TWI516304B - Exhaust denitrification catalyst and its manufacturing method - Google Patents

Exhaust denitrification catalyst and its manufacturing method Download PDF

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TWI516304B
TWI516304B TW100132245A TW100132245A TWI516304B TW I516304 B TWI516304 B TW I516304B TW 100132245 A TW100132245 A TW 100132245A TW 100132245 A TW100132245 A TW 100132245A TW I516304 B TWI516304 B TW I516304B
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Taiwan
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catalyst
salt
zeolite
titanium oxide
phosphoric acid
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TW100132245A
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TW201223624A (en
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Yasuyoshi Kato
Seiji Ikemoto
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Mitsubishi Hitachi Power Sys
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Description

排氣脫硝觸媒及其製造方法
本發明有關排氣脫硝觸媒(exit gas denitrating catalyst)及其製造方法，特別是有關因燃燒排氣中所含之砷(As)、磷(P)、鉀(K)等觸媒毒物(catalyst poison)所引起之劣化較低，且經大幅提升在350℃以上的脫硝性能(denitrating ability)之氨觸媒還原(ammonia catalytic reduction)用排氣脫硝觸媒及其製造方法。
以氧化鈦作為主成分之氨觸媒還原用脫硝觸媒，係因活性較高且耐久性優異之故，在國內外廣用為鍋爐(boiler)等的排煙處理(flue gas treatment)，而成為脫硝觸媒之主流(專利文獻1)。
近年來，能源需求急增之結果，開始採用磺黃成份高的煤碳(高S(硫)炭)或PRB炭(高磷瀝青炭(phosphorus rich bituminous coal))、或者生質(biomass)等種種燃料，隨著，在使用時的排煙脫硝觸媒的劣化亦產生多種形態。其代表性者，可例舉：因燃燒高S炭時發生之砷(As)化合物所引起之劣化，因燃燒PRB炭之排氣中容易發生之磷(P)化合物所引起之劣化，因燃燒生質之排氣中發生之鉀(K)化合物所引起之劣化。此種均為因累積性(accumulative)的觸媒毒所引起的劣化，一般周知，累積在觸媒後即會短期間內引起大幅度的脫硝性能的低落之事實。
針對此等問題，本申請案發明人等，已發明一種能防止上述毒物吸附‧累積於氧化鈦之Ti-V-Mo-P系的觸媒並已提出申請(未公告專利文獻2)。
[先前技術文獻]
[專利文獻]
專利文獻1：日本專利特開昭50-128681號公報
專利文獻2：日本專利特願2010-026577號公報
有關上述先前申請案之觸媒，係不僅對As、P、K化合物具有高的耐久性、尚具有SO2(二氧化硫)氧化率較低、Hg(汞)氧化活性較高等種種優點者，但唯一需要改善之處，係當反應溫度從350℃上升為400℃時的脫硝性能的上升度較通常的觸媒為小之處。燃燒高S炭之鍋爐的排煙脫硝作業多在400℃附近的溫度，故如能改善在上述之400℃時的脫硝性能，則必定能成為更優異的觸媒。
本申請案發明所欲解決之課題，在於提供一種在不致損及Ti-V-Mo-P系觸媒的優異的耐久性之下能改善於350℃以上之脫硝率，且性能‧耐久性優異的觸媒。
有關上述先前申請案之未周知的觸媒，係根據使屬於觸媒毒的一種之磷酸吸附於氧化鈦所具有之觸媒毒的吸附點(adsorption point)、以阻止源自排氣之觸媒毒對觸媒的吸附藉以防止劣化之想法所產生者。於該磷酸所吸附之點，亦吸附有屬於活性成分之V(釩)、屬於助觸媒成分(promotor component)之Mo(鉬)或W(鎢)等的氧化物，其結果，觸媒上(亦即，氧化鈦上)的吸附點，即被此等成分所完全覆蓋。其結果，來自排氣的觸媒毒的吸附會大幅度減少，惟另一方面，卻有NH3(氨)的吸附點的減少、及吸附力的減弱等的副作用。其結果，NH3的吸附量在高溫下減少，即使溫度上升至350℃以上，仍然難於提升脫硝性能，以致會發生達到不能再高之現象。
本申請案發明人等，為改善該缺點起見，雖然設想不吸附As、P等觸媒毒而強烈吸附NH3之成分之添加‧補充之作法，並採用多種化學物質加以研究，惟均吸附觸媒成分中的P化合物、或排氣中的P或As化合物後喪失NH3吸附性能，以致未能使用，惟獨高二氧化矽沸石(high silica zeolite)的情形則獲得顯著的改善效果，終於完成本發明。
為達成上述課題起見，本申請案中所申請專利之發明，係如下所述。
(1)一種排氣脫硝觸媒，係由鈦(Ti)、磷(P)的氧化物，及鉬(Mo)及/或鎢(W)，以及釩(V)氧化物，與SiO2/Al2O3比值在20以上的高二氧化矽沸石所成之觸媒組成物，其特徵為：將(1)氧化鈦，及對氧化鈦以H3PO4 計為超過1且在15wt%以下的磷酸或磷酸的銨鹽，及(2)對氧化鈦分別為超過0且在8atom%以下的鉬(Mo)及/或鎢(W)的含氧酸或含氧酸鹽及釩(V)的含氧酸鹽或釩基鹽(vanadyl salt)，以及(3)對氧化鈦為超過0且在20wt%以下的高二氧化矽沸石，在水的存在下加以混練、乾燥、燒成者。
(2)如(1)記載之脫硝觸媒，其中高二氧化矽沸石為絲光沸石(mordenite)。
(3)一種排氣脫硝觸媒之製造方法，其特徵為：預先在水的存在下使氧化鈦、與磷酸或磷酸的銨鹽相接觸以於氧化鈦表面使磷酸離子吸附後，添加鉬(Mo)及/或鎢(W)的含氧酸或含氧酸鹽，及釩(V)的含氧酸鹽或釩基鹽、及高二氧化矽沸石，在水的存在下加以混練、乾燥、燒成。
如採用本發明，則能提升耐久性高的觸媒成分在350℃以上的脫硝性能，以實現高活性且高耐久性的脫硝觸媒。其結果，能減少美國等，多在400℃附近運轉之為來自燃燒高S媒燃燒高S炭鍋爐之排氣脫硝裝置所使用之觸媒使用量以使裝置作成小型(compact)。
沸石具有多數10Å(埃厘米)以下的細孔，而其內部具有能強烈吸附NH3之優異的吸附點。如該吸附點被觸媒成分或排氣中的毒成分所破壞時則不能發揮添加效果，惟所幸，在觸媒調製階段時，Mo、V、W、P成分係作成其含氧酸鹽所添加，且由於其等離子係較10Å為大之故， 在觸媒調製階段時，沸石上的NH3吸附處(adsorption site)能維持為完好。又，排氣中的As或P的化合物，係作成所相當之氧化物的蒸氣而飛來，惟由於其大小亦較10Å為大之故不致於進入細孔內，而使用時仍能維持NH3的吸附點。
如此，沸石細孔內的NH3吸附點，能維持在觸媒調製階段，以及使用階段的整個期間當中，並能補充當觸媒在使用溫度超過350℃使用之情形所發生之Ti-Mo-V-P成分的NH3吸附量的減少以維持高的脫硝性能。
本發明，如上所述，係在調製階段及使用階段之整個期間當中，由於能從P或活性成分的含氧酸鹽類保護NH3的吸附點之沸石、與耐久性高的觸媒成分的搭配之結果，始能達成之劃時代的觸媒。
[發明之最佳實施形態]
如上所述，本發明之觸媒，係藉由採用吸附有磷酸離子之TiO2以防止觸媒毒對觸媒的侵犯，同時利用沸石成分以維持NH3的吸附點等兩種成分的協調作用而始能實現者，故需要考慮下列各點。
能被氧化鈦所吸附之PO4離子，係TiO2的每表面積為約0.05wt%，於通常所使用之100至300m2/g的TiO2原料中，5至15wt%係能吸附之最大量，故如超此以上時則缺少能吸附NH3之OH基，以致引起大幅度的活性低落。因此，雖因TiO2原料的種類而有所不同，通常H3PO4的添加量作成TiO2的15wt%以下，較佳為作成 10wt%以下時即能使耐久性及脫硝活性兩全而容易獲得好結果。又，添加量的低限並無限定，惟為能顯示顯著的抗毒性起見，較佳為對TiO2選定為1wt%以上。
與吸附有磷酸離子之TiO2搭配之活性成分而言，能使用鉬(Mo)及或/鎢(W)的含氧酸或含氧酸鹽及釩(V)的含氧酸鹽或釩基鹽，而其添加量並不特別加以限制，惟可對TiO2各選定為0以上8atom%以下。如TiO2原料的比表面積大時選定高值、比表面積小時即選定低值，則可作成脫硝性能為高、SO2(二氧化硫)的氧化性能為低之故很合適。此等活性成分的添加方法可採取任何方法，惟在水的存在下混練或加熱混練之方法為較符合經濟性而優異。
為與上述觸媒成分搭配之沸石成分，較佳為SiO2/Al2O3比值在20以上的絲光沸石或五輪(pentacyl)型沸石(ZSM-5)，在SiO2/Al2O3比值在20以上、30以下時容易獲得好結果。如該比值過小時，則會被排氣中或觸媒成分中的S分破壞構造，如過高時，則NH3的活性點減少以致難於獲得高的活性提升率。
載持活性成分後的觸媒成分，係除依周知的方法成型為蜂窩(honeycomb)狀使用之外，尚可作成經加工為網狀之金屬基板或陶瓷纖維的網狀物中按填補篩孔之方式塗佈而使其板狀化後將經成型間隔部為波浪型等者層壓之構造體使用。特別是由於後者係含有鉀化合物之灰不易堆積於觸媒間之故容易獲得好結果。
再者，亦能實施本身為與本發明無直接關係之為成型之用的黏合劑(binder)之矽石溶膠(silicasol)等黏合劑，以強化作為目的之無機纖維的添加，其結果所得之觸媒當然亦屬於本發明之範圍內。
以下，將採用具體例以詳細說明本發明內容。
[實施例1]
將氧化鈦(石原產業社製，比表面積290m2/g)900g、85%磷酸84.5g、矽石溶膠(日產化學社製、商品名OS溶膠)219g、以及水5568g置入揑合機(kneader)並混練45分鐘，以使磷酸吸附於TiO2表面。對此添加鉬酸銨113g、偏釩酸銨105g，H型絲光沸石(東曹社製、商品名TSZ-650、SiO2/Al2O3比值=23)90g後再混練1小時，以使Mo與V的化合物載持於吸附有磷酸之TiO2表面。然後，在徐徐添加矽石鋁氧系陶瓷纖維(東芝精密花線(fine flex)社製)151g之下混練30分鐘，製得均勻的漿糊(paste)狀物。將所得漿糊置放於經將厚度0.2mm的SUS(不銹鋼)430製鋼板金屬網(metal lath)加工之厚度0.7mm的基材上，將此夾在兩片聚乙烯片材並經過加壓輥輪，按填補金屬網基材的篩孔之方式加以塗佈。將此風乾後，在500℃下燒成2小時，製得觸媒。本觸媒的組成為Ti/Mo/V=88/5/7原子比，而H3PO4添加量、及沸石添加量，係對TiO2各為8wt%及10wt%。
[實施例2及3]
除於實施例1中，將磷酸添加量分別變更為10.6g及42.4g以外，其餘則按與實施例1同樣方式調製觸媒。
[實施例4]
除於實施例1中，將磷酸的添加量變更為159g，將偏釩酸銨的添加量變更為121g，以及將H型絲光沸石變更為東曹社製、商品名TSZ-640(SiO2/Al2O3=22)180g以外，其餘則與實施例1同樣方式調製觸媒。本觸媒的組成為Ti/Mo/V=88/5/8原子比，H3PO4及沸石添加量，係對TiO2各為15wt%及20wt%。
[實施例5及6]
除將實施例1所用之氧化鈦變更為比表面積90m2/g的氧化鈦之同時，將觸媒的磷酸添加量對TiO2變更為4wt%、再將偏釩酸銨及鉬酸銨，變更為分別6.8g及61.8g、以及27.7g及62.7g、將H型絲光沸石變更為東曹社製、商品名TSZ-660(SiO2/Al2O3=31)27g以外，其餘則按與實施例1同樣方式調製觸媒。本觸媒之組成為，Ti/Mo/V=96.5/3/0.5原子比及95/3/2原子比，H3PO4及沸石添加量，係對TiO2分別為4wt%及3wt%。
[實施例7]
除將實施例1的觸媒所用之鉬酸銨113g變更為偏鎢酸銨162g，將H型絲光沸石的添加量變更為9g以外，其餘則按與實施例1同樣方式調製觸媒。本觸媒之組成為Ti/W/V=88/5/7原子比，H3PO4及沸石添加量，係對TiO2分別為8wt%及1wt%。
[比較例1至7]
除於實施例1至7中，不實施沸石的添加以外，其餘則作成同樣方式以調製觸媒。
[比較例8至11]
除於實施例1、5至7中，不實施磷酸的添加-吸附處理以外，其餘則作成同樣方式以調製觸媒。
[試驗例1]
將實施例1至7及比較例1至7的觸媒裁成寬20mm×長100mm，並依表1的條件測定各觸媒之脫硝性能。將所得結果綜合表示於表2中。
表2中，如進行本發明之實施例的觸媒的性能與比較例的觸媒的性能之比較時發現，在350℃下時兩者的差較小，惟在400℃下則依實施例之觸媒的性能顯著性較高，可知係經改善350℃以上的脫硝性能之優異的觸媒之事實。
[試驗例2及3]
為明確顯示本申請案發明之觸媒的優異之處起見，將實施例1、5至7以及比較例8至17的觸媒裁成寬20mm×長100mm，並將碳酸鉀的水溶液對觸媒成分以K2O計按能成為0.5wt%添加之方式含浸後在150℃下乾燥以進行模擬因生質燃燒灰中所含之鉀化合物所引起之劣化之試驗。
另外，於實施例1、5至7以及比較例8至17的觸媒中將亞砷酸的水溶液對觸媒成分按AS2O3能成為2wt%之方式含浸後在350℃下燒成1小時以實施模擬於高S碳排氣中之劣化之試驗。
就上述2種模擬試驗後的觸媒及模擬試驗前的觸媒，依表3的條件測定脫硝性能，以評價各觸媒的抗毒性。將所得結果，綜合表示於表4中。
於表4中，如進行實施例與比較例的各觸媒的性能之比較時發現，依本申請案發明之實施例之觸媒係因鉀及砷化合物所引起之劣化極小，可知係耐久性優異之事實。
從本結果與先前所示之試驗例的結果可知，本發明之觸媒係不僅在350℃以上的高溫特性優異，尚具有不易因K、As等的觸媒毒所引起之劣化之特徵之優異的觸媒之事實。

Claims (3)

  1. 一種排氣脫硝觸媒，係由鈦(Ti)、磷(P)的氧化物，及鉬(Mo)及/或鎢(W)，以及釩(V)氧化物，與SiO2/Al2O3比值在20以上的高二氧化矽沸石所成之觸媒組成物，其特徵為：將(1)氧化鈦、及對氧化鈦而言以H3PO4計為超過1且在15wt%以下的磷酸或磷酸之銨鹽，及(2)對氧化鈦而言分別為超過0且在8 atom%以下的鉬(Mo)及/或鎢(W)的含氧酸或含氧酸鹽及釩(V)的含氧酸鹽或釩基鹽，以及(3)對氧化鈦而言為超過0且在20wt%以下的高二氧化矽沸石，在水的存在下加以混練、乾燥、燒成者。
  2. 如申請專利範圍第1項之脫硝觸媒，其中高二氧化矽沸石為絲光沸石。
  3. 一種排氣脫硝觸媒之製造方法，其特徵為：預先在水的存在下使氧化鈦與磷酸或磷酸之銨鹽接觸以於氧化鈦表面使磷酸離子吸附後，添加鉬(Mo)及/或鎢(W)的含氧酸或含氧酸鹽，及釩(V)的含氧酸鹽或釩基鹽，及高二氧化矽沸石，在水的存在下加以混練、乾燥、燒成。
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EP2614886B1 (en) 2021-06-16
TW201223624A (en) 2012-06-16
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EP2614886A4 (en) 2017-09-06
CN103025428B (zh) 2016-08-03
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WO2012033039A1 (ja) 2012-03-15
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