JP5787901B2 - 脱硝触媒用担体、脱硝触媒及び脱硝装置 - Google Patents
脱硝触媒用担体、脱硝触媒及び脱硝装置 Download PDFInfo
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- JP5787901B2 JP5787901B2 JP2012549716A JP2012549716A JP5787901B2 JP 5787901 B2 JP5787901 B2 JP 5787901B2 JP 2012549716 A JP2012549716 A JP 2012549716A JP 2012549716 A JP2012549716 A JP 2012549716A JP 5787901 B2 JP5787901 B2 JP 5787901B2
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- exhaust gas
- denitration
- coal
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Description
すなわち、本発明にかかる脱硝触媒用担体は、TiO2を含み、ハニカム構造を有し、且つその比表面積が100m2/gを超えるAsを含む石炭焚ボイラ排ガス用の脱硝触媒用担体である。
本発明の脱硝触媒用担体は、TiO2を含み、ハニカム構造を有し、更に、ハニカム構造を有するように成形された脱硝触媒用担体について測定した比表面積が100m2/gを超えるものである。比表面積を大きくすることにより、As吸着許容量の増大が図られ、As被毒耐性が向上し、脱硝触媒の後流側へのAsの流入を抑制することができる。比表面積は大きい程好ましく、特に100〜160m2/gが好ましい。
比表面積は、窒素ガス吸着法により測定し得られた値である。
本明細書において「TiO2を含」むとは、TiO2を単独で含有する場合と、Tiが他の元素とともに複合酸化物を形成している場合と、TiO2を混合物として含有する場合のいずれをも含む概念である。
本発明の脱硝触媒用担体はハニカム構造を有しており、中でも、反応流路として複数の貫通孔を有するハニカム構造体であることが好ましい。このような脱硝触媒用担体として、例えば図1に示されるような担体が挙げられるが、これに限定されるものではない。ハニカム構造は、断面が矩形のものに限定されず、例えば、円状、楕円状、三角形、五角形、六角形等の断面を有していてもよい。
Tiのほかに2種以上の元素Mを含む複合酸化物とする場合、TiとSiとをベースとしてその他の元素を加えることが好ましい。2種以上の元素Mを含有する場合も、その比表面積に応じて1種の元素を組み合わせたときと同等かさらにAs被毒耐性を向上させた担体を得ることができる。
Siアルコキシドは、一般式Si(OR2)4(Rは炭素数1〜20、好ましくは1〜5のアルキル基)で表され、例えば、Si(OCH3)4、Si(OC2H5)4、Si(O−isoC3H7)4、Si(O−tertC4H9)4等があげられる。
Pアルコキシドとしては、例えば、P(OCH3)3、PO(OCH3)3等が挙げられる。
Bアルコキシドとしては、例えば、B(OCH3)3、B(OC2H5)3等が挙げられる。
Zrアルコキシドとしては、例えば、Zr(OCH3)4、Zr(OC2H5)4、Zr(O−nC3H7)4、Zr(O−isoC3H7)4、Zr(O−nC4H9)4等が挙げられる。
Wアルコキシドは、一般式W(OR)6(Rは炭素数1〜20、好ましくは1〜5のアルキル基)で表され、例えば、W(OCH3)4、W(OC2H5)4、W(O−isoC3H7)4、W(O−tertC4H9)4等があげられる。
混合液を所望により中和し沈殿物を得た後、さらに5分以上、望ましくは2時間以上攪拌して熟成させる。熟成は加水分解と同程度の温度で行うことが望ましい。すなわち、熟成温度は50℃以上が好ましく、80〜100℃がより好ましい。熟成により、新たに酸素原子を介した異種の担体元素同士の結合及び比表面積が増加する。
本発明の担体は、上述したゾルゲル法以外に、従来公知の共沈法により製造されたものであってもよい。
(比較用担体1の調製)
337.6gのTi源であるTi(O−iC3H7)4に80℃の水4.4リットルを添加して加水分解し、さらに2時間、同温度の水中で攪拌して熟成させた。生成したゾルをろ過し、生成したアルコールを充分に洗浄し乾燥させた後、500℃で5時間加熱して焼成した。
100重量部のTiO2に対して、メタバナジン酸アンモニウム(NH4VO3)とパラタングステン酸アンモニウム{(NH4)10W12O41・5H2O}をV2O5は5重量部、WO3は8重量部となるように10wt%メチルアミン水溶液に溶解し、TiO2粉末に含浸させて乾燥後、500℃で5時間焼成し触媒粉末を得た。
この触媒粉末100重量部に対して、バインダとしてグラスファイバを3重量部、カオリンを3重量部、さらに有機可塑剤として酢酸セルロースを3重量部とアンモニア水溶液を添加して混練した。この混練物を押出成型し、乾燥後500℃で5時間焼成することにより、格子間隔(S)7.5mm、壁厚(T)1.0mmの比較用ハニカム成型担体を得た(図1参照)。
(一体型ハニカム成型担体1〜9の調製)
Ti源であるTi(O−iC3H7)4とSi源であるSi(OCH3)3、P源であるP(OCH3)3、B源であるB(OCH3)3、Zr源であるZr(OCH3)4、および/または、W源であるパラタングステン酸アンモニウム{(NH4)10W12O41・5H2O}とを、各元素の酸化物の配合比に換算して表3に示す配合比となるように所定量混合し80℃の水に添加して加水分解し、さらに2時間、同温度の水中で攪拌して熟成させた。生成したゾルをろ過し、生成したアルコールを充分に洗浄し乾燥させた後、500℃で5時間加熱して焼成し二成分系または三成分系の各複合酸化物1〜9を得た。
100重量部の複合酸化物1〜9に対して、メタバナジン酸アンモニウム(NH4VO3)とパラタングステン酸アンモニウム{(NH4)10W12O41・5H2O}をV2O5は5重量部、WO3は8重量部となるように10wt%メチルアミン水溶液に溶解し、複合酸化物粉末に含浸させて乾燥後、500℃で5時間焼成し触媒粉末を得た。
この触媒粉末100重量部に対して、バインダとしてグラスファイバを3重量部、カオリンを3重量部、さらに有機可塑剤として酢酸セルロースを3重量部とアンモニア水溶液を添加して混練した。この混練物を押出成型し、乾燥後500℃で5時間焼成することにより、格子間隔(S)7.5mm、壁厚(T)1.0mmの一体型ハニカム成型担体1〜9を得た(図1参照)。
メタバナジン酸アンモニウム(NH4VO3)3.9gとパラタングステン酸アンモニウム{(NH4)10W12O41・5H2O}9.0gを10wt%メチルアミン水溶液55ミリリットルに溶解し、前述のTiO2,または、複合酸化物1〜9の粉末それぞれ89.0gに含浸させて乾燥後、500℃で5時間焼成し、前記担体に3wt%のV2O5及び8wt%のWO3を担持させた触媒粉を得た。得られたV2O5及びWO3を含有する触媒20重量部に対して水80重量部を加え、ボールミルで充分攪拌し、ウォッシュコート用スラリとした。該ウォッシュコート用スラリに前述の一体型ハニカム成型担体を浸漬し、取り出した後、余分なスラリを吹きはらい200℃で乾燥させた、コート量は基材1リットル(見かけ容量)あたり50gとし、このコート物を比較用ハニカム触媒およびハニカム触媒1〜9とした。
劣化度は、Asを200ppm含むサンプルガスを比較用ハニカム触媒およびハニカム触媒1〜9に1時間導通した前後での脱硝率の低減率を示したものであり、下記式(1)および(2)で評価した。
劣化度=(As導通後脱硝率)/(初期脱硝率) 式(1)
(脱硝率)=[(入口NOx−出口NOx)/入口NO]×100 式(2)
また、TiO2をベースとする三成分系(実施例5〜9)においても比表面積の増大が図られることで二成分系(実施例1〜4)と同様にAs負荷後の劣化を抑制できることがわかった。
さらに図2に示すように、複合酸化物が、二成分系であるか三成分系であるかもしくは複合元素の種類によらず、比表面積と劣化度との間に相関が見られることがわかった。
T 壁厚
Claims (7)
- TiO2を含み、ハニカム構造を有し、さらにSi、B、P、Zr及びWからなる群より選択される1種または2種以上の元素を含有する複合酸化物であり、且つその比表面積が100m2/gを超える、Asを含む石炭焚ボイラ排ガス用の脱硝触媒用担体。
- 前記担体中のTiO2の重量と前記元素の酸化物であるSiO2、B2O3、P2O5、ZrO2及びWO3の合計重量との重量比は、50:50〜99:1の範囲内であることを特徴とする請求項1に記載のAsを含む石炭焚ボイラ排ガス用の脱硝触媒用担体。
- 前記担体が、共沈法またはゾルゲル法により製造されたものであることを特徴とする請求項1または2に記載のAsを含む石炭焚ボイラ排ガス用の脱硝触媒用担体。
- 前記担体の比表面積は160m2/g以下であることを特徴とする請求項1から3の何れか一項に記載のAsを含む石炭焚ボイラ排ガス用の脱硝触媒用担体。
- 前記担体のハニカム構造は、反応流路として複数の貫通孔を有し、その断面が円状、楕円状、三角形、五角形及び六角形の何れかであることを特徴とする請求項1から4の何れか一項に記載のAsを含む石炭焚ボイラ排ガス用の脱硝触媒用担体。
- 請求項1から5の何れか一項に記載の前記担体に、V2O5、WO3及びMоO3からなる群より選択される1種以上の脱硝活性金属を担持させてなることを特徴とするAsを含む石炭焚ボイラ排ガス用の脱硝触媒。
- 請求項6に記載の前記Asを含む排ガス用の脱硝触媒を備えたAsを含む石炭焚ボイラ排ガス用の脱硝装置。
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