも第一イオン化ポテン
シャル（以下、I.p.と呼ぶ）の大きな金属又はその酸化
物を担持させることにより、２配位格子酸素（Ｏ3 ）の
チャージが低下するということを見出した。Therefore, the present inventors aimed to reduce the adsorption of SO 2 by two-coordinated lattice oxygen (O 3 ),
In order to reduce the charge of the two-coordinate lattice oxygen (O 3 ),
By supporting a metal or an oxide thereof having a first ionization potential (hereinafter, referred to as Ip) higher than V together with V 2 O 5 on the carrier, the charge of two-coordinate lattice oxygen (O 3 ) is reduced. I found that.
【００２５】本発明の脱硝触媒は、図８に示した酸化チ
タンからなる担体１１に、重量比で１〜３％のＶ2 Ｏ5
を主成分とする触媒成分と、同じく重量比で１〜３％の
ＶよりもI.p.が大きな金属又はその酸化物からなる第２
触媒成分を担持させたものである。The denitration catalyst of the present invention, a carrier 11 made of titanium oxide as shown in FIG. 8, V 1 to 3 percent by weight 2 O 5
And a second catalyst comprising a metal or an oxide thereof having a larger Ip than V by 1 to 3% by weight.
The catalyst component is supported.
【００２６】ここで、各種金属元素の第一イオン化ポテ
ンシャル（ｅＶ）を表１に示す。Here, Table 1 shows the first ionization potential (eV) of various metal elements.
【００２７】[0027]
【表１】 [Table 1]
【００２８】表１に示すように、I.p.がＶ（６．７４ｅ
Ｖ）よりも大きな金属元素としては、I.p.の小さい順
に、Ｃｒ、Ｚｒ、Ｎｂ、Ａｃ、Ｈｆ、Ｍｏ、Ｔｅ、Ｂ
ｉ、Ｓｎ、Ｒｕ、Ｐｂ、Ｍｎ、…、Ｔａ、Ｗ、Ｐｄ、Ｚ
ｎなどが挙げられる。As shown in Table 1, Ip is V (6.74e
As metal elements larger than V), Cr, Zr, Nb, Ac, Hf, Mo, Te, B
i, Sn, Ru, Pb, Mn,..., Ta, W, Pd, Z
n.
【００２９】第一イオン化ポテンシャル（ｅＶ）と脱硝
性能との関係を図２に示す。図２中の縦軸は、担体にＶ
2 Ｏ5 を主成分とする触媒成分とＶよりも大きなI.p.を
有する金属（又はその酸化物）からなる第２触媒成分と
を担持させた脱硝触媒の脱硝率と、担体にＶ2 Ｏ5 を主
成分とする触媒成分のみを担持させた脱硝触媒の脱硝率
との比を示している（比が大きい（脱硝性能が高い）ほ
ど良好）。尚、脱硝反応温度は３８０℃とした。FIG. 2 shows the relationship between the first ionization potential (eV) and the denitration performance. The vertical axis in FIG.
The denitration rate of a denitration catalyst supporting a catalyst component containing 2 O 5 as a main component and a second catalyst component made of a metal (or an oxide thereof) having an Ip greater than V, and V 2 O 5 as a carrier The graph shows the ratio to the denitration rate of the denitration catalyst supporting only the catalyst component as the main component (the larger the ratio (the higher the denitration performance), the better). The denitration reaction temperature was 380 ° C.
【００３０】図２に示すように、担体にＶ2 Ｏ5 を主成
分とする触媒成分とＶよりも大きなI.p.を有する金属
（図２中ではＣｒ、Ｚｒ、Ｎｂ、Ｈｆ、Ｍｏ、Ｍｎ）か
らなる第２触媒成分とを担持させた脱硝触媒において
は、金属のI.p.が大きくなればなるほど、脱硝性能が低
下する傾向が伺える。また、担体にＶ2 Ｏ5 を主成分と
する触媒成分とＶよりも小さいI.p.を有する金属（図２
中ではＡｌ、Ｓｃ）からなる第２触媒成分とを担持させ
た脱硝触媒においては、脱硝性能が著しく低くなること
が伺える。すなわち、触媒成分と共に担体に担持させる
金属のI.p.が、Ｖよりも大きすぎる場合およびＶよりも
小さい場合、脱硝触媒の本来の目的である脱硝性能の低
下を招いてしまう。尚、Ｍｇを第２触媒成分として担持
させた脱硝触媒の脱硝性能は、０．５未満であったため
図示を省略している。As shown in FIG. 2, the carrier is composed of a catalyst component mainly composed of V 2 O 5 and a metal having a higher Ip than V (Cr, Zr, Nb, Hf, Mo, Mn in FIG. 2). In the denitration catalyst supporting the second catalyst component, the denitration performance tends to decrease as the metal Ip increases. In addition, a catalyst component mainly composed of V 2 O 5 and a metal having an Ip smaller than V (FIG. 2)
Among them, it can be seen that the denitration performance of the denitration catalyst supporting the second catalyst component composed of Al and Sc) is extremely low. That is, when the Ip of the metal supported on the carrier together with the catalyst component is too large or smaller than V, the denitration performance, which is the original purpose of the denitration catalyst, is reduced. The denitration performance of the denitration catalyst supporting Mg as the second catalyst component was less than 0.5, and is not shown.
【００３１】第一イオン化ポテンシャル（ｅＶ）とＳＯ
2 吸着量との関係を図３に示す。図３中の縦軸は、担体
にＶ2 Ｏ5 を主成分とする触媒成分と各金属（又はその
酸化物）からなる第２触媒成分とを担持させた脱硝触媒
のＳＯ2 吸着量を示している（ＳＯ2 吸着量が少ないほ
ど良好）。First ionization potential (eV) and SO
The relationship between the 2 adsorption amount shown in FIG. The vertical axis in FIG. 3 indicates the SO 2 adsorption amount of the denitration catalyst in which the catalyst component mainly composed of V 2 O 5 and the second catalyst component composed of each metal (or oxide thereof) are supported on the carrier. (The smaller the SO 2 adsorption amount, the better).
【００３２】図３に示すように、Ｖをピークとして、Ｖ
よりも大きなI.p.を有する金属を担持させるほどＳＯ2
の吸着量が少なくなり、延いては、ＳＯ3 への転化が抑
制される。ただし、I.p.が７．４５ｅＶ程度で、ＳＯ2
の吸着量減少効果は飽和するため、I.p.が７．４５ｅＶ
よりも大きな金属を担持させてもＳＯ2 の吸着量は殆ど
変わらなくなる。As shown in FIG. 3, V is a peak and V
The more the metal having a larger Ip is supported, the more SO 2
Is reduced, and the conversion to SO 3 is suppressed. However, when Ip is about 7.45 eV and SO 2
Since the effect of reducing the amount of adsorption is saturated, Ip is 7.45 eV
Even if a larger metal is supported, the adsorption amount of SO 2 hardly changes.
【００３３】よって、図２、図３の結果から、I.p.がＶ
よりも大きく、かつ、７．４５ｅＶ未満の金属（又はそ
の酸化物）を第２触媒成分として担体に担持させること
で、脱硝性能の低下が殆どなく、かつ、ＳＯ2 の吸着量
が少ない脱硝触媒を得ることができる。Therefore, from the results of FIGS. 2 and 3, Ip is V
A metal (or oxide thereof) larger than 7.45 eV and supported on a carrier as the second catalyst component, so that the denitration performance is hardly reduced and the SO 2 adsorption amount is small. Can be obtained.
【００３４】脱硝性能とＳＯ2 吸着能との関係を図１に
示す。図１中の横軸は、担体にＶ2Ｏ5 を主成分とする
触媒成分とＶよりも大きなI.p.を有する金属（又はその
酸化物）からなる第２触媒成分とを担持させた脱硝触媒
の脱硝性能と、担体にＶ2 Ｏ5 を主成分とする触媒成分
のみを担持させた脱硝触媒の脱硝性能との比を示してい
る（比が大きい（脱硝性能高い）ほど良好）。また、縦
軸は、担体にＶ2 Ｏ5を主成分とする触媒成分とＶより
も大きなI.p.を有する金属（又はその酸化物）からなる
第２触媒成分とを担持させた脱硝触媒のＳＯ2 吸着量
と、担体にＶ2 Ｏ5 を主成分とする触媒成分のみを担持
させた脱硝触媒のＳＯ2 吸着量との比を示している（比
が小さい（ＳＯ2 吸着能が低い）ほど良好）。さらに、
図１中の黒丸印は本発明の脱硝触媒における第２触媒成
分金属を示し、白丸印は従来の脱硝触媒における第２触
媒成分金属を示している。FIG. 1 shows the relationship between the denitration performance and the SO 2 adsorption performance. The abscissa in FIG. 1 represents a denitration catalyst in which a catalyst component mainly composed of V 2 O 5 and a second catalyst component composed of a metal (or an oxide thereof) having an Ip greater than V are supported on a carrier. The graph shows the ratio between the denitration performance and the denitration performance of a denitration catalyst in which only a catalyst component mainly composed of V 2 O 5 is supported on a carrier (the larger the ratio (the higher the denitration performance), the better). The vertical axis indicates the SO 2 of the denitration catalyst in which the carrier carries a catalyst component mainly composed of V 2 O 5 and a second catalyst component composed of a metal (or an oxide thereof) having an Ip greater than V. It shows the ratio between the adsorption amount and the SO 2 adsorption amount of a denitration catalyst in which only a catalyst component mainly composed of V 2 O 5 is supported on a carrier (the smaller the ratio (the lower the SO 2 adsorption capacity), the better) ). further,
The black circles in FIG. 1 indicate the second catalyst component metal in the denitration catalyst of the present invention, and the white circles indicate the second catalyst component metal in the conventional denitration catalyst.
【００３５】図１に示すように、本発明の脱硝触媒にお
ける第２触媒成分金属は、ＳＯ2 吸着能が低いため、Ｓ
Ｏ3 への転化率が低くなることは言うまでもなく、担体
にＶ2 Ｏ5 を主成分とする触媒成分のみを担持させた脱
硝触媒の脱硝性能と比較して、脱硝性能の低下を２０％
未満に抑制することができ、良好な脱硝性能も併せ持っ
ていることが伺える。As shown in FIG. 1, the second catalyst component metal in the denitration catalyst of the present invention has a low SO 2 adsorption capacity,
Needless to say, the conversion rate to O 3 is lowered, and the denitration performance is reduced by 20% as compared with the denitration performance of the denitration catalyst in which only the catalyst component mainly composed of V 2 O 5 is supported on the carrier.
It can be seen that it also has good denitration performance.
【００３６】これに対して、従来の脱硝触媒における第
２触媒成分金属は、本発明の脱硝触媒における第２触媒
成分金属よりもＳＯ2 吸着能が全般的に低く、ＳＯ2 吸
着能だけに関して言えば良好であるものの、担体にＶ2
Ｏ5 を主成分とする触媒成分のみを担持させた脱硝触媒
の脱硝性能と比較して、脱硝性能の低下が２０〜６０％
にも達し、脱硝性能が著しく悪いことが伺える。On the other hand, the second catalyst component metal in the conventional denitration catalyst generally has lower SO 2 adsorption ability than the second catalyst component metal in the denitration catalyst of the present invention, and it can be said that only the SO 2 adsorption ability is concerned. Is good, but V 2
O 5 as compared to the denitrification performance of the denitration catalyst supported only catalyst component composed mainly of a reduction in the denitration performance 20% to 60%
It can be said that the denitration performance is extremely poor.
【００３７】本発明の脱硝触媒における第２触媒成分金
属としては、Ｃｒ、Ｚｒ、Ｎｂ、Ａｃ、Ｈｆ、Ｍｏ、Ｔ
ｅ、Ｂｉ、Ｓｎ、Ｒｕ、Ｐｂ、Ｍｎの中から選択される
少なくとも一種が好ましく、更に好ましくは、図１中の
斜線領域内の金属（図１中ではＮｂ、Ｈｆ）が挙げられ
る。As the second catalyst component metal in the denitration catalyst of the present invention, Cr, Zr, Nb, Ac, Hf, Mo, T
At least one selected from the group consisting of e, Bi, Sn, Ru, Pb, and Mn is preferable, and more preferably, metals (Nb and Hf in FIG. 1) in a hatched region in FIG.
【００３８】触媒成分および第２触媒成分を担持させる
担体１１としては、図８に示したハニカム構造体に特に
限定するものではなく、例えば、球体、円筒体、粉末
体、或いは多孔質状平板体などが挙げられる。The carrier 11 for supporting the catalyst component and the second catalyst component is not particularly limited to the honeycomb structure shown in FIG. 8, and may be, for example, a sphere, a cylinder, a powder, or a porous plate. And the like.
【００３９】担体１１の構成材は、酸化チタンに特に限
定するものではなく、例えば、酸化タングステン、シリ
カ、シリカ／アルミナなどが挙げられる。The constituent material of the carrier 11 is not particularly limited to titanium oxide, but includes, for example, tungsten oxide, silica, silica / alumina and the like.
【００４０】本発明の脱硝触媒によれば、担体１１に、
担体１１に対する重量比がそれぞれ１〜３％のＶ2 Ｏ5
を主成分とする触媒成分とＶよりもI.p.が大きな金属又
はその酸化物からなる第２触媒成分とを担持させている
ため、それらの金属又はその酸化物がＶ2 Ｏ5 における
Ｖのチャージを吸収し、それによって、２配位格子酸素
（Ｏ3 ）のチャージが小さくなり、２配位格子酸素（Ｏ
3 ）に吸着されるＳＯ2 の量が減少してＳＯ3 への転化
率が下がる。According to the denitration catalyst of the present invention, the carrier 11
V 2 O 5 having a weight ratio to the carrier 11 of 1 to 3%, respectively.
And a second catalyst component composed of a metal or an oxide thereof having a larger Ip than V, so that the metal or the oxide thereof can charge V in V 2 O 5 . So that the charge of the two-coordinate lattice oxygen (O 3 ) is reduced,
The amount of SO 2 that is adsorbed to 3) conversion to SO 3 drops decreases.
【００４１】また、担体１１に担持させる触媒成分（Ｖ
2 Ｏ5 ）の量を少なくしているわけではなく、かつ、脱
硝率が良好な金属又はその酸化物を選択して第２触媒成
分としてＶ2 Ｏ5 と共に担持させているため、脱硝開始
初期の脱硝率が下がることはない。Further, the catalyst component (V
Since the amount of 2 O 5 ) is not reduced and a metal or oxide thereof having a good denitration rate is selected and supported together with V 2 O 5 as the second catalyst component, the initial stage of denitration start The denitration rate does not decrease.
【００４２】さらに、オリマルジョン等のようなＶ分を
多く含有した燃料を燃焼させ、燃焼灰中のＶ2 Ｏ5 が脱
硝触媒に付着したとしても、ＶよりもI.p.の大きい金属
又はその酸化物を、十分に（担体１１に対して、重量比
で１〜３％）担持させているため、その影響は小さなも
のとなり、その結果、ＳＯ3 への転化率が上昇すること
はない。Further, even if V 2 O 5 in the combustion ash adheres to the denitration catalyst by burning a fuel containing a large amount of V, such as orimulsion, etc., a metal having a larger Ip than V or its oxide is removed. However, since it is sufficiently supported (1 to 3% by weight with respect to the carrier 11), the effect is small, and as a result, the conversion rate to SO 3 does not increase.
【００４３】また更に、本発明の脱硝触媒を火力発電所
などの排ガス処理に用いることで、ＳＯ3 生成による排
煙の紫煙化のおそれが殆どなく、ＳＯ3 とアンモニアガ
スとが反応して析出する硫安（又は酸性硫安）による脱
硝触媒の性能劣化を防ぐことができる。Further, by using the denitration catalyst of the present invention for exhaust gas treatment of a thermal power plant or the like, there is almost no possibility that the exhaust gas becomes purple smoke due to SO 3 generation, and SO 3 and ammonia gas react and precipitate. The performance of the denitration catalyst can be prevented from deteriorating due to ammonium sulfate (or acidic ammonium sulfate).
【００４４】尚、本発明の脱硝触媒は、図７に示したよ
うに、火力発電所などにおけるボイラ１の排ガスＧに限
らず、その他に、ゴミ焼却炉の排ガス、ガス化炉のガス
化ガスなどに対しても適用することができる。As shown in FIG. 7, the denitration catalyst of the present invention is not limited to the exhaust gas G of the boiler 1 in a thermal power plant or the like, but also the exhaust gas of a garbage incinerator and the gasified gas of a gasification furnace. It can be applied to such as.
【００４５】[0045]
【発明の効果】以上要するに本発明によれば、担体に、
Ｖ2 Ｏ5 を主成分とする触媒成分とＶよりもイオン化ポ
テンシャルが大きな金属又はその酸化物からなる第２触
媒成分とを担持させることで、触媒成分による良好な脱
硝性能を保ちつつ、Ｖ2 Ｏ5 における２配位格子酸素
（Ｏ3 ）のチャージが小さくなることから、２配位格子
酸素（Ｏ3 ）に吸着されるＳＯ2 の量が減少してＳＯ3
への転化率が低くなるという優れた効果を発揮する。In summary, according to the present invention, the carrier comprises:
V 2 O 5 of the catalyst component and V mainly comprising by supporting the second catalyst component ionization potential consisting of large metal or an oxide thereof, while maintaining good denitration performance by the catalytic component, V 2 Since the charge of the two-coordinate lattice oxygen (O 3 ) in O 5 becomes small, the amount of SO 2 adsorbed on the two-coordinate lattice oxygen (O 3 ) decreases, and the SO 3
It has an excellent effect that the conversion rate to carbon is reduced.
【図１】脱硝性能とＳＯ2 吸着能との関係を示す図であ
る。FIG. 1 is a graph showing the relationship between denitration performance and SO 2 adsorption performance.
【図２】第一イオン化ポテンシャル（ｅＶ）と脱硝性能
との関係を示す図である。FIG. 2 is a diagram showing a relationship between first ionization potential (eV) and denitration performance.
【図３】第一イオン化ポテンシャル（ｅＶ）とＳＯ2 吸
着量との関係を示す図である。FIG. 3 is a diagram showing a relationship between a first ionization potential (eV) and an SO 2 adsorption amount.
【図４】Ｖ2 Ｏ5 の結晶構造モデルを示す図である。FIG. 4 is a diagram showing a crystal structure model of V 2 O 5 .
【図５】Ｖ2 Ｏ5 の各Ｏ原子におけるエネルギーとピー
ク強度との関係を示す図である。FIG. 5 is a diagram showing a relationship between energy and peak intensity in each O atom of V 2 O 5 .
【図６】脱硝反応におけるＳＯ2 の吸着量とＳＯ3 への
転化率との関係を示す図である。FIG. 6 is a diagram showing the relationship between the adsorption amount of SO 2 and the conversion to SO 3 in the denitration reaction.
【図７】ボイラの排ガスのフローを示す概略図である。FIG. 7 is a schematic diagram showing a flow of exhaust gas from a boiler.
【図８】脱硝触媒の斜視図である。FIG. 8 is a perspective view of a denitration catalyst.
１１ 担体 １２ 脱硝触媒 11 carrier 12 denitration catalyst
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 27/057 Ｂ０１Ｄ 53/36 １０２Ｂ Ｂ０１Ｊ 23/64 １０２Ａ (72)発明者 高橋 克巳 神奈川県横浜市磯子区新中原町１番地 石 川島播磨重工業株式会社機械・プラント開 発センター内 (72)発明者 居橋 渉 神奈川県横浜市磯子区新中原町１番地 石 川島播磨重工業株式会社機械・プラント開 発センター内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 27/057 B01D 53/36 102B B01J 23/64 102A (72) Inventor Katsumi Takahashi Isogo-ku, Yokohama-shi, Kanagawa No. 1 Shin-Nakahara-cho Ishi Kawashima-Harima Heavy Industries Co., Ltd. Machinery and Plant Development Center (72) Inventor Wataru Ibashi 1-shi Shin-Nakahara-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture
Claims (3)
触媒成分を担持させた脱硝触媒において、上記担体に、
上記触媒成分と第一イオン化ポテンシャルがＶよりも大
きい金属及びその酸化物からなる第２触媒成分とを担持
させたことを特徴とする脱硝触媒。1. A denitration catalyst comprising a carrier carrying a catalyst component containing vanadium pentoxide as a main component, wherein the carrier comprises:
A denitration catalyst comprising the catalyst component and a second catalyst component comprising a metal having a first ionization potential greater than V and an oxide thereof.
酸化バナジウム、および重量比で１〜３％の上記金属及
びその酸化物を担持させた請求項１記載の脱硝触媒。2. The denitration catalyst according to claim 1, wherein the carrier supports 1 to 3% by weight of the vanadium pentoxide and 1 to 3% by weight of the metal and its oxide.
Ｈｆ、Ｍｏ、Ｔｅ、Ｂｉ、Ｓｎ、Ｒｕ、Ｐｂ、Ｍｎの中
から選択される少なくとも一つである請求項１記載の脱
硝触媒。3. The method according to claim 1, wherein the metal is Cr, Zr, Nb, Ac,
The denitration catalyst according to claim 1, wherein the catalyst is at least one selected from Hf, Mo, Te, Bi, Sn, Ru, Pb, and Mn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12479499A JP4505873B2 (en) | 1998-08-19 | 1999-04-30 | Denitration method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23291798 | 1998-08-19 | ||
| JP10-232917 | 1998-08-19 | ||
| JP12479499A JP4505873B2 (en) | 1998-08-19 | 1999-04-30 | Denitration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000126591A true JP2000126591A (en) | 2000-05-09 |
| JP4505873B2 JP4505873B2 (en) | 2010-07-21 |
Family
ID=26461394
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12479499A Expired - Fee Related JP4505873B2 (en) | 1998-08-19 | 1999-04-30 | Denitration method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007037593A1 (en) * | 2005-09-27 | 2007-04-05 | Korea Power Engineering Company, Inc. | Vanadium/titania catalyst comprising natural manganese ore for removing nitrogen oxides and dioxin in wide operating temperature rangeand method of using the same |
| CN107262119A (en) * | 2017-07-14 | 2017-10-20 | 邢台旭阳科技有限公司 | A kind of middle low temperature resistant to sulfur catalyst for denitrating flue gas |
| CN108144601A (en) * | 2018-02-05 | 2018-06-12 | 安徽弘昇环境工程科技有限公司 | A kind of SCR ultralow temperature denitrating catalyst and preparation method thereof |
| CN112121831A (en) * | 2020-10-30 | 2020-12-25 | 山东信能达工程科技有限公司 | Wide-temperature sulfur-resistant water-resistant vanadium-titanium denitration catalyst and preparation method thereof |
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| CN108144601A (en) * | 2018-02-05 | 2018-06-12 | 安徽弘昇环境工程科技有限公司 | A kind of SCR ultralow temperature denitrating catalyst and preparation method thereof |
| CN112121831A (en) * | 2020-10-30 | 2020-12-25 | 山东信能达工程科技有限公司 | Wide-temperature sulfur-resistant water-resistant vanadium-titanium denitration catalyst and preparation method thereof |
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|---|---|
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