CN112108144A - 一种硼纤维复合材料负载钒钨钛低温脱硝催化剂及其制备方法 - Google Patents
一种硼纤维复合材料负载钒钨钛低温脱硝催化剂及其制备方法 Download PDFInfo
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Abstract
一种硼纤维复合材料负载钒钨钛低温脱硝催化剂及其制备方法,属于催化脱硝领域。首先制备出较高活性的钒钨钛催化剂,然后研磨至细粉加入去离子水中,再加入纤维素胶制成一定浓度的浆液。将硼纤维复合材料载体浸入在纤维素胶溶液里预处理,烘干后再浸入上述催化剂浆液中,多次涂覆后烘干焙烧,得到硼纤维复合材料负载的钒钨钛催化剂。本发明具有较轻的重量,灵活的使用条件,较高的低温脱硝活性等优点,在140℃~300℃有较好的脱硝活性,可适用于低温SCR脱硝***,降低了成本,减轻了维护压力,适用于工业生产。
Description
技术领域
本发明属于工业低温SCR脱硝领域,主要涉及一种硼纤维复合材料负载钒钛基低温脱硝催化剂及其制备方法。
背景技术
氮氧化物(NOx)是涉及环境问题最多的大气污染物,它是温室效应、酸雨、臭氧层破坏、水体富营养化、光化学烟雾和雾霾的主要前驱物,对人类健康和生态环境造成极大危害,所以目前对氮氧化物的治理尤为重要。
工业上氮氧化物治理最有效的方法是SCR(选择性催化还原)脱硝技术,其中中高温SCR技术的发展比较完善,但低温SCR技术依然存在众多技术问题有待解决,包括低温活性差,投入成本高,占地面积大等缺点,所以目前高活性的低温SCR催化剂和合适的催化剂载体是研究重点。
目前工业用整体式催化剂有以堇青石为载体的蜂窝状催化剂、玻璃纤维负载的波纹板式催化剂等,本发明所用的硼纤维复合材料载体具有质量轻,涂覆效果好,装配灵活等优势,是一种适用于工业催化剂的优势材料。
发明内容
本发明为了改善现有的催化剂载体质量大、占地面积大、运行成本高等问题,提供了一种硼纤维复合材料负载钒钛基低温脱硝催化剂及其制备方法。
本发明采用的技术方案为:
本发明涉及一种低温SCR钒钛基催化剂的制备,并采用浸渍法将其负载至硼纤维复合材料载体上。
本发明涉及的硼纤维复合材料负载催化剂的制备方法,步骤如下:
1)将制得的钒钛基低温脱硝催化剂和纤维素胶加入去离子水中,水浴加热至40-60℃,搅拌均匀,得到催化剂浆液,其中钒钛基低温脱硝催化剂浆液的浓度80-240g/L,钒钛基低温脱硝催化剂和纤维素胶的质量比为(15-25):1;
2)将硼纤维复合材料浸入浓度为2%-6%的纤维素胶水溶液中浸泡处理,沥出烘干,备用;
3)将步骤2)处理好的硼纤维复合材料浸入步骤1)中的催化剂浆液中,快速浸渍均匀,然后转移至烘箱中烘干;
4)将步骤3)的硼纤维复合材料再次浸入步骤1)中的催化剂浆液中,快速浸渍均匀,然后转移至烘箱中烘干,重负1-4次;
5)将步骤4)烘干的载体催化剂置于马弗炉中480-500℃焙烧2-4小时,得到硼纤维复合材料负载钒钨钛低温脱硝催化剂。
所述的硼纤维复合材料是硼纤维和环氧树脂的复合材料。
所述的纤维素胶优选羧甲基纤维素钠CMC。
上述所述的钒钛基低温脱硝催化剂,各组分含量分别是:TiO2为87.5-94.5wt%,V2O5为1~5wt%,WO3为3.5~7.5wt%。所述的钒钛基低温脱硝催化剂的制备方法,包括如下步骤:
1)取50ml去离子水于烧杯中,加热至40-60℃,再按顺序加入草酸、偏钒酸铵、钨酸铵,搅拌至完全溶解;
2)将载体二氧化钛缓慢加入步骤1)溶液中,在40-60℃条件下继续搅拌至溶液呈粘稠状;
3)将步骤2)中粘稠状催化剂先置于烘箱中烘干4小时,再置于马弗炉中分段焙烧,200-250℃焙烧1-2小时,470-550℃焙烧2-4小时,得到基础钒钨钛催化剂。
4)将步骤3)中催化剂研磨至40目以下的细粉备用。
硼纤维复合材料负载钒钛基低温脱硝催化剂可应用于140℃—300℃的烟气条下进行脱硝。
本发明的优点在于:
本发明所使用的硼纤维复合材料质量轻,体积密度仅70kg/m3,大大减轻了整体催化剂装载质量。
本发明所使用的硼纤维复合材料负载效果好,每1kg载体可负载2kg催化剂,保证了催化剂的低温活性。
本发明使用了工业广泛应用的钒钛基低温脱硝催化剂负载,此类催化剂的研究较完善,活性效果较好,使用范围较广,使用成本较低,且可适用工业应用的不同空速要求。
附图说明
表1是硼纤维复合材料涂覆催化剂的负载情况;
图1是硼纤维复合材料的表面形貌图;
图2是硼纤维复合材料的元素分析图,其中的Si为测试引入的杂质,Ca为添加剂元素;
图3是硼纤维复合材料涂覆催化剂后的在空速6000h-1下的脱硝效率图。
图4是硼纤维复合材料涂覆催化剂后的在空速12000h-1下的脱硝效率图。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明并不限于以下实施例。
所述的载体板为硼纤维和环氧树脂的复合材料,具体成分见图1。
实施例1
准确称取16.6g草酸,溶于400ml去离子水中,60℃水浴超声搅拌溶解完全,加入7.7g偏钒酸铵,超声搅拌溶于呈深蓝色,再加入14.6g钨酸铵,超声搅拌半小时至溶解完全,最后加入182g锐钛矿型二氧化钛载体,60℃超声搅拌至溶液呈粘稠状;将其转移至烘箱中烘干,然后置于马弗炉中250℃焙烧一小时,500℃焙烧三小时,取出后自然冷却至室温,研磨筛分至20目以下备用。将制备的200g粉体催化剂和10g羧甲基纤维素钠加入1000ml去离子水中,超声搅拌均匀,制成200g/L的催化剂浆液,备用。
实施例2
将载体板浸入纤维素胶溶液中软化后卷成筒状;筒状载体置于烘箱中3h烘干;将筒状载体浸入实施例1中制备的浆液中,10秒后沥出;将浸渍后的载体置于烘箱中烘干30min;重复上述浸渍步骤,将载体浸渍三次;涂覆好的载体烘干后置于马弗炉中510℃焙烧3小时,得到1#载体催化剂;
实施例3
将载体板浸入纤维素胶溶液中软化后卷成筒状;筒状载体置于烘箱中3h烘干,将筒状载体浸入实施例1制备的浆液中,10秒后沥出,将浸渍后的载体置于烘箱中烘干30min,重复上述浸渍步骤,将载体浸渍两次,涂覆好的载体烘干后置于马弗炉中490℃焙烧3小时,得到2#载体催化剂。
表1
涂覆量:表示每次涂覆完毕之后,负载的催化剂质量,即涂覆后载体总质量减去载体质量。
测试例1
将实施例2中的1#和实施例3中的2#载体催化剂分别置入直径20mm的石英反应管中,在120-300℃范围内进行脱硝活性测试,原料气组成:O2(5%),NO(700ppm),NH3(700ppm),N2为平衡气,空速为6000h-1。脱硝效率结果如图3所示,可以看出在180℃-300℃,催化剂都具有大于90%的活性,且220℃以后都接近于100%。
测试例2
将实施例2中的1#和实施例3中的2#载体催化剂分别置入直径20mm的石英反应管中,在120-300℃范围内进行脱硝活性测试,原料气组成:O2(5%),NO(700ppm),NH3(700ppm),N2为平衡气,空速为12000h-1。脱硝效率结果如图4所示,可以看出在170℃,催化剂可具有大于70%的活性,且220℃以后能达到90%以上的效率。
测试1和2的区别仅是空速不同?是的,为了测试较高空速下催化剂是否可以用。
Claims (7)
1.一种硼纤维复合材料负载催化剂的制备方法,其特征在于,步骤如下:
1)将制得的钒钛基低温脱硝催化剂和纤维素胶加入去离子水中,水浴加热至40-60℃,搅拌均匀,得到催化剂浆液,其中钒钛基低温脱硝催化剂的浓度80—240g/L,钒钛基低温脱硝催化剂和纤维素胶的质量比为(15-25):1;
2)将硼纤维复合材料浸入浓度为2-6wt%的纤维素胶水溶液中浸泡处理,沥出烘干,备用;
3)将步骤2)处理好的硼纤维复合材料浸入步骤1)中的催化剂浆液中,快速浸渍均匀,然后转移至烘箱中烘干;
4)将步骤3)的硼纤维复合材料再次浸入步骤1)中的催化剂浆液中,快速浸渍均匀,然后转移至烘箱中烘干,重负1-4次;
5)将步骤4)烘干的载体催化剂置于马弗炉中480-500℃焙烧2-4小时,得到硼纤维复合材料负载钒钨钛低温脱硝催化剂。
2.按照权利要求1所述的一种硼纤维复合材料负载催化剂的制备方法,其特征在于,所述的硼纤维复合材料是硼纤维和环氧树脂的复合材料。
3.按照权利要求1所述的一种硼纤维复合材料负载催化剂的制备方法,其特征在于,所述的纤维素胶优选羧甲基纤维素钠CMC。
4.按照权利要求1所述的一种硼纤维复合材料负载催化剂的制备方法,其特征在于,上述所述的钒钛基低温脱硝催化剂,各组分含量分别是:TiO2为87.5-94.5wt%,V2O5为1~5wt%,WO3为3.5~7.5wt%。
5.按照权利要求4所述的一种硼纤维复合材料负载催化剂的制备方法,其特征在于,所述的钒钛基低温脱硝催化剂的制备方法,包括如下步骤:
1)取50ml去离子水于烧杯中,加热至40-60℃,再按顺序加入草酸、偏钒酸铵、钨酸铵,搅拌至完全溶解;
2)将载体二氧化钛缓慢加入步骤1)溶液中,在40-60℃条件下继续搅拌至溶液呈粘稠状;
3)将步骤2)中粘稠状催化剂先置于烘箱中烘干4小时,再置于马弗炉中分段焙烧,200-250℃焙烧1-2小时,470-550℃焙烧2-4小时,得到基础钒钨钛催化剂。
4)将步骤3)中催化剂研磨至40目以下的细粉备用。
6.按照权利要求1-5任一项所述的方法制备得到的硼纤维复合材料负载催化剂。
7.按照权利要求1-5任一项所述的方法制备得到的硼纤维复合材料负载催化剂的应用,应用于140℃—300℃的烟气条下进行脱硝。
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