CN113385030A - 一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法及应用 - Google Patents
一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法及应用 Download PDFInfo
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Abstract
一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法及应用属于环境材料、环境催化及环境保护领域。本发明以硅酸盐类矿物作为原料,采用简单沉淀法制备脱硝多孔材料,用于水泥窑炉NOx减排。所述脱硝材料制备的原料储量丰富,类型齐全、获取简便;制备脱硝材料成本低,流程短,工艺简单,适合工业化生产;脱硝性能好,900~1000℃脱硝率可达到93%以上。本发明在脱硝过程中可以改善氨利用率,提高脱硝效率,避免出现氨逃逸等污染问题,保护环境,并对硅酸盐类矿物进行有效利用,具有可观的经济和环保效益。
Description
技术领域
本发明属于环境催化材料及环境保护领域,具体为一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法及应用。
背景技术
我国氮氧化物(NOx)排放总量居高不下,是一系列环境问题的根源所在。水泥熟料在煅烧过程中会排放大量NOx和粉尘,是现今工业NOx排放的主要污染源,因此,NOx减排已成为水泥行业的重点任务。
目前水泥行业通常使用的NOx减排技术都需要使用氨水或者尿素作为还原剂,存在氨逃逸的问题,容易造成二次污染。面对传统NOx减排材料存在的问题,研究一种可以提高还原剂脱硝性能的高温催化脱硝材料备受关注。
硅酸盐类矿物是含有硅酸根的矿物的总称,可以看作SiO2和其他氧化物(多为金属氧化物)的结合体。这类矿物具有良好的吸附性,热稳定性和阳离子交换性。改性的硅酸盐类矿物良好的催化活性、稳定性和吸附性,在污水处理等多个领域得到了人们的关注。并且改性的硅酸盐类矿物是良好的载体材料,可以负载活性金属材料,提高催化性能。
我国硅酸盐类矿物储量丰富,有着类型齐全、储量丰富、质地优良等特点,部分矿物已在陶瓷、造纸、石油化工和建筑材料等领域应用广泛,但是将硅酸盐类矿物应用在水泥行业脱硝领域的研究却很少,之前研究的多孔材料,主要是设计用于选择性催化还原技术(SCR)脱硝的催化剂,而在选择性非催化还原技术(SNCR)中,通常不使用催化剂,使用此类脱硝材料作为催化剂,可以提高SNCR技术的脱硝性能。并且由于其成分与水泥相似相容,可以随水泥生料进入预热器和分解炉内,在较高温度下完成脱硝反应,在不影响水泥性能的同时,完成NOx减排,具有巨大的经济和环保效益。
发明内容
本发明的目的是提供一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法及应用。
本发明的制备步骤具体如下:
将纯净的硅酸盐类矿物在500℃条件下焙烧2h;随后加入3mol/L盐酸,硅酸盐类矿物与盐酸固液质量比为1:5.5~6.5,混合搅拌2h;加入去离子水,使固液质量比调节至1:10.5~11.5,继续搅拌30min,形成均匀的悬浮液;向混合溶液中加入NaOH溶液,至pH=7,搅拌30min;离心分离出底部沉淀,60℃条件下干燥12h,制得脱硝材料。
本发明的脱硝率测试是以NO作为还原气体,模拟烟气组成为1000ppm的NO,N2为平衡气,气体流速2000ml/min,反应空速为27000h-1。首先将催化材料造粒,取粒度在50目~100目之间的颗粒进行测试,量取2g,SCR脱硝反应在900~1000℃温度条件下进行,本发明制备的脱硝材料的脱硝效率最高可达95%。
进一步,硅酸盐类矿物可选择膨润土、硅藻土的一种。
本发明优点:
(1)制备所有原料资源丰富、获取便捷,分布广泛,成本低廉。且制备工艺简单,节约能耗,适合水泥行业使用。
(2)使用盐酸是将膨润土中的蒙脱石结构酸改性,使之形成介孔结构,增加材料表面的阳离子交换能力和氧空位,更好的与NO结合,增加其吸附催化能力。酸的选择上,考虑到膨润土中阳离子种类,以及酸根对于催化剂后续离子筛选,盐酸是最合适的选择,。其次NaOH的主要作用是为了调节ph值,使Fe离子等活性离子沉淀,筛选其他杂质离子,同时NaOH中的Na离子不会影响钠基膨润土的化学组成。
(3)硅酸盐类矿物制备脱硝材料用于水泥NOx减排,可以改善氨水或尿素等还原剂的利用率,提高高温SNCR工艺的脱硝效率,避免发生氨逃逸等污染问题,对环境友好,利于生态保护。
(4)硅酸盐类矿物与水泥成分相似相容,可以与水泥生料混合,在较高温度下完成脱硝反应,不影响水泥性能。
具体实施方式
实施例一:
将纯净的钠基膨润土放入马弗炉中,500℃焙烧2h;称取膨润土粉末10g,加入3mol/L盐酸60ml,与膨润土粉末混合,搅拌2h;加入50ml去离子水继续搅拌30min;向混合溶液中加入2mol/L的NaOH溶液,至pH=7,搅拌30min;离心分离出底部沉淀,60℃干燥12h,制得多孔催化材料粉末。
脱硝率测试:模拟烟气成分1000ppm的NO,N2为保护气,气体流速2000ml/min,反应空速为27000h-1。在900℃~1000℃的温度范围内脱硝率可达93%以上。
实施例二:
将纯净的硅藻土放入马弗炉中,500℃焙烧2h;称取硅藻土粉末10g,加入3mol/L盐酸60ml,与硅藻土粉末混合,搅拌2h;加入50ml去离子水继续搅拌30min;向混合溶液中加入2mol/L的NaOH溶液,至pH=7,搅拌30min;离心分离出底部沉淀,60℃干燥12h,制得多孔催化材料粉末。
脱硝率测试:模拟烟气成分1000ppm的NO,N2为保护气,气体流速2000ml/min,反应空速为27000h-1。在900℃~1000℃的温度范围内脱硝率可达90%以上。
实施例三:
称取纯净的膨润土粉末10g,加入3mol/L盐酸60ml,与膨润土粉末混合,搅拌2h;加入50ml去离子水继续搅拌30min;向混合溶液中加入2mol/L的NaOH溶液,至pH=7,搅拌30min;离心分离出底部沉淀,60℃干燥12h,制得多孔催化材料粉末。
脱硝率测试:模拟烟气成分1000ppm的NO,N2为保护气,气体流速2000ml/min,反应空速为27000h-1。在900℃~1000℃的温度范围内脱硝率可达80%以上。
Claims (3)
1.一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法,其特征在于:将硅酸盐类矿物在500℃条件下焙烧2h;焙烧后在硅酸盐矿物中,加入3mol/L的盐酸,硅酸盐类矿物与盐酸固液质量比为1:5.5~6.5,混合搅拌2h;加入去离子水,使固液质量比调节至1:10.5~11.5,继续搅拌30min,形成均匀的悬浮液;向混合溶液中加入NaOH溶液,至pH=7,搅拌30min;离心分离出底部沉淀,60℃干燥12h,制得多孔材料粉末。
2.根据权利要求1所述的一种利用硅酸盐类矿物制备水泥窑烟气脱硝材料的方法,其特征在于:硅酸盐类矿物选择膨润土、硅藻土中的一种。
3.采用如权利要求1所述方法所制备的粉末在作为水泥窑烟气脱硝材料的应用。
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