CN107847862A - Nh3过量剂量耐受的scr催化剂 - Google Patents
Nh3过量剂量耐受的scr催化剂 Download PDFInfo
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- CN107847862A CN107847862A CN201680042218.0A CN201680042218A CN107847862A CN 107847862 A CN107847862 A CN 107847862A CN 201680042218 A CN201680042218 A CN 201680042218A CN 107847862 A CN107847862 A CN 107847862A
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- scr catalyst
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- scr
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Abstract
公开了催化剂,其具有低氨储存量的载体载铂与Cu‑SCR催化剂或Fe‑SCR催化剂的共混物。催化剂还可以包含一种或两种另外的SCR催化剂。催化剂可以以多种构造中的一种存在。公开了包含这些催化剂的催化制品。催化制品可用于废气气体中NOx的选择性催化还原(SCR)和降低氨逸出量。描述了用于生产这样的制品的方法。还描述了将催化制品用于SCR工艺的方法,其中氨逸出量降低。
Description
发明领域
本发明涉及用于选择性催化还原(SCR)的催化剂、包含SCR催化剂的制品和制造这样的制品和使用这样的制品来减少氮氧化物(NOx)的方法。
本发明的背景技术
柴油发动机、固定式燃气轮机和其它系统中烃燃烧产生了废气气体,所述废气气体需要处理以除去氮氧化物(NOx),所述废气气体包含NO(一氧化氮)和NO2(二氧化氮),NO为所形成的NOx的主要部分。已知的是NOx导致多种人体健康问题,以及导致多种有害的环境影响,包括形成雾霾和酸雨。为了缓解来自废气气体中NOx的人类和环境影响,期望的是消除这些不期望的组分,其优选通过不产生其它有害或有毒物质的方法。
本发明涉及通过在包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物的催化剂的存在下使氮氧化物与含氮还原剂接触,将气体(例如车辆贫燃内燃发动机的废气气体)中的氮氧化物转化成氮气的方法。
由含氮化合物,例如氨或尿素选择性催化还原(SCR)NOx首先被开发用于处理工业固定应用。SCR技术首先在1970年代晚期在日本用于热电厂,并且从1980年代中期以来广泛应用于欧洲。在美国,在1990年代将SCR系统引入用于燃气轮机并且在更近期已经用于燃煤电厂。除了燃煤废热发电厂和燃气轮机,SCR应用还包括化学处理工业中的锅炉和精炼厂加热器和设施、炉、焦炭炉、城市废物设施和焚烧炉。在更近期,在欧洲、日本和美国,研发了基于SCR技术的NOx还原系统用于多种车辆(机动)应用,例如用于处理柴油废气气体。
NH3SCR系统中发生若干化学反应,其全部代表将NOx还原成氮气的期望的反应。主导反应由反应(1)代表。
4NO+4NH3+O2→4N2+6H2O(1)
与氧竞争性的非选择性反应可能产生次级排放物或可能非生产性地消耗氨。一种这样的非选择性反应是氨的完全氧化,显示在反应(2)中。
4NH3+5O2→4NO+6H2O(2)
而且,副反应可能导致不期望的产物例如N2O,如由反应(3)代表的。
4NH3+5NO+3O2→4N2O+6H2O(3)
期望的是具有这样的催化剂,其提供了增加的氮气(N2)收率和减少的N2O形成。
发明内容
在一个方面中,本发明涉及催化制品,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。
在另一方面,本发明涉及催化制品,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层叠覆第一涂层沿入口至出口的轴的长度的至少20%。
在另一方面,本发明涉及包含催化制品和用于转化废气气体中NOx和NH3的装置的废气系统,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。
在又一方面,本发明涉及包含催化制品和用于转化废气气体中NOx和NH3的装置的废气系统,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层叠覆第一涂层沿入口至出口的轴的长度的至少20%。
在又另一方面,本发明涉及用于改善在约200℃-约350℃的温度下的来自废气气体中的氨的N2收率的方法,所述方法包括使包含氨的废气气体与催化制品接触,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。
在又一方面,减少由废气气体中的NOx和NH3形成的N2O的方法,所述方法包括使包含氨的废气气体与催化制品接触,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。
在进一步的方面中,处理包含NH3和NOx的废气气体的方法,所述方法包括使包含氨的废气气体与催化制品接触,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。
附图说明
图1(a)为这样的图,其显示%NO转化率,使用实施例1-5,使用100ppm NO,100ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图1(b)为这样的图,其显示N2O形成的量,使用实施例1-5,使用100ppm NO,100ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图1(c)为这样的图,其显示%NH3转化率,使用实施例1-5,使用100ppm NO,100ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图1(d)为这样的图,其显示%的N2收率,使用实施例1-5,使用100ppm NO,100ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图2(a)为这样的图,其显示%NO转化率,使用实施例1-5,使用100ppm NO,100ppm或140ppm NH3(ANR=1.0或1.4),10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=60,000h-1下。
图2(b)为这样的图,其显示N2O形成的量,使用实施例1-5,使用100ppm NO,100ppm或140ppm NH3(ANR=1.0或1.4),10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=60,000h-1下。
图2(c)为这样的图,其显示%NH3转化率,使用实施例1-5,使用100ppm NO,100ppm或140ppm NH3(ANR=1.0或1.4),10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=60,000h-1下。
图2(d)为这样的图,其显示%的N2收率,使用实施例1-5,使用100ppm NO,100ppm或140ppm NH3(ANR=1.0或1.4),10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=60,000h-1下。
图3(a)为这样的图,其显示%NO转化率,使用系统1-4,使用300ppm NO,500ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图3(b)为这样的图,其显示N2O形成的量,使用系统1-4,使用300ppm NO,500ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图3(c)为这样的图,其显示%NH3转化率,使用系统1-4,使用300ppm NO,500ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
图3(d)为这样的图,其显示%的N2收率,使用系统1-4,使用300ppm NO,500ppmNH3,10%的O2,4.5%的CO2,4.5%的H2O,余量N2,在SV=120,000h-1下。
发明详述
如本说明书和所附权利要求中使用的,单数形式的“a”、“an”和“the”包括多数多数指示物,除非上下文清楚地另有指示。因此,例如,对“催化剂”的引述包括两种或更多种催化剂的混合物,等等。
如本文所用的,术语“氨逸出”,意为穿过SCR催化剂的未反应的氨的量。
术语“具有低氨储存量的载体”意为储存小于0.001mmol NH3/m3载体的载体。具有低氨储存量的载体优选为骨架类型选自以下的分子筛或沸石:AEI、ANA、ATS、BEA、CDO、CFI、CHA、CON、DDR、ERI、FAU、FER、GON、IFR、IFW、IFY、IHW、IMF、IRN、IRY、ISV、ITE、ITG、ITN、ITR、ITW、IWR、IWS、IWV、IWW、JOZ、LTA、LTF、MEL、MEP、MFI、MRE、MSE、MTF、MTN、MTT、MTW、MVY、MWW、NON、NSI、RRO、RSN、RTE、RTH、RUT、RWR、SEW、SFE、SFF、SFG、SFH、SFN、SFS、SFV、SGT、SOD、SSF、SSO、SSY、STF、STO、STT、SVR、SVV、TON、TUN、UOS、UOV、UTL、UWY、VET、VNI。更优选地,分子筛或沸石的骨架类型选自BEA、CDO、CON、FAU、MEL、MFI和MWW,甚至更优选骨架类型选自BEA和MFI。
如本文所用的,术语“煅烧(calcine)”,或“煅烧(calcination)”,意为在空气或氧气中加热材料。该定义与煅烧的IUPAC定义一致。(IUPAC.Compendium of ChemicalTerminology,2nd ed.(the"Gold Book")。A.D.McNaught和A.Wilkinson编译。BlackwellScientific Publications,Oxford(1997)。XML在线更正版本:http://goldbook.iupac.org(2006-),M.Nic,J.Jirat,B.Kosata生成;A.Jenkins编译更新。ISBN0-9678550-9-8。doi:10.1351/goldbook)。进行煅烧以将金属盐分解并且促进催化剂内的金属离子交换并且还将催化剂粘附至基材。煅烧中使用的温度取决于待煅烧的材料中的组分并且通常为约300℃-约900℃,持续大约1-8小时。在一些情况下,煅烧可以进行至最高约1200℃的温度。在涉及本文描述的方法的应用中,煅烧通常在约400℃-约700℃的温度下进行大约1-8小时,优选在约400℃-约650℃的温度下进行大约1-4小时。
如本文所用的,术语“约”意为大约并且指的是所关联术语的值的任选±25%,优选±10%,更优选地,±5%,或最优选±1%。
在就各种数值要素提供的一个或多个范围时,所述一个或多个范围可以包括值,除非另有规定。
如本文所用的,术语“N2选择性”意为氨到氮气的百分比转化率。
在本发明的一个方面中,催化剂包含具有低氨储存量的载体载铂与第一SCR催化剂的组合。具有低氨储存量的载体载铂与第一SCR催化剂的组合为(a)具有低氨储存量的载体载铂与第一SCR催化剂的共混物,或(b)双层,其具有包含第一SCR催化剂的顶部层和包含具有低氨储存量的载体载铂的底部层,其中底部层可以置于基材上。具有低氨储存量的载体可以为含硅载体,其中含硅载体可以包含二氧化硅或二氧化硅与氧化铝的比例为至少以下之一的沸石:≥100,≥200,≥250,≥300,≥400,≥500,≥750和≥1000。在本发明的各方面,第一SCR催化剂优选为Cu-SCR催化剂或Fe-SCR催化剂,更优选Cu-SCR催化剂。
共混物中第一SCR催化剂的量与具有低氨储存量的载体载铂的量的比例可以为3:1-300:1(包括端值),基于这些组分的重量计。共混物中第一SCR催化剂的量与具有低氨储存量的载体载铂的量的优选比例为7:1-100:1(包括端值),基于这些组分的重量计。更优选地,共混物中第一SCR催化剂的量与具有低氨储存量的载体载铂的量的比例为10:1-50:1(包括端值),基于这些组分的重量计。
术语“活性组分载量”是指共混物中铂的载体的重量+铂的重量+第一SCR催化剂的重量。铂可以以约0.01-约0.25wt%(包括端值)的活性组分载量存在于催化剂中。优选地,铂可以以0.04-0.2wt%(包括端值)的活性组分载量存在于催化剂中。更优选地,铂可以以0.07-0.17wt%(包括端值)的活性组分载量存在于催化剂中。最优选地,铂可以以0.05-0.15wt%(包括端值)的活性组分载量存在于催化剂中。
SCR催化剂
在各种实施方案中,组合物可以包含一种、两种或三种SCR催化剂。第一SCR催化剂,其总是存在于组合物中,可以存在于:(1)与具有低氨储存量的载体载Pt的共混物中或(2)顶部层中(在催化剂存在于双层中并且Pt存在于底部层中时)。第一SCR催化剂优选为Cu-SCR催化剂或Fe-SCR催化剂,更优选Cu-SCR催化剂。Cu-SCR催化剂包含铜和分子筛。Fe-SCR催化剂包含铁和分子筛。分子筛进一步描述如下。铜或铁可以位于分子筛的骨架内和/或分子筛内的骨架外(可交换)位点中。
第二和第三SCR催化剂可以相同或不同。第二和第三SCR催化剂可以为贱金属的氧化物、分子筛、经金属交换的分子筛或其混合物。贱金属可以选自钒(V)、钼(Mo)和钨(W)、铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu),及其混合物。由耐火金属氧化物(例如氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈及其组合)上负载的钒组成的SCR组合物是公知的并且广泛地在商业上用于机动应用中。典型的组合物描述在美国专利号4,010,238和4,085,193中,其全部内容以引用方式并入本文。商业上尤其是移动应用中使用的组合物包含TiO2、WO3和V2O5分别以5-20wt%和0.5-6wt%的浓度分散在其上。第二SCR催化剂可以包含促进的-Ce-Zr或促进的-MnO2。这些催化剂可以包含其它无机材料例如SiO2和ZrO2,其充当粘合剂和促进剂。
在SCR催化剂为贱金属或混合的贱金属氧化物时,催化剂制品可以进一步包含至少一种贱金属促进剂。如本文所用的,“促进剂”理解意为在添加至催化剂中时增加催化剂活性的物质。贱金属促进剂可以为金属、金属氧化物或其混合物的形式。至少一种贱金属催化剂促进剂可以选自钕(Nd)、钡(Ba)、铈(Ce)、镧(La)、镨(Pr)、镁(Mg)、钙(Ca)、锰(Mn)、锌(Zn)、铌(Nb)、锆(Zr)、钼(Mo)、锡(Sn)、钽(Ta)、锶(Sr)及其氧化物。至少一种贱金属催化剂促进剂可以优选为MnO2、Mn2O3、Fe2O3、SnO2、CuO、CoO、CeO2及其混合物。至少一种贱金属催化剂促进剂可以以水溶液中的盐(例如硝酸盐或乙酸盐)的形式添加至催化剂。至少一种贱金属催化剂促进剂和至少一种贱金属催化剂(例如,铜)可以从水溶液浸渍至(一种或多种)氧化物载体材料上,可以添加至包含(一种或多种)氧化物载体材料的载体涂层中,或可以浸渍至先前用载体涂层涂覆的载体上。
SCR催化剂可以包含分子筛或经金属交换的分子筛。如本文使用的,“分子筛”理解意为包含精准和均一尺寸的孔,可以作为吸附剂用于气体或液体的亚稳定材料。小到足以穿过孔的分子被吸附,而较大的分子不被吸附。分子筛可以为沸石分子筛、非沸石分子筛或其混合物。
沸石分子筛为具有International Zeolite Association(IZA)发布的Databaseof Zeolite Structures中列出的骨架结构的任何一种的微孔硅铝酸盐。骨架结构包括但不限于CHA、FAU、BEA、MFI、MOR类型的那些。具有这些结构的沸石的非限定性实例包括菱沸石、八面沸石、沸石Y、超稳定沸石Y、β沸石、丝光沸石、硅质岩、沸石X和ZSM-5。硅铝酸盐沸石可以具有至少约5,优选至少约20的二氧化硅/氧化铝摩尔比例(SAR)(定义为SiO2/Al2O3),有用的范围为约10-200。
SCR催化剂的任一种可以包含小孔、中孔或大孔分子筛或其组合。“小孔分子筛”为包含8个四面体原子的最大环尺寸的分子筛。“中孔分子筛”为包含10个四面体原子的最大环尺寸的分子筛。“大孔分子筛”为包含12个四面体原子的最大环尺寸的分子筛。第二和/或第三SCR催化剂可以包含小孔分子筛选自硅铝酸盐分子筛、金属-取代硅铝酸盐分子筛、铝磷酸盐(AlPO)分子筛、金属-取代铝磷酸盐(MeAlPO)分子筛、硅铝磷酸盐(SAPO)分子筛和金属取代硅铝磷酸盐(MeAPSO)分子筛,及其混合物。
SCR催化剂的任一种可以包含小孔分子筛,所述小孔分子筛选自以下骨架类型:ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SFW、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON,及其混合物和/或共生物。优选小孔分子筛选自以下骨架类型:CHA,LEV,AEI,AFX,ERI,SFW,KFI,DDR和ITE。
SCR催化剂的任一种可以包含中孔分子筛,所述中孔分子筛选自以下骨架类型:AEL、AFO、AHT、BOF、BOZ、CGF、CGS、CHI、DAC、EUO、FER、HEU、IMF、ITH、ITR、JRY、JSR、JST、LAU、LOV、MEL、MFI、MFS、MRE、MTT、MVY、MWW、NAB、NAT、NES、OBW、PAR、PCR、PON、PUN、RRO、RSN、SFF、SFG、STF、STI、STT、STW、SVR、SZR、TER、TON、TUN、UOS、VSV、WEI和WEN,及其混合物和/或共生物。优选地,中孔分子筛选自以下骨架类型:MFI、FER和STT。
SCR催化剂的任一种可以包含大孔分子筛,所述大孔分子筛选自以下骨架类型:AFI、AFR、AFS、AFY、ASV、ATO、ATS、BEA、BEC、BOG、BPH、BSV、CAN、CON、CZP、DFO、EMT、EON、EZT、FAU、GME、GON、IFR、ISV、ITG、IWR、IWS、IWV、IWW、JSR、LTF、LTL、MAZ、MEI、MOR、MOZ、MSE、MTW、NPO、OFF、OKO、OSI、RON、RWY、SAF、SAO、SBE、SBS、SBT、SEW、SFE、SFO、SFS、SFV、SOF、SOS、STO、SSF、SSY、USI、UWY和VET,及其混合物和/或共生物。优选地,大孔分子筛选自以下骨架类型:MOR、OFF和BEA。
经金属交换的分子筛可以具有沉积至分子筛的通道、空穴或笼内或外部表面上的骨架外位点上的来自周期表VB、VIB、VIIB、VIIIB、IB或IIB族之一的至少一种金属。金属可以具有若干形式之一,包括但不限于零价金属原子或簇、孤立的阳离子、单核或多核氧基阳离子(oxycation),或作为扩展的金属氧化物。优选地,金属可以为铁、铜,及其混合物,或其组合。
使用金属前体在适合的溶剂中的混合物或溶液将金属与沸石组合。术语“金属前体”意为可以分散在沸石上以赋予催化-活性金属组分的任何化合物或络合物。由于使用其它溶剂的经济和环境问题两者,优选溶剂为水。在使用铜(其为优选的金属)时,适合的络合物或化合物包括但不限于,无水和水合硫酸铜、硝酸铜、乙酸铜、乙酰基丙酮酸铜、氧化铜、氢氧化铜,和铜氨络合物(例如[Cu(NH3)4]2+)的盐。本发明不局限于特定类型、组合物或纯度的金属前体。可以将分子筛添加至金属组分的溶液以形成悬浮液,然后允许其反应,以便金属组分分散在沸石上。金属可以分散在孔通道中以及分子筛的外表面上。金属可以以离子形式或作为金属氧化物分散。例如,铜可以作为铜(II)离子、铜(I)离子或作为氧化铜分散。可以将包含金属的分子筛与悬浮液的液体相分离,洗涤,并且干燥。然后可以将所得的包含金属的分子筛煅烧以将金属固定在分子筛中。优选地,第二和第三催化剂包含Cu-SCR,和Fe-SCR、钒、促进的Ce-Zr或促进的MnO2。
经金属交换的分子筛可以包含约0.10wt%和约10wt%的位于分子筛的通道、空穴或笼内或外部表面上的骨架外位点上的VB、VIB、VIIB、VIIIB、IB或IIB族金属。优选地,骨架外金属可以以约0.2wt%和约5wt%的量存在。
经金属交换的分子筛可以为负载在小孔分子筛上的铜(Cu),其具有催化剂总重量的约0.1-约20.0wt%的铜。更优选铜以催化剂总重量的约0.5wt%-约15wt%存在。最优选铜以催化剂总重量的约1wt%-约9wt%存在。
在本发明的第一方面,具有低氨储存量的载体载铂与第一SCR催化剂的共混物可以进一步包含钯(Pd)、金(Au)、银(Ag)、钌(Ru)或铑(Rh)中的至少一种。
用于催化剂的基材可以为通常用于制备包含流通式或过滤器式结构,例如蜂窝式结构、挤出载体、金属基材或SCRF的汽车催化剂的任何材料。优选基材具有多个从基材入口延伸至出口面的细小、平行气体流动通路,使得通路对流体流动是开放的。这样的单块载体可以包含每平方英寸横截面最高约700或更多个流动通路(或“泡孔”),尽管可以使用少得多的流动通路。例如,载体可以具有约7-600,更通常约100-600个泡孔/平方英寸(“cpsi”)。通路(其是从流体入口至其流体出口的基本上直的路径)由壁(SCR催化剂作为“载体涂层”涂覆至所述壁上)限定,以便流动穿过通路的气体接触催化材料。单块基材的流动通路为薄壁通道,其可以具有任何适合的横截面积形状,例如梯形、矩形、方形、三角形、正弦形、六边形、椭圆形、圆形等。本发明不限于特定的基材类型、材料或几何形状。
陶瓷基材可以由任何适合的耐火材料(例如堇青石、堇青石-α氧化铝、α-氧化铝、碳化硅、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅氧化镁、锆硅酸盐、硅线石、镁硅酸盐、锆石、叶长石、硅铝酸盐及其混合物)制造。
壁流动基材也可以由陶瓷纤维复合材料材料形成,例如由堇青石和碳化硅形成的那些。这样的材料能够经受在处理废气料流中遇到的环境,特别是高温。
基材可以高孔隙率基材。术语“高孔隙率基材”是指具有约40%-约80%的孔隙率的基材。高孔隙率基材可以具有优选至少约45%的孔隙率,更优选至少约50%的孔隙率。高孔隙率基材可以具有优选小于约75%的孔隙率,更优选小于约70%的孔隙率。术语孔隙率,如本文所用的,是指总孔隙率,优选如使用水银孔隙率法测量的。
优选地,基材可以堇青石、高孔隙率堇青石、金属基材、挤出SCR、过滤器或SCRF。
可以使用本领域中已知的方法,将包含具有低NH3储存量的载体载铂与第一SCR催化剂的共混物(其中第一SCR催化剂优选为Cu-SCR催化剂或Fe-SCR催化剂)的载体涂层施涂至基材的入口侧。在施涂载体涂层之后,可以将组合物干燥和煅烧。在组合物包含第二SCR时,可以将第二SCR在单独的载体涂层中施涂至具有底部层的经煅烧的制品,如以上描述的。在施涂第二载体涂层之后,可以将其干燥和煅烧,如针对第一层所进行的。
可以将具有含铂层的基材在300℃-1200℃,优选400℃-700℃,和更优选450℃-650℃的温度下干燥和煅烧。煅烧优选在干燥条件下进行,但是其也可以水热地(即,在一些水份含量的存在下)进行。煅烧可以进行约30分钟-约4小时,优选约30分钟-约2小时,更优选约30分钟-约1小时的时间。
在本发明的一个方面中,废气系统包含(1)催化制品和(2)用于转化废气气体中NOx和NH3的装置,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。就至少部分的系统操作时间而言,废气系统可以具有>1.0的ANR。废气系统可以进一步包含提供<100%的NOx转化率的第三SCR催化剂,其中第三SCR催化剂为仅Cu-沸石的SCR催化剂并且第三催化剂放置在催化剂制品的废气气体流动上游,所述催化剂制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。第二SCR催化剂可以包含促进的-Ce-Zr或促进的-MnO2。
在本发明的另一方面,废气系统包含(1)催化制品和(2)用于转化废气气体中NOx和NH3的装置,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层叠覆第一涂层沿入口至出口的轴的长度的至少20%。就至少部分的系统操作时间而言,废气系统可以具有>1.0的ANR。废气系统可以进一步包含提供<100%的NOx转化率的第三SCR催化剂,其中第三SCR催化剂为仅Cu-沸石的SCR催化剂并且第三催化剂放置在催化剂制品的废气气体流动上游,所述催化剂制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。第二SCR催化剂可以包含促进的-Ce-Zr或促进的-MnO2。
在本发明的另一方面,改善在约200℃-约350℃的温度下的来自废气气体中的氨的N2收率的方法包括使包含氨的废气气体与催化制品接触,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。相比于包含其中第一SCR催化剂作为第一层存在并且负载的铂存在于第二层中并且包含NH3和NO的气体穿过第一层然后穿过第二层的类似配制物的催化剂,收率的改善可以为约10%-约20%。
在本发明的另一方面,减少由废气气体中的NOx和NH3形成的N2O的方法包括使包含氨的废气气体与催化制品接触,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。相比于包含其中第一SCR催化剂作为第一层存在并且负载的铂存在于第二层中并且包含NH3和NO的气体穿过第一层然后穿过第二层的类似配制物的催化剂,N2O形成的减少可以为约20%-约80%。
在本发明的另一方面,使用催化制品处理包含NH3和NOx的废气气体的方法,所述催化制品包含:基材;第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;入口和出口,其中第一涂层置于基材上,第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂并且第二涂层至少部分地叠覆第一涂层。
以下实施例仅仅展示本发明;本领域技术人员会认识到本发明的精神和权利要求的范围内的多种变型。
实施例
实施例1-双层配制物-具有Cu-SCR顶部层的氧化铝载Pt
将具有氧化铝底部层载Pt和SCR顶部层的双层配制物用作对比实施例。
使用载体涂层将底部层施涂至陶瓷基材,所述载体涂层包含氧化铝载0.3wt%的Pt。将载体涂层施涂至陶瓷基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。制品上Pt的载量为3g/ft3。
使用包含Cu-CHA的第二载体涂层将顶部层施涂至使用底部层涂覆的基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。顶部层中Cu-CHA的载量为1.8g/in3。该材料为实施例1。通过将实施例1的样品在620℃下在包含10%的H2O的气氛中老化50小时制备经老化的样品。
实施例2-双层配制物-较高载量的氧化铝载Pt,Cu-SCR顶部层
将氧化铝底部层载Pt和SCR顶部层的双层配制物用作对比实施例。
使用载体涂层将底部层施涂至陶瓷基材,所述载体涂层包含氧化铝和裸沸石的共混物载的0.17wt%的Pt。将载体涂层施涂至陶瓷基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。制品上Pt的载量为3g/ft3。
使用包含Cu-CHA的第二载体涂层将顶部层施涂至使用底部层涂覆的基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。顶部层中Cu-CHA的载量为2.7g/in3。该材料为实施例2。通过将实施例2的样品在620℃下在包含10%的H2O的气氛中老化50小时制备经老化的样品。
实施例3-MFI沸石(SAR=2100)载1wt%的Pt与底部层中的Cu-CHA和顶部层中的Cu-CHA的双层共混物,Pt底部层的完全长度被Cu-CHA顶部层覆盖。
使用载体涂层将底部层施涂至陶瓷基材,所述载体涂层包含ZSM-5(SAR=2100的MFI骨架)载4wt%的Pt与Cu-CHA的共混物。将载体涂层施涂至陶瓷基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。制品上Pt、沸石和Cu-CHA的载量分别为3g/ft3、0.18g/in3和1.8g/in3。
使用包含Cu-CHA的第二载体涂层将顶部层施涂至使用底部层涂覆的基材,并且然后使用真空将载体涂层顺着基材牵动至基材长度的约50%的距离。在约500℃下将制品干燥和煅烧约1小时。顶部层中Cu-CHA的载量为1.8g/in3。在沿着制品的长度的恰当的位置处将制品切割以形成新的较小的制品,其100%的共混物底部层被Cu-CHA顶部层覆盖。该材料为实施例3。通过将实施例3的样品在620℃下在包含10%的H2O的气氛中老化50小时制备经老化的样品。
实施例4-MFI沸石(SAR=2100)载2wt%的Pt与底部层中的Cu-CHA和顶部层中的Cu-CHA的双层共混物,Pt底部层的完全长度被Cu-CHA顶部层覆盖。
使用载体涂层将底部层施涂至陶瓷基材,所述载体涂层包含ZSM-5(SAR=2100的MFI骨架)载4wt%的Pt与Cu-CHA的共混物。将载体涂层施涂至陶瓷基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。制品上Pt、沸石和Cu-CHA的载量分别为3g/ft3,0.09g/in3,和0.9g/in3。
使用包含Cu-CHA的第二载体涂层将顶部层施涂至使用底部层涂覆的基材,并且然后使用真空将载体涂层顺着基材牵动至基材长度的约50%的距离。在约500℃下将制品干燥和煅烧约1小时。顶部层中Cu-CHA的载量为1.8g/in3。在沿着制品的长度的恰当的位置处将制品切割以形成新的较小的制品,其100%的共混物底部层被Cu-CHA顶部层覆盖。该材料为实施例4。通过将实施例4的样品在620℃下在包含10%的H2O的气氛中老化50小时制备经老化的样品。
实施例5-MFI沸石(SAR=2100)载4wt%的Pt与底部层中的Cu-CHA和顶部层中的Cu-CHA的双层共混物,Pt底部层的完全长度被Cu-CHA顶部层覆盖。
使用载体涂层将底部层施涂至陶瓷基材,所述载体涂层包含ZSM-5(SAR=2100的MFI骨架)载4wt%的Pt与Cu-CHA的共混物。将载体涂层施涂至陶瓷基材,并且然后使用真空将载体涂层顺着基材牵动。在约500℃下将制品干燥和煅烧约1小时。制品上Pt、沸石和Cu-CHA的载量分别为3g/ft3,0.045g/in3,和0.9g/in3。
使用包含Cu-CHA的第二载体涂层将顶部层施涂至使用底部层涂覆的基材,并且然后使用真空将载体涂层顺着基材牵动至基材长度的约50%的距离。在约500℃下将制品干燥和煅烧约1小时。顶部层中Cu-CHA的载量为1.8g/in3。在沿着制品的长度的恰当的位置处将制品切割以形成新的较小的制品,其100%的共混物底部层被Cu-CHA顶部层覆盖。该材料为实施例5。通过将实施例5的样品在620℃下在包含10%的H2O的气氛中老化50小时制备经老化的样品。
图1显示了实施例1-5的在GHSV=120,000h-1下的NO+NH3反应性能。相比于实施例1和2,实施例3、4和5显著减少了N2O形成,在200-300℃,N2O减少最高为85%。实施例3、4和5中NO转化率和N2收率也显著更高。这些结果说明在实施例3、4和5中,Cu上的SCR反应得到促进并且Pt上的非选择性NH3+NO反应(主要产物为N2O)并且伴生的Pt上的NH3氧化(其减少了Cu上的SCR反应可得的NH3)得到最小化。尽管实施例2、4和5包含相同量的Cu-SCR催化剂,在实施例4和5中,N2O的形成低得多并且NO转化率高得多。这些结果表明沸石载Pt+Cu-SCR共混物底部层组合物对减少的N2O形成减少和改善的N2选择性负主要责任,而通过简单地增加顶部层中的Cu-SCR的量可以实现的益处极少。
图2显示了实施例1、3和5中在GHSV=60,000h-1下具有不同ANR(氨与NO比例)的NO+NH3反应性能。将ANR从1.0增加至1.4改善了全部催化剂中的NO转化率,表明对于优化的NOx去除效率,ANR>1是期望的。在1.4的高ANR(即,没有足够NO来与全部NH3反应,导致来自Cu-SCR组分的NH3逸出)下,全部三个催化剂测试显示在250℃以上几乎没有NH3逸出。因为在全部三种催化剂中对NH3氧化具有高度活性的Pt的存在,这是预期的。然而,在实施例3和5中,在250℃下,NO转化率高了约10%并且N2O形成低了75%。实施例3和5证明了在NOx和NH3都存在于进料中时Cu-催化的SCR反应得到促进并且Pt-催化的非选择性NO+NH3反应得到最小化。
系统的比较:
系统 组合物
1) 100%的Cu-SCR上游(SV=75,000h-1)+实施例1下游(SV=120,000h-1)
2) 50%的Cu-SCR上游(SV=150,000h-1)+实施例1下游(SV=120,000h-1)
3) 100%的Cu-SCR上游(SV=75,000h-1)+实施例5下游(SV=120,000h-1)
4) 50%的Cu-SCR上游(SV=150,000h-1)+实施例5下游(SV=120,000h-1)
图3显示了具有在上游中各种体积的Cu-SCR催化剂和Cu-SCR下游的实施例1和5的系统上的NO+NH3反应性能。
系统1与系统3的比较:
两个系统在前部具有相同的完全尺寸的SCR,具有足以完全地除去300ppm NO+300ppm NH3的体积。后部ASC催化剂仅仅对氧化200ppm的未反应的NH3负责。如预期的,在NO和NH3转化率上,两个系统之间区别极小。然而,系统3中N2O形成低得多,其中实施例5为下游(作为ASC催化剂),这归因于其N2O形成更低。
系统2与系统4的比较:
两个系统在前部具有相同的半尺寸的SCR,具有不足以完全除去300ppm NO的体积,导致NO和NH3逸出。在实施例1下游的情况下,由于前SCR体积减小,NO转化率显著降低并且N2O形成显著增加,表示Pt上发生NH3氧化和非选择性NH3+NO反应。相反,在实施例5下游的情况下,NO转化率没有明显的降低并且N2O形成几乎没有增加,表明Pt上的非选择性NH3+NO反应得到最小化。
前述实施例仅仅意图作为展示;所附权利要求限定了本发明的范围。
Claims (15)
1.催化制品,其包含基材,所述基材具有入口和出口并且涂覆有:第一涂层,其包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物;第二涂层,其包含第二SCR催化剂;
其中所述第二涂层至少部分地叠覆所述第一涂层,并且其中所述第一SCR催化剂为Cu-SCR催化剂或Fe-SCR催化剂。
2.根据权利要求1所述的催化制品,其中所述第二涂层完全地叠覆所述第一涂层。
3.根据权利要求1所述的催化制品,其中所述具有低氨储存量的载体为含硅载体,所述含硅载体包括二氧化硅或二氧化硅与氧化铝的比例为以下的至少之一的沸石:≥100。
4.根据权利要求1所述的催化制,其中包含具有低氨储存量的载体载铂的共混物进一步包含钯(Pd)、金(Au)、银(Ag)、钌(Ru)或铑(Rh)中的至少一种。
5.根据权利要求1所述的催化制品,其中所述第一SCR催化剂包含承载在分子筛上的Cu或Fe,所述分子筛选自以下骨架类型:ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZON、BEA、MFI和FER及其混合物和/或共生物。
6.根据权利要求1所述的催化制品,其中所述第二SCR催化剂为负载于分子筛上的贱金属,其中所述贱金属选自钒(V)、钼(Mo)和钨(W)、铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、和铜(Cu),及其混合物。
7.根据权利要求1所述的催化制品,其中相比于包含其中第一SCR催化剂作为第一层存在并且铂存在于第二层中并且包含NH3和NO的气体穿过第一层然后穿过第二层的类似配制物的催化剂,该催化剂提供了在约200℃-约300℃的温度下的来自氨的N2收率的改善,其中N2收率的改善为至少10%。
8.根据权利要求1所述的催化制品,其中相比于包含其中第一SCR催化剂作为第一层存在并且铂存在于第二层中并且包含NH3和NO的气体穿过第一层然后穿过第二层的类似配制物的催化剂,该催化剂提供了在约200℃-约350℃的温度下的减少的由NH3和NOx形成的N2O。
9.根据权利要求1所述的催化制品,其中所述基材为堇青石、高孔隙率堇青石、金属基材、挤出蜂窝体或过滤器。
10.根据权利要求1所述的催化制品,其中所述第二SCR催化剂位于所述催化剂的入口侧上,所述催化剂包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物。
11.根据权利要求1所述的催化制品,其中所述第二SCR催化剂位于所述催化剂的出口侧上,所述催化剂包含具有低氨储存量的载体载铂与第一SCR催化剂的共混物。
12.根据权利要求11所述的催化制品,其中所述第二SCR催化剂包含促进的-Ce-Zr或促进的-MnO2。
13.根据权利要求1所述的催化剂制品,其中所述第二涂层叠覆所述第一涂层沿入口至出口的轴的长度的至少20%。
14.改善在约200℃-约350℃的温度下的来自废气气体中的氨和NOx的N2收率的方法,所述方法包括使包含氨的废气气体与根据权利要求1所述的催化制品接触。
15.处理包含氨和NOx的废气气体的方法,所述方法包括使包含氨的废气气体与根据权利要求1所述的催化制品接触。
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| CN109833907A (zh) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | 一种具备储放氨性能的低温耐硫焦炉烟气脱硝催化剂 |
| CN109833907B (zh) * | 2017-11-29 | 2021-10-15 | 中国科学院大连化学物理研究所 | 一种具备储放氨性能的低温耐硫焦炉烟气脱硝催化剂 |
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| CN110961148A (zh) * | 2019-12-14 | 2020-04-07 | 中触媒新材料股份有限公司 | 一种aei/lev结构共生复合分子筛及其制备方法和scr应用 |
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| CN110961144A (zh) * | 2019-12-14 | 2020-04-07 | 中触媒新材料股份有限公司 | 一种具有cha/lev拓扑结构共生复合分子筛及其制备方法和scr应用 |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102527239B1 (ko) | 2023-05-02 |
| WO2016205441A1 (en) | 2016-12-22 |
| JP2018526194A (ja) | 2018-09-13 |
| EP3310462A1 (en) | 2018-04-25 |
| RU2018101694A (ru) | 2019-07-19 |
| JP6830451B2 (ja) | 2021-02-17 |
| US20190299160A1 (en) | 2019-10-03 |
| RU2715539C2 (ru) | 2020-02-28 |
| CN107847862B (zh) | 2020-12-18 |
| RU2018101694A3 (zh) | 2019-07-24 |
| KR20180034400A (ko) | 2018-04-04 |
| DE102016111000A1 (de) | 2016-12-22 |
| GB2541500A (en) | 2017-02-22 |
| US9878287B2 (en) | 2018-01-30 |
| US20160367937A1 (en) | 2016-12-22 |
| GB201610521D0 (en) | 2016-08-03 |
| US20180147530A1 (en) | 2018-05-31 |
| GB2541500B (en) | 2019-06-26 |
| EP3310462B1 (en) | 2019-07-31 |
| US10322372B2 (en) | 2019-06-18 |
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