CN107744819B - 一种环境友好型脱硝催化剂的制备方法 - Google Patents
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Abstract
本发明属于化工环保技术领域,公开了一种硫铁矿渣的脱硝催化剂的制备方法,是通过硫铁矿渣预处理→硫铁矿渣改性→活性组分负载得到的;通过将经过预处理的硫铁矿渣置于蔗糖溶液中,然后依次经水热处理、过滤、干燥、焙烧得到涂覆有碳微球涂层的改性硫铁矿渣,进而向改性钢渣中负载五氧化二钒、硝酸钇和硫酸铈活性组分最终得到基于硫铁矿渣的脱硝催化剂。本发明以硫铁矿渣为原料,通过对其进行改性将其转变为新型的脱硝催化剂,该催化剂为能在200~400oC范围内具有较高的反应活性。
Description
技术领域
本发明属于化工环保技术领域,涉及一种脱硝催化剂,特别是涉及一种基于硫铁矿渣的脱硝催化剂的制备方法。
背景技术
随着我国城市化进程的高速推进、经济的快速增长,以及人民生活水平的不断提高,国内对煤炭等化石能源的消耗量不断提升,这些燃料在燃烧过程中排放出大量的氮氧化物(NOx)会对空气形成污染,进而对人类的健康和生态环境造成威胁和破坏。目前大气中的NOx一方面来自机动车排放的尾气,另一方面产生于燃煤锅炉产生的烟气。NH3-SCR技术是去除NOx高效稳定的技术,在燃煤电厂脱硝过程中已经应用多年。NH3-SCR技术的核心是催化剂体系,目前主要应用的是V2O5-WO3(MO3)/TiO2催化剂,该催化体系在中温段具有优异的NOx净化效率和抗SO2中毒性能,但是仍然存在活性温度窗口窄(300oC~400oC)、低温活性差、高温条件下N2选择性低等不足。因此,开发出反应活性好、操作窗口较宽的新型环境友好型脱硝催化剂成为目前研究的热点。
目前脱硝催化剂的生产技术主要被国外少数公司垄断,如丹麦的托普索、日本的触媒化成等。目前我国生产的SCR催化剂也主要依靠引进国外技术,其尚未真正实现国产化。近些年,我国研发的SCR催化剂主要是以锐钛型TiO2或分子筛为载体的催化剂,但是其制作成本较高,阻碍了其广泛的应用。因此,寻求新型廉价环保的SCR催化剂对于推动固定源烟气脱硝的普及具有重要的使用价值。
发明内容
针对现有NH3-SCR脱硝催化剂中存在的不足,本发明公开了一种基于硫铁矿渣的脱硝催化剂及其制备方法,以硫铁矿渣为原料,通过对其进行改性将其转变为新型的脱硝催化剂,该催化剂为能在200~400oC范围内具有高的反应活性。
本发明是采用如下技术方案实现的:
一方面,本发明公开了一种基于硫铁矿渣的脱硝催化剂的制备方法,是通过以下步骤实现的:
1)硫铁矿渣预处理:将硫铁矿渣原料破碎,筛分出60~80目的硫铁矿渣溶于质量浓度为2~5%的稀硝酸溶液中,在室温下搅拌4~8h后进行过滤,将滤出的(即未溶解的)硫铁矿渣过滤洗涤至中性后,在105℃条件下干燥处理12h;
2)硫铁矿渣改性:向去离子水中加入蔗糖并在室温下搅拌使其完全溶溶解,得到蔗糖溶液;然后向蔗糖溶液中加入经步骤1)处理得到的硫铁矿渣,继续搅拌10~15min,得到混合物A;将混合物A转移至水热反应釜中,在180~220℃条件下处理2~4h,得到混合物B;将混合物B过滤得到的滤饼用乙醇洗涤2~4次后,在110℃的条件下干燥处理6h后于500℃的氮气气氛下焙烧4h,得到涂覆有碳微球涂层的改性硫铁矿渣;
3)活性组分负载:将等重量的V2O5和草酸溶于去离子水中,在室温下搅拌使其完全溶解;随后向其中加入硝酸钇和硫酸铈并继续搅拌30min,然后向其中加入步骤2)中所得的改性硫铁矿渣,得到混合物C;将混合物C置于水热反应釜中于140~160℃下处理24~36h,然后将其在60~80℃的水浴搅拌条件下进行缓慢蒸发,直至其表面的水分消失后,再置于105℃的条件下干燥处理12h,而后转移至高温加热炉中在N2保护的气氛下于500℃继续处理5h后进行压片成型,得到催化剂。
作为一种优选实施方式,步骤3)中,所述V2O5与改性硫铁矿渣的重量比为1%~3%,硝酸钇与改性硫铁矿渣的重量比为2%~5%;硫酸铈的重量与改性硫铁矿渣的重量比为8%~12%。
作为一种优选实施方式,步骤1)中,硫铁矿渣和硝酸溶液的质量体积比为0.2~0.4g/mL。
作为一种优选实施方式,步骤1)中,蔗糖与去离子水的质量体积比为0.5g/mL,硫铁矿渣与蔗糖的重量比为1:1。
与现有技术相比,本发明具有如下有益效果:
(1) 本发明的催化剂采用改性硫铁矿渣作为催化剂载体,其大大降低了催化剂的生产费用,催化剂的整体制备工艺简单,易于放大;同时为硫铁矿渣的资源化利用提供了一条新途径,使其附加值获得提升;
(2)本发明利用稀硝酸对硫铁矿渣进行预处理可以去除矿渣中的部分杂质,增大空隙宽度,改善空隙结构,同时破坏内部的晶格结构,削弱粒子间的相互作用,增大其表面积;此外,酸化处理过程中H+还可以置换出比其体积大的Ca+, K+, Na+等进一步增大孔隙,增强NH3和NO在其表面上的吸附性能;
(3)本发明在硫铁矿渣的表面涂覆了碳微球,从而可以使硫铁矿渣的比表面积从原来的20m2/g提高到改性后的400~600m2/g,一方面有利于活性组分在其表面的分散,为催化反应提供更多的反应活性位点;另一方面较高的比表面积有利于NO和NH3在其表面的吸附,从而加强催化反应的进行;同时可以在一定程度上抑制硫酸铵盐对其活性位的覆盖,从而提高其抗硫中毒性能;
(4)本发明的催化剂在制备过程中掺入的硝酸钇一方面可以与V2O5作用结合生成钒酸钇提高催化剂的热稳定性,降低V2O5在反应环境下发生升华的可能性;另一方面硝酸钇可与硫酸铈相互作用,进而强化脱硝活性;同时,采用碳微球对硫铁矿渣进行包覆,碳微球表面丰富的氧空位有利于NO和NH3在其表面的活化,从而强化其反应活性;同时,碳微球表面丰富的氧空位也有利于反应过程中生成的硫酸铵盐的分解,进而加强其抗硫活性。
具体实施方式
为了使本技术领域人员更好地理解本发明的技术方案,并使本发明的上述特征、目的及优点更加清晰易懂,现结合实施例对本发明做进一步解释说明,应当指出的是,在此列出的所有实施例仅仅是说明性的,并不意味着对本发明范围进行限定。以下实施例中所使用的硫铁矿渣的成分组成如表1所示:
表1硫铁矿渣成分组成
实施例1
1)硫铁矿渣预处理:将硫铁矿渣原料破碎,筛分出60~80目的硫铁矿渣溶于质量浓度为2%的稀硝酸溶液中,在室温下搅拌6h后进行过滤,将滤出的(即未溶解的)硫铁矿渣过滤洗涤至中性后,在105℃条件下干燥处理12h;
2)硫铁矿渣改性:称取100g蔗糖溶于200mL去离子水中在室温下搅拌使其完全溶溶解,得到蔗糖溶液;然后向蔗糖溶液中加入100g步骤1)中所得的硫铁矿渣并继续搅拌处理10min,得到混合物A;将混合物A转移至水热反应釜中,在220℃条件下处理2h,得到混合物B;将混合物B过滤得到的滤饼用乙醇洗涤4次后,在110℃的条件下干燥处理6h后于500℃的氮气气氛下焙烧4h,得到涂覆有碳微球涂层的改性硫铁矿渣;
3)活性组分负载:称取2gV2O5和2g草酸溶于200mL去离子水中,在室温下搅拌使其完全溶解;随后向其中加入3g硝酸钇和8g硫酸铈并继续搅拌30min,然后向其中加入100g步骤2)中所得的改性硫铁矿渣,得到混合物C;将混合物C置于水热反应釜中于140℃下处理36h,然后将其在80℃的水浴搅拌条件下进行缓慢蒸发,直至其表面的水分消失后,再置于105℃的条件下干燥处理12h,而后转移至高温加热炉中在N2保护的气氛下于500℃继续处理5h后进行压片成型,得到催化剂1。
实施例2
1)硫铁矿渣预处理:将硫铁矿渣原料破碎,筛分出60~80目的硫铁矿渣溶于质量浓度为5%的稀硝酸溶液中,在室温下搅拌4h后进行过滤,将滤出的(即未溶解的)硫铁矿渣过滤洗涤至中性后,在105℃条件下干燥处理12h;
2)硫铁矿渣改性:称取100g蔗糖溶于200mL去离子水中在室温下搅拌使其完全溶溶解,得到蔗糖溶液;然后向蔗糖溶液中加入100g步骤1)中所得的硫铁矿渣并继续搅拌处理15min,得到混合物A;将混合物A转移至水热反应釜中,在180℃条件下处理4h,得到混合物B;将混合物B过滤得到的滤饼用乙醇洗涤4次后,在110℃的条件下干燥处理6h后于500℃的氮气气氛下焙烧4h,得到涂覆有碳微球涂层的改性硫铁矿渣;
3)活性组分负载:称取3gV2O5和3g草酸溶于200mL去离子水中,在室温下搅拌使其完全溶解;随后向其中加入5g硝酸钇和12g硫酸铈并继续搅拌30min,然后向其中加入100g步骤2)中所得的改性硫铁矿渣,得到混合物C;将混合物C置于水热反应釜中于160℃下处理24h,然后将其在60℃的水浴搅拌条件下进行缓慢蒸发,直至其表面的水分消失后,再置于105℃的条件下干燥处理12h,而后转移至高温加热炉中在N2保护的气氛下于500℃继续处理5h后进行压片成型,得到催化剂2。
实施例3
1)硫铁矿渣预处理:将硫铁矿渣原料破碎,筛分出60~80目的硫铁矿渣溶于质量浓度为3%的稀硝酸溶液中,在室温下搅拌6h后进行过滤,将滤出的(即未溶解的)硫铁矿渣过滤洗涤至中性后,在105℃条件下干燥处理12h;
2)硫铁矿渣改性:称取100g蔗糖溶于200mL去离子水中在室温下搅拌使其完全溶溶解,得到蔗糖溶液;然后向蔗糖溶液中加入100g步骤1)中所得的硫铁矿渣并继续搅拌处理15min,得到混合物A;将混合物A转移至水热反应釜中,在200℃条件下处理3h,得到混合物B;将混合物B过滤得到的滤饼用乙醇洗涤4次后,在110℃的条件下干燥处理6h后于500℃的氮气气氛下焙烧4h,得到涂覆有碳微球涂层的改性硫铁矿渣;
3)活性组分负载:称取2gV2O5和2g草酸溶于200mL去离子水中,在室温下搅拌使其完全溶解;随后向其中加入4g硝酸钇和10g硫酸铈并继续搅拌30min,然后向其中加入100g步骤2)中所得的改性硫铁矿渣,得到混合物C;将混合物C置于水热反应釜中于150℃下处理30h,然后将其在70℃的水浴搅拌条件下进行缓慢蒸发,直至其表面的水分消失后,再置于105℃的条件下干燥处理12h,而后转移至高温加热炉中在N2保护的气氛下于500℃继续处理5h后进行压片成型,得到催化剂3。
对上述实施例1~3所得催化剂进行性能测试,测试条件为:在固定床反应器中进行,模拟烟气组成为:1000ppmNH3,1000ppm NO,5% O2, 100ppm SO2(需要时),10%H2O(需要时),N2为平衡气,总流量为600mL/min,反应空速为30000 h-1, 反应温度为150~450℃,反应产物中NO和NO2含量用烟气分析仪KM9106进行分析测定,具体测试结果如下表1.2所示。
表1.2活性评价结果
实施例4
将实施例2中制得的催化剂2,在固定床反应器上考察SO2和H2O对催化反应活性的影响。反应混合气的组成为[NH3]=[NO]=1000ppm,[O2]=6%,[SO2]=500ppm,[H2O]=10%,N2为平衡气,反应空速为30,000h-1,反应温度为300oC。实验结果表明:在通入SO2和H2O 12h后,NOx的转化率略有下降3~5%,在实验考察的48h内基本保持稳定,当SO2和H2O 去除后催化活性基本恢复到99%的NOx转化率。
Claims (4)
1.一种基于硫铁矿渣的脱硝催化剂的制备方法,其特征在于是通过如下步骤实现的:
1)硫铁矿渣预处理:将硫铁矿渣原料破碎,筛分出60~80目的硫铁矿渣溶于质量浓度为2~5%的稀硝酸溶液中,在室温下搅拌4~8h后进行过滤,将滤出的硫铁矿渣过滤洗涤至中性后,在105℃条件下干燥处理12h;
2)硫铁矿渣改性:向去离子水中加入蔗糖并在室温下搅拌使其完全溶溶解,得到蔗糖溶液;然后向蔗糖溶液中加入经步骤1)处理得到的硫铁矿渣,继续搅拌10~15min,得到混合物A;将混合物A转移至水热反应釜中,在180~220℃条件下处理2~4h,得到混合物B;将混合物B过滤得到的滤饼用乙醇洗涤2~4次后,在110℃的条件下干燥处理6h后于500℃的氮气气氛下焙烧4h,得到涂覆有碳微球涂层的改性硫铁矿渣;
3)活性组分负载:将等重量的V2O5和草酸溶于去离子水中,在室温下搅拌使其完全溶解;随后向其中加入硝酸钇和硫酸铈并继续搅拌30min,然后向其中加入步骤2)所得的改性硫铁矿渣,得到混合物C;将混合物C置于水热反应釜中于140~160℃下处理24~36h后降至室温,然后将其在60~80℃的水浴搅拌条件下进行缓慢蒸发,直至其表面的水分消失后,再置于105℃的条件下干燥处理12h,而后转移至高温加热炉中在N2保护的气氛下于500℃继续处理5h后进行压片成型,得到催化剂。
2.如权利要求1所述的制备方法,其特征在于:步骤3)中,所述V2O5与改性硫铁矿渣的重量比为1%~3%,所述硝酸钇与改性硫铁矿渣的重量比为2%~5%;所述硫酸铈的重量与改性硫铁矿渣的重量比为8%~12%。
3.如权利要求1所述的制备方法,其特征在于:步骤1)中,硫铁矿渣和硝酸溶液的质量体积比为0.2~0.4g/mL。
4.如权利要求1所述的制备方法,其特征在于:步骤2)中,蔗糖与去离子水的质量体积比为0.5g/mL,硫铁矿渣与蔗糖的重量比为1:1。
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