CN108348852A - 载体界面孔隙集中埋没型scr催化剂结构体 - Google Patents

载体界面孔隙集中埋没型scr催化剂结构体 Download PDF

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CN108348852A
CN108348852A CN201680062234.6A CN201680062234A CN108348852A CN 108348852 A CN108348852 A CN 108348852A CN 201680062234 A CN201680062234 A CN 201680062234A CN 108348852 A CN108348852 A CN 108348852A
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carrier
scr catalyst
interface hole
type scr
catalyst
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韩贤植
李泰宇
安陵均
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Xi Xing Catalyst Co Ltd
Heesung Catalysts Corp
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Abstract

本发明涉及一种载体界面孔隙集中埋没型SCR催化剂结构体，具体地，涉及载体界面孔隙集中沉积型或埋没型SCR催化剂结构体，其作为适用于高硫含量废气处理的载体埋没型SCR催化剂，催化剂活性物质集中沉积于载体界面孔隙内，而在载体内壁及例如载体深处的除载体界面外的部分实际上不存在催化剂活性物质。

Description

载体界面孔隙集中埋没型SCR催化剂结构体
技术领域
本发明涉及一种载体界面孔隙集中埋没型SCR催化剂结构体。具体讲，就是涉及一种载体界面孔隙集中沉积型或埋没型SCR催化剂结构体，针对可用于高硫含量废气处理的载体埋没型SCR催化剂，催化剂活性物质集中沉积于载体界面孔隙内，而在载体内壁及除载体界面的部分(例如，载体深处)实际上不存在催化剂活性物质。
背景技术
一般来说，工业、多用途锅炉、发动机及炉(furnace)领域都采用可对从系统中排放的氮氧化物进行控制的选择性催化剂还原(SCR：selective catalytic reductio n)系统。SCR系统用于减少从锅炉、发动机与炉的废气中氮氧化物的排放。简言之，在上述系统中，氨(或尿素等还原剂)被喷射到有催化剂的锅炉的废气流中，氨从废弃中还原大量的氮氧化物从而转换为水与氮。利用于SCR系统的脱氮氧化物催化剂成本较高，因此优选能够对废气/氨/催化剂反应的化学计量进行控制。这种脱氮氧化物等催化剂活性物质被耐火无机材料或金属材质的载体支撑。
用于SCR系统的催化剂中的涂覆型催化剂是具有如下结构的催化剂，即将活性物质涂覆于陶瓷或金属材质的蜂窝型形态的载体上的结构。简单讲，可以使用具有从蜂窝型结构的载体流入面或排出面延长的细小并列气体流动通路形态的单块载体(monolithiccarrier)，所述通路是开放的，因此流体可以通过这些通路流动。在这种情况下，从流体流入口到流体排出口的实际上为直线路径的通路中催化剂活性物质涂覆为洗涂层(washcoat)，通过所述通路流动的废气与被涂覆的催化剂物质接触。单块载体的流动通路可以呈梯形、长方形、正方形、正弦曲线形态、六边形、椭圆形、圆形等任意合适的截面形态及大小，采用内壁较薄的通道结构。这种结构体每平方英寸的截面上大约具有10～900个以上的气体流入开口(即，单元)。
本申请人研发出了载体孔隙埋没型SCR催化剂结构体(专利第1,336,597号)。针对由载体及催化剂活性物质构成的高硫含量废气的氮氧化物处理用催化剂结构体，所述孔隙埋没型SCR催化剂的催化剂活性物质只沉积于载体内部孔隙内，实际上在载体内壁上不会存在催化剂活性物质。
发明内容
所要解决的技术问题
但是，申请人意识到随着通过载体通路流动的废气流速，孔隙埋没型SCR催化剂的性能会下降。即，通过通路的废气速度越快，能够通过载体气孔的可能性越低。因此，催化剂活性物质实际上只沉积于载体内部孔隙内的载体孔隙埋没型SCR催化剂结构体的效率会减半。另外，昂贵的催化剂活性物质会沉积到不与废气接触的载体内部深处，由此会导致材料成本升高。
解决技术问题的方法
本发明就是为解决用于处理高硫含量废气的现有载体孔隙埋没型SCR催化剂结构体存在的问题而研发的，本发明涉及一种载体界面孔隙集中沉积型或埋没型S CR催化剂结构体，该结构体中催化剂活性物质只集中沉积于载体界面孔隙内，而在载体内壁及除载体界面以外实际上不存在催化剂活性物质。非限制性地，对于依据本发明的载体界面孔隙集中沉积型或埋没型SCR催化剂结构体来说，载体呈蜂窝型结构并具有20％～80％多孔性，可以由堇青石、碳化硅、堇青石-a-氧化铝、氮化硅、锆莫来石、锂辉石、氧化铝-二氧化硅-氧化镁、硅酸锆、硅线石、硅酸镁、锆石、透锂长石、a-氧化铝、硅酸铝等构成。优选地，由堇青石构成。对于依据本发明的载体界面孔隙集中沉积型SCR催化剂结构体来说，沉积于载体内部的催化剂活性物质可以是：将钨氧化物(WO3)或钼氧化物(MoO3)与钒氧化物(V2O5)一起添加到钛氧化物(TiO2)中形成的钒系列；沸石系列；或基本金属(base metal)氧化物，但并非仅限定于此。
发明效果
依据本发明的载体界面孔隙集中埋没型SCR催化剂，即使在通过载体通路流动的废气流速增加的情况下，废气及催化剂活性成分也能进行有效接触，由此可以防止现有孔隙埋没型SCR催化剂性能下降。同时，无需使昂贵的催化剂活性物质载持在废气不接触的载体深处，由此可以节约材料成本及改善工艺效率。
附图说明
图1是示出现有埋没型SCR催化剂结构体及依据本发明的界面孔隙集中埋没型SCR催化剂结构体内反应情况的概略图；
图2现有埋没型SCR催化剂结构体及依据本发明的界面孔隙集中埋没型SCR催化剂结构体截面的电子显微镜照片；
图3是现有埋没型SCR催化剂结构体及依据本发明的界面孔隙集中埋没型SC R催化剂结构体内的SCR催化剂活性度比较图。
具体实施方式
在依据本发明的载体界面孔隙集中埋没型SCR催化剂结构体中，催化剂活性物质集中沉积于载体界面孔隙内，而在载体内壁表面及除载体界面的部分(例如，载体深处)实际上不存在催化剂活性物质。
定义：
本申请中使用的“界面”是指在载体(也称“支撑体”)内壁与载体上形成的气孔(也称“通路”)间的接触面。”界面孔隙”是指存在于界面上的载体内壁孔隙。在本申请中，将存在于内壁厚度的20％以内的载体内壁孔隙定义为界面孔隙。但是，该领域的技术人员能够理解，随着载体本身的孔隙率，界面孔隙可以位于内壁厚度的20％以上至50％以内。本申请中使用的”沉积”或”埋没”是指催化剂活性物质向形成于载体上的界面孔隙内部渗透并在孔隙内部得到支撑。实际上，除了界面孔隙外，催化剂活性物质不会载持于载体内部。
构成：
在本发明中，为了使催化剂活性物质沉积于载体内部，以便实现本发明的目的，在载体全部容积中孔隙所占容积的比率即多孔度优选为20％～80％。如果多孔度为20％以下，就无法将催化剂活性物质涂覆于内壁上。如果多孔度为80％以上，其机械强度就会下降。因此，一般将其控制在40～70％。更加优选地，最好使用具有50～65％多孔度的载体。为了使发电厂或船舶柴油发动机排放的废气经过催化剂时压力下降达到最小化，载体优选构成为蜂窝型形态。虽然本领域的技术人员对于蜂窝型或蜂巢形态的结构非常熟悉，但是下面还是作以简要描述。蜂窝型或蜂巢形结构带有从载体流入前面或排出后面延长的并列气体流动通路，所述通路的前面及后面是开放的，从而带有从气体流入前面到排出后面实际上为直线路径的开放通路，即通道，这些通道由较薄的内壁形成。
依据本发明的载体可以由能够提供上述高度的多孔性的陶瓷材质构成，可由堇青石、碳化硅、堇青石-a-氧化铝、氮化硅、氧化铝-二氧化硅-氧化镁、硅酸锆、硅线石、硅酸镁、锆石、透锂长石、a-氧化铝、硅酸铝等构成，优选地，由堇青石构成。催化剂活性物质沉积于在载体上形成的众多孔隙内，沉积于载体内部的物质可以是：将钨氧化物(WO3)或钼氧化物(MoO3)与钒氧化物(V2O5)一起添加到钛氧化物(TiO2)中形成的钒系列；沸石系列；或基本金属(base metal)氧化物，但并非仅限定于此。
依据本发明的界面孔隙集中埋没型SCR催化剂制造方法，为了使载体内壁表面不存在催化剂活性物质，以及为了确保除了界面孔隙外催化剂活性物质不会渗透到载体深处，而实施定量化处理。因此，实际上所有的催化剂活性物质沉积于载体界面孔隙内，而在内壁表面实际上不存在催化剂活性物质。本申请的所述制造方法与现有埋没型SCR催化剂制造方法没有什么不同。即，现有埋没型SCR催化剂，为了确保其在载体内壁形成厚厚的涂层，而对催化剂活性料浆进行定量。但是，依据本发明的界面孔隙集中埋没型SCR催化剂，为了确保所有的催化剂活性物质实际上只渗透到载体界面细孔内部，而对催化剂活性料浆进行定量，此后再将多孔性载体浸泡于所述料浆中，最后经焙烧制作而成。即，依据本发明的埋没型SCR催化剂，通过以下几个步骤就能够很容易地制造出来，即，(a)对载体的多孔度进行测定的步骤；(b)决定能够全量只沉积于载体界面孔隙内的催化剂活性料浆的物性(粒度、粘度、含量)的步骤；(c)使催化剂活性料浆沉积于载体的步骤；(d)将通过步骤(c)获得的催化剂进行煅烧的步骤。(c)步骤中的定量沉积方法通过本申请人发明的专利第1,271,434号(催化剂支撑体定量涂覆装置及方法)就可以实现。
但是，依据本发明的界面孔隙集中沉积型或埋没型SCR催化剂制造方法，可以通过多种处理方法进行制造。非限制性地，可以通过改变催化剂活性料浆的物性而使催化剂活性成分只集中载持于界面孔隙内。例如，可以推进提高粘性的方案。另外，可以通过调节涂覆工序中的工艺因素(例如，时间、压力等)而使催化剂活性成分只沉积于界面孔隙内。同时，利用热塑性高分子物质使内壁的一部分构成针对载体深处的阻挡层，使所述料浆只载持于界面孔隙内，然后在煅烧过程中使所述高分子物质燃烧，从而可以获得仅埋没在界面孔隙的催化剂结构体。
最佳实施形态：
图1是示出现有埋没型SCR催化剂结构体及依据本发明的界面集中埋没型SC R催化剂结构体内反应情况的概略图。与本申请的界面集中埋没型对比，可以将现有埋没型SCR催化剂结构体定义为分散埋没型。本发明中采用的载体是一种具有高度多孔性的载体，例如，堇青石材质的蜂窝结构载体(直径1英寸，长度2英寸，46cpsi)，该载体能够使通过涂覆装置使用的催化剂活性成分实质上全部沉积。因此，如图1所示，虽然分散沉积型催化剂是一种洗涂层(催化剂活性成分)全部沉积在载体内部而在载体内壁实际上不存在洗涂层的结构体，但是与之对比，本申请的界面集中埋没型催化剂集中于载体内壁界面上，从而在界面孔隙以一定的厚度涂敷。因此，催化剂活性成分只集中于载体界面孔隙内，而不会沉积到载体深处，由此可以解决现有分散埋没型催化剂存在的问题，即性能降低及有关材料费与工序效率的问题。
图2是使用具有55％多孔度的堇青石材质的载体时分散埋没型(左侧)及依据本发明的集中埋没型SCR催化剂(右侧)中的催化剂活性物质(Ti)的分布照片。即，从右侧照片中可以看出，催化剂活性成分只集中于界面孔隙内。左侧样品的催化剂活性成分Dry Gain(D/G)为100g/L，右侧样品为将100g/L的催化剂活性成分施加到55％多孔度的堇青石载体中，催化剂活性成分只集中载持在界面孔隙内。实际上，催化剂成分大部分渗透到载体界面孔隙内，而在表面实际上不存在对活性作出贡献的催化剂成分。
图3是现有分散埋没型SCR催化剂(绿色)及依据本发明的界面集中埋没型SCR催化剂(蓝色)活性度比较图。每种催化剂活性成分沉积于3％的V2O5/TiO2、Dry Gain为100g/L、多孔度为55％的堇青石材质的载体(46cpsi)内部。这两种催化剂的活性评估条件为空间速度(SV)：21,000 1/hr，供给气体成分：400ppm NO、400ppm NH3。如图3所示，在孔隙扩散(pore diffusion)对催化剂性能产生影响的低温区域，界面集中埋没型催化剂的性能比现有催化剂更加优秀。

Claims (6)

1.一种载体界面孔隙集中埋没型SCR催化剂结构体，其特征在于：
该结构体为由载体及催化剂活性物质构成用于处理废气中氮氧化物的催化剂结构体，催化剂活性物质集中沉积于载体界面孔隙内，而在载体内壁及除载体界面外的部分实际上不存在催化剂活性物质。
2.根据权利要求1所述的载体界面孔隙集中埋没型SCR催化剂结构体，其特征在于：
界面孔隙存在于构成载体的内壁厚度的50%以内。
3.根据权利要求1或2所述的载体界面孔隙集中埋没型SCR催化剂结构体，其特征在于：
所述载体的多孔度在20%∼80%的范围内。
4.根据权利要求1或2所述的载体界面孔隙集中埋没型SCR催化剂结构体，其特征在于：
所述载体为蜂窝型结构。
5.根据权利要求1或2所述的载体界面孔隙集中埋没型SCR催化剂结构体，其特征在于：
所述载体从由堇青石、碳化硅、堇青石-α-氧化铝、氮化硅、锆莫来石、锂辉石、氧化铝-二氧化硅-氧化镁、硅酸锆、硅线石、硅酸镁、锆石、透锂长石、a-氧化铝及硅酸铝构成的陶瓷材质中选择。
6.根据权利要求1所述的载体界面孔隙集中埋没型SCR催化剂结构体，其特征在于：
所述催化剂活性物质从由将钨氧化物（WO3）或钼氧化物（MoO3）与钒氧化物（V2O5）一起添加到钛氧化物（TiO2）中形成的钒系列、沸石系列及基本金属（base metal）氧化物构成的组中选择。
CN201680062234.6A 2015-11-02 2016-10-26 载体界面孔隙集中埋没型scr催化剂结构体 Pending CN108348852A (zh)

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