JPWO2020216460A5

JPWO2020216460A5 -

Info

Publication number: JPWO2020216460A5
Application number: JP2021563342A
Authority: JP
Publication date: 2023-12-01
Anticipated expiration: 2039-08-26

Description

本発明の触媒は、１～２０重量％、好ましくは２～１０重量％のコーティングを含む。本発明で使用するとき、用語「触媒」は、セラミックキャンドルフィルタ基材及びコーティングを包含する。 The catalyst of the present invention contains 1 to 20% by weight of coating, preferably 2 to 10% by weight. As used herein, the term "catalyst" includes ceramic candle filter substrates and coatings.

結果を図２に示す。
本願は特許請求の範囲に記載の発明に係るものであるが、本願の開示は以下も包含する：
１．窒素酸化物の選択的触媒還元（ＳＣＲ）で使用するための触媒であって、
セラミックキャンドルフィルタ基材と、
チタンの酸化物を含む酸化金属担体、及びバナジウムの酸化物を含む触媒金属酸化物を含み、バナジウム／チタンの質量比が０．０３～０．２７であるコーティングと、を含み、
質量比は、バナジウム金属及びチタン金属の質量に基づいて計算され、
前記触媒は、１～２０重量％の触媒活性物質を含み、
前記触媒金属酸化物は、前記酸化金属担体の表面上に吸着されている、触媒。
２．バナジウムの酸化物を含む前記コーティングの前記触媒金属酸化物が、五酸化バナジウム（Ｖ _２Ｏ _５）を含む、前記１．に記載の触媒。
３．バナジウムの酸化物を含む前記コーティングの前記触媒金属酸化物が、加えて、タングステン及び／又はモリブデン及び／又はアンチモンの酸化物を含む、前記２．に記載の触媒。
４．チタンの酸化物を含む前記コーティングの前記酸化金属担体が、二酸化チタンを含む、前記１．～３．のいずれか一項に記載の触媒。
５．チタンの酸化物を含む前記コーティングの前記酸化金属担体が、加えて、アルミニウム、セリウム、ジルコニウム、又は混合物の酸化物、これらの酸化物のうちの少なくとも１つを含む混合酸化物若しくは化合物を含む、前記４．に記載の触媒。
６．前記酸化金属担体が、１～１０００ｎｍの一次粒径を有する単一の又は凝集した二酸化チタンのナノ粒子のいずれかからなる、前記１．～５．のいずれか一項に記載の触媒。
７．バナジウム／チタンの質量比は０．０３～０．２７であり、質量比は、バナジウム金属及びチタン金属の質量に基づいて計算される、前記１．～６．のいずれか一項に記載の触媒。
８．白金族金属を含まない、前記１．～７．のいずれか一項に記載の触媒。
９．前記１．～８のいずれか一項に記載の触媒を調製するためのプロセスであって、
ａ）セラミックキャンドルフィルタ基材を用意するステップと、
ｂ）酸化チタンを含む酸化金属担体の粒子上に分散されたバナジウム化合物を含む１つ以上の触媒金属前駆体化合物を含む、水性含浸液体を用意するステップであって、
前記含浸液体は、
ｉ．前記１つ以上の触媒金属前駆体化合物及び前記酸化金属担体を水に添加し、このように得られた混合物に酸を連続的に添加して、前記１つ以上の触媒前駆体金属化合物の表面電荷が負であり、前記酸化金属担体のゼータ電位が正である値で、前記混合物のｐＨを維持するステップと、
ｉｉ．前記１つ以上の触媒金属前駆体化合物を前記酸化金属担体の表面上に吸着させるステップと、任意選択的に、
ｉｉｉ．このように調製されたウォッシュコートスラリーの７超のｐＨ値を得る量で、分散剤を、このように調製された混合物に添加するステップと、
ｉｖ．任意選択的に前記混合物を粉砕するステップと、によって調製される、水性含浸液体を用意するステップと、
ｃ）前記得られた含浸液体を、前記セラミックキャンドルフィルタ基材に含浸させるステップと、
ｄ）前記含浸されたセラミックキャンドルフィルタ基材を、１５０～６００℃の温度で乾燥及び熱活性化して、前記１つ以上の金属前駆体化合物をそれらの触媒活性形態に変換するステップと、を含む、プロセス。
１０．バナジウム化合物を含む前記触媒金属前駆体化合物が、メタバナジン酸アンモニウムである、前記９．に記載のプロセス。
１１．前記水性含浸液体が、その液体に可溶性の第一級アミンを含む、前記９．又は１０．に記載のプロセス。
１２．前記第一級アミンが、モノエチルアミンである、前記１１．に記載のプロセス。
１３．自動車及び固定発生源からのオフガスを処理するための、並びに前記オフガスに含有される窒素酸化物を選択的に還元するための方法であって、前記オフガスを、前記１．～９．のいずれか一項に記載の触媒に通過させる、方法。 The results are shown in Figure 2.
Although this application relates to the invention described in the claims, the disclosure of this application also includes the following:
1. A catalyst for use in selective catalytic reduction (SCR) of nitrogen oxides, the catalyst comprising:
Ceramic candle filter base material,
an oxidized metal support comprising an oxide of titanium; and a coating comprising a catalytic metal oxide comprising an oxide of vanadium, the mass ratio of vanadium/titanium being from 0.03 to 0.27;
The mass ratio is calculated based on the mass of vanadium metal and titanium metal,
The catalyst contains 1 to 20% by weight of catalytically active material,
The catalyst, wherein the catalytic metal oxide is adsorbed on the surface of the oxidized metal support.
2. 1. wherein the catalytic metal oxide of the coating comprising an oxide of vanadium comprises vanadium pentoxide (V ₂ O ₅ ). Catalysts described in.
3. 2. wherein said catalytic metal oxide of said coating comprising an oxide of vanadium additionally comprises an oxide of tungsten and/or molybdenum and/or antimony; Catalysts described in.
4. 1. wherein the oxidized metal support of the coating comprising an oxide of titanium comprises titanium dioxide. ~3. The catalyst according to any one of the following.
5. the oxidized metal support of the coating comprising an oxide of titanium additionally comprises an oxide of aluminum, cerium, zirconium or a mixture, a mixed oxide or a compound comprising at least one of these oxides; Above 4. Catalysts described in.
6. 1. wherein said metal oxide support consists of either single or aggregated titanium dioxide nanoparticles having a primary particle size of 1 to 1000 nm. ~5. The catalyst according to any one of the following.
7. The mass ratio of vanadium/titanium is 0.03 to 0.27, and the mass ratio is calculated based on the mass of vanadium metal and titanium metal. ~6. The catalyst according to any one of the following.
8. 1 above, which does not contain platinum group metals. ~7. The catalyst according to any one of the following.
9. Said 1. 8. A process for preparing a catalyst according to any one of claims 1 to 8, comprising:
a) providing a ceramic candle filter substrate;
b) providing an aqueous impregnating liquid comprising one or more catalytic metal precursor compounds comprising a vanadium compound dispersed on particles of an oxidized metal support comprising titanium oxide;
The impregnating liquid is
i. The one or more catalytic metal precursor compounds and the oxidized metal support are added to water, and an acid is continuously added to the mixture thus obtained to improve the surface of the one or more catalytic metal precursor compounds. maintaining the pH of the mixture at a value where the charge is negative and the zeta potential of the oxidized metal support is positive;
ii. adsorbing the one or more catalytic metal precursor compounds onto the surface of the oxidized metal support; and optionally,
iii. adding a dispersant to the mixture thus prepared in an amount to obtain a pH value of greater than 7 of the washcoat slurry thus prepared;
iv. optionally grinding the mixture; and providing an aqueous impregnating liquid prepared by
c) impregnating the ceramic candle filter substrate with the obtained impregnating liquid;
d) drying and thermally activating the impregnated ceramic candle filter substrate at a temperature of 150-600°C to convert the one or more metal precursor compounds into their catalytically active form; ,process.
10. Item 9 above, wherein the catalytic metal precursor compound containing a vanadium compound is ammonium metavanadate. The process described in.
11. Item 9 above, wherein the aqueous impregnating liquid contains a primary amine soluble in the liquid. or 10. The process described in.
12. 11. above, wherein the primary amine is monoethylamine. The process described in.
13. 1. A method for treating off-gas from motor vehicles and stationary sources and for selectively reducing nitrogen oxides contained in said off-gas, comprising: ~9. a method according to any one of the preceding claims.

Claims

A process for preparing a catalyst for use in selective catalytic reduction (SCR) of nitrogen oxides, the process comprising:
The catalyst is
・Ceramic candle filter base material,
- a coating comprising an oxidized metal support comprising an oxide of titanium and a catalytic metal oxide comprising an oxide of vanadium, the mass ratio of vanadium/titanium being 0.03 to 0.27;
The mass ratio is calculated based on the mass of vanadium metal and titanium metal,
the catalyst comprises 1-20% by weight of the coating, and
the catalytic metal oxide is adsorbed on the surface of the oxidized metal support;
The process includes:
a) providing a ceramic candle filter substrate;
b) providing an aqueous impregnating liquid comprising one or more catalytic metal precursor compounds comprising a vanadium compound dispersed on particles of an oxidized metal support comprising titanium oxide;
The impregnating liquid is
i. The one or more catalytic metal precursor compounds and the oxidized metal support are added to water, and an acid is continuously added to the mixture thus obtained to improve the surface of the one or more catalytic metal precursor compounds. maintaining the pH of the mixture at a value where the charge is negative and the zeta potential of the oxidized metal support is positive;
ii. adsorbing the one or more catalytic metal precursor compounds onto the surface of the oxidized metal support; and optionally,
iii. adding a dispersant to the mixture thus prepared in an amount to obtain a pH value of greater than 7 of the washcoat slurry thus prepared;
iv. optionally grinding the mixture; and providing an aqueous impregnating liquid prepared by
c) impregnating the ceramic candle filter substrate with the obtained impregnating liquid;
d) drying and thermally activating the impregnated ceramic candle filter substrate at a temperature of 150-600°C to convert the one or more metal precursor compounds into their catalytically active form; ,process.

2. The process of claim 1 , wherein the catalytic metal precursor compound comprising a vanadium compound is ammonium metavanadate.

3. A process according to claim 1 or 2 , wherein the aqueous impregnating liquid comprises a primary amine soluble therein.

4. The process of claim 3 , wherein the primary amine is monoethylamine.

The catalytic metal oxide of the coating comprising an oxide of vanadium is vanadium pentoxide (V _２2 O _５5 ) The process according to any one of claims 1 to 4.

6. Process according to claim 5, wherein the catalytic metal oxide of the coating comprising oxides of vanadium additionally comprises oxides of tungsten and/or molybdenum and/or antimony.

Process according to any one of claims 1 to 6, wherein the oxidized metal carrier of the coating comprising an oxide of titanium comprises titanium dioxide.

the oxidized metal carrier of the coating comprising an oxide of titanium additionally comprises an oxide of aluminum, cerium, zirconium or a mixture, a mixed oxide or a compound comprising at least one of these oxides; Process according to claim 7.

Process according to any one of claims 1 to 8, wherein the oxidized metal support consists of either single or aggregated titanium dioxide nanoparticles with a primary particle size of 1 to 1000 nm.

10. According to any one of claims 1 to 9, the mass ratio of vanadium/titanium in the coating is between 0.03 and 0.27, the mass ratio being calculated based on the mass of vanadium metal and titanium metal. Process described.

Process according to any one of claims 1 to 10, wherein the catalyst is free of platinum group metals.