CN106807390A - 一种W型火焰锅炉NOx超净排放的方法及其SCO除氨催化剂 - Google Patents
一种W型火焰锅炉NOx超净排放的方法及其SCO除氨催化剂 Download PDFInfo
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Abstract
本发明一种W型火焰锅炉NOx超净排放的方法及其SCO除氨催化剂;该工艺简单,脱硝效率高,氨逃逸低;同时,SCO催化剂制备简单,活性高,成本低。所述的SCO除氨催化剂,包括活性组分和载体;所述的活性组分由活性组分前躯体煅烧得到,所述的活性组分前驱体为铈盐、铜盐、钴盐和钒盐;所述的铈盐、铜盐或钴盐均为硝酸盐、醋酸盐或硫酸盐,钒盐为偏钒酸铵或乙酰丙酮氧钒;所述的载体为锐钛矿型纳米TiO2或纳米α‑Al2O3;其中,铈元素占催化剂的质量分数为1~20%,铜元素占催化剂的质量分数为0~15%,钴元素占催化剂的质量分数为0~15%,钒元素占催化剂的质量分数为0.5~5%。
Description
技术领域
本发明涉及W型火焰锅炉NOx超净排放方法,具体为一种W型火焰锅炉NOx超净排放的方法及其SCO除氨催化剂。
背景技术
随着国家对环保的重视,超净排放正成为电力环保领域研究的热点。所谓超净排放是指通过适当的技术使燃煤机组的大气主要污染物排放标准达到天然气燃气机组的排放标准(烟尘5mg/m3,SO2 35mg/m3,NOx 50mg/m3)。其中,NOx超净排放是整个超净排放的核心技术之一。目前,实现燃煤机组NOx超净排放的方法主要有:燃烧器的低氮改造以及SCR脱硝工艺优化。一般来说,燃烧器低氮改造可将NOx浓度降低200-300mg/m3,而SCR催化剂的脱硝效率设计值通常为90%。这就意味着,上述方法仅适合NOx排放值较低(NOx≤800mg/m3)的锅炉,而对于排放值较高的W型火焰锅炉,这些方法很难实现NOx的超净排放。
W型火焰锅炉是我国大型电站锅炉燃用低挥发份燃料的主要燃烧方式之一。目前国内已投运的大型W型火焰锅炉有近200台。此类锅炉的特点是NOx排放值高,额定出力工况下NOx排放值一般在850-1300mg/m3之间,现有超净排放技术无法在不增加氨逃逸的前提下将该值降至50mg/m3,因此,开发适用于W型火焰锅炉NOx超净排放技术显得尤为必要与重要。
发明内容
针对现有技术中存在的问题,本发明提供一种W型火焰锅炉NOx超净排放的方法及其SCO除氨催化剂;该工艺简单,脱硝效率高,氨逃逸低;同时,SCO催化剂制备简单,活性高,成本低。
本发明是通过以下技术方案来实现:
一种W型火焰锅炉NOx超净排放的SCO除氨催化剂,包括活性组分和载体;
所述的活性组分由活性组分前躯体煅烧得到,所述的活性组分前驱体为铈盐、铜盐、钴盐和钒盐;所述的铈盐、铜盐或钴盐均为硝酸盐、醋酸盐或硫酸盐,钒盐为偏钒酸铵或乙酰丙酮氧钒;
所述的载体为锐钛矿型纳米TiO2或纳米α-Al2O3;
其中,铈元素占催化剂的质量分数为1~20%,铜元素占催化剂的质量分数为0~15%,钴元素占催化剂的质量分数为0~15%,钒元素占催化剂的质量分数为0.5~5%。
优选的,所述的活性组分相对于载体的质量分数为5~20%。
优选的,所述催化剂为粉末状或蜂窝状或板式或波纹板式。
优选的,粉末状催化剂采用浸渍煅烧法或者溶胶凝胶法制备得到;蜂窝状、板式或波纹板式催化剂均采用SCR催化剂的制备工艺制备得到。
优选的,所述的活性组分由活性组分前躯体在300-700℃的温度下煅烧得到。
一种W型火焰锅炉NOx超净排放的方法,将本发明所述的SCO除氨催化剂设置在W型火焰锅炉SCR脱硝段中,且布置在SCR脱硝催化剂下游;通过调节SCR脱硝段中的喷氨量增加氨氮比提高脱硝效率,脱硝后烟气中过剩的氨气在下游SCO除氨催化剂的作用下按照式(1)进行催化氧化,最终转化为N2和水。
4NH3+3O2→2N2+6H2O (1)
优选的,SCR脱硝段前烟气中的氨氮比为0.8~1.2。
优选的,SCR脱硝入口烟气中中氨气含量为300~800ppm,二氧化硫含量为200~3000ppm,氧气含量为4~10%,NOx含量为300~800ppm,水蒸气含量1~10%,烟温为280~420℃,空速为2000~8000h-1。
与现有技术相比,本发明具有以下有益的技术效果:
本发明提供的催化剂以来源广泛、价格低廉的铜、钴、铈氧化物代替钌、银等贵金属作为活性组分,有效降低了催化剂的成本;其中,钒氧化物能有效提高催化表面酸性,更高效的络合NH3;铜、铈氧化物具有较好的储/释氧能力以及良好的Ce3+/Ce4+,Cu2+/Cu+切换能力,能很好的氧化吸附在催化剂上的NH3;钴氧化物可高效络合NO,通过NH3-SCR途径提高氨的转换效率。将四种组分同时引入催化剂中作为活性组分,从而使本发明提供的催化剂可实现在电厂常规SCR脱硝温度段高效除氨的作用。催化剂活性高,有较强的抗硫性和抗水蒸气能力。
进一步的,催化剂通过成熟的制备方法制备合成,适合工业化生产。
本发明将选择性催化氧化(SCO)的除氨催化剂置于SCR脱硝催化剂的下游,在提高W型火焰锅炉脱硝效率的同时,并没有提高氨逃逸,防止了空预器堵塞的发生。填补相关技术空白,具有重要的科学意义和工程应用价值。
附图说明
图1为本发明实例中所述的除氨催化剂的布置示意图。
图中:1为SCR脱硝段,2为SCR脱硝催化剂层,3为SCO除氨催化剂层。
具体实施方式
下面结合具体的实施例对本发明做进一步的详细说明,所述是对本发明的解释而不是限定。
本发明所述的SCO除氨催化剂使用时,如图1所示,将SCO除氨催化剂设置在W型火焰锅炉SCR脱硝段1中,且布置在SCR脱硝催化剂层2的下游;通过调节SCR脱硝段中的喷氨量增加氨氮比提高脱硝效率,脱硝后烟气中过剩的氨气在下游的SCO除氨催化剂层3的作用下催化氧化为N2和水。
将本发明所述的除氨催化剂放在管式炉反应器内进行催化剂的活性测试,采用SCR+SCO催化剂双层布置方式,其中SCO除氨催化剂采用SCR蜂窝催化剂的制备工艺制备得到。模拟烟气条件为氨气含量为300~800ppm,二氧化硫含量为200~3000ppm,氧气含量为4~10%,NOx含量为300~800ppm,水蒸气含量1~10%,烟温为280~420℃,气体空速为2000~8000h-1。
按式(2)计算脱硝效率。
在式(2)中,η表示脱硝效率,[NOx]in表示入管式炉前的模拟烟气中的NOx含量,单位为ppm;[NOx]out表示入管式炉后的模拟烟气中的NOx含量,单位为ppm。氨气逃逸量用化学吸收法来检测,单位为ppm。
实施例1
SCO除氨催化剂载体选纳米α-Al2O3,其中铈元素占催化剂的质量分数为9%,铜元素占催化剂的质量分数为5%,钴元素占催化剂的质量分数为2%,钒元素占催化剂的质量分数为0.5%。模拟烟气条件为:NH3含量为500ppm,SO2含量为200ppm,O2含量为(v/v)6%,NOx含量为500ppm,水蒸气为5%,烟温为300℃,空速为4000h-1。
实施例2
SCO除氨催化剂载体选纳米氧化钛,其中铈元素占催化剂的质量分数为12%,铜元素占催化剂的质量分数为3%,钴元素占催化剂的质量分数为2%,钒元素占催化剂的质量分数为1%。模拟烟气条件为:NH3含量为500ppm,SO2含量为1000ppm,O2含量为(v/v)7%,NOx含量为500ppm,水蒸气为5%,烟温为350℃,空速为2000h-1。
实施例3
SCO除氨催化剂载体选纳米氧化钛,其中铈元素占催化剂的质量分数为10%,铜元素占催化剂的质量分数为2%,钴元素占催化剂的质量分数为2%,钒元素占催化剂的质量分数为0.5%。模拟烟气条件为:NH3含量为600ppm,SO2含量为2000ppm,O2含量为(v/v)6%,NOx含量为500ppm,水蒸气为5%,烟温为380℃,空速为5000h-1。
实施例4
SCO除氨催化剂载体选纳米氧化钛,其中铈元素占催化剂的质量分数为,5%,铜元素占催化剂的质量分数为4%,钴元素占催化剂的质量分数为3%,钒元素占催化剂的质量分数为2%。模拟烟气条件为:NH3含量为400ppm,SO2含量为1000ppm,O2含量为(v/v)6%,NOx含量为500ppm,水蒸气为5%,烟温为280℃,空速为6000h-1。
实施例5
SCO除氨催化剂载体选纳米氧化钛,其中铈元素占催化剂的质量分数为5%,铜元素占催化剂的质量分数为10%,钴元素占催化剂的质量分数为4%,钒元素占催化剂的质量分数为2.5%。模拟烟气条件为:NH3含量为550ppm,SO2含量为1000ppm,O2含量为(v/v)6%,NOx含量为600ppm,水蒸气为10%,烟温为400℃,空速为3000h-1。
实施例6
SCO除氨催化剂载体选纳米氧化钛,其中铈元素占催化剂的质量分数为4%,铜元素占催化剂的质量分数为13%,钴元素占催化剂的质量分数为2%,钒元素占催化剂的质量分数为0.5%。模拟烟气条件为:NH3含量为700ppm,SO2含量为200ppm,O2含量为(v/v)6%,NOx含量为600ppm,水蒸气为10%,烟温为320℃,空速为7000h-1。
实施例7
SCO除氨催化剂载体选纳米氧化钛,其中铈元素占催化剂的质量分数为15%,铜元素占催化剂的质量分数为2%,钴元素占催化剂的质量分数为2%,钒元素占催化剂的质量分数为0.5%。模拟烟气条件为:NH3含量为700ppm,SO2含量为200ppm,O2含量为(v/v)6%,NOx含量为600ppm,水蒸气为10%,烟温为420℃,空速为8000h-1,
实施例8
SCO除氨催化剂载体选纳米α-Al2O3,其中铈元素占催化剂的质量分数为15%,铜元素占催化剂的质量分数为2%,钴元素占催化剂的质量分数为2%,钒元素占催化剂的质量分数为0.5%。模拟烟气条件为:NH3含量为400ppm,SO2含量为200ppm,O2含量为(v/v)6%,NOx含量为400ppm,水蒸气为10%,烟温为280℃,空速为4500h-1。
以上实例的数据统计如表1所示。
表1实施例1-8的脱硝效率和氨逃逸量。
本方法以铈盐、铜盐、钴盐、钒盐为主催化剂前驱体。纳米氧化钛或纳米α-Al2O3为载体,SCO除氨催化剂置于SCR脱硝催化剂的下游。当SCO除氨催化剂中铈元素为4%~15%,铜元素为2%~10%,钴元素为2%~4%,钒元素为0.5%~2.5%,载体为纳米氧化钛,烟气温度为300~400℃,氨氮比为0.9~1.2,烟气组分含量为电厂运行工况时,该方法对NOx的脱除率可高达96%以上,且氨逃逸小于3ppm。本发明公开的方法工艺布置简单可行,所述催化剂活性高,有较强的抗硫性和抗水蒸气能力,制备方法采用传统工艺流程,适合工业化生产,在W型火焰锅炉NOx超净排放领域具有广阔的应用前景。
Claims (8)
1.一种W型火焰锅炉NOx超净排放的SCO除氨催化剂,其特征在于,包括活性组分和载体;
所述的活性组分由活性组分前躯体煅烧得到,所述的活性组分前驱体为铈盐、铜盐、钴盐和钒盐;所述的铈盐、铜盐或钴盐均为硝酸盐、醋酸盐或硫酸盐,钒盐为偏钒酸铵或乙酰丙酮氧钒;
所述的载体为锐钛矿型纳米TiO2或纳米α-Al2O3;
其中,铈元素占催化剂的质量分数为1~20%,铜元素占催化剂的质量分数为0~15%,钴元素占催化剂的质量分数为0~15%,钒元素占催化剂的质量分数为0.5~5%。
2.根据权利要求1所述的一种W型火焰锅炉NOx超净排放的SCO除氨催化剂,其特征在于,所述的活性组分相对于载体的质量分数为5~20%。
3.根据权利要求1所述的一种W型火焰锅炉NOx超净排放的SCO除氨催化剂,其特征在于,所述催化剂为粉末状或蜂窝状或板式或波纹板式。
4.根据权利要求3所述的一种W型火焰锅炉NOx超净排放的SCO除氨催化剂,其特征在于,粉末状催化剂采用浸渍煅烧法或者溶胶凝胶法制备得到;蜂窝状、板式或波纹板式催化剂均采用SCR催化剂的制备工艺制备得到。
5.根据权利要求1所述的一种W型火焰锅炉NOx超净排放的SCO除氨催化剂,其特征在于,所述的活性组分由活性组分前躯体在300-700℃的温度下煅烧得到。
6.一种W型火焰锅炉NOx超净排放的方法,其特征在于,将如权利要求1-5中任意一项所述的SCO除氨催化剂设置在W型火焰锅炉SCR脱硝段中,且布置在SCR脱硝催化剂下游;通过调节SCR脱硝段中的喷氨量增加氨氮比提高脱硝效率,脱硝后烟气中过剩的氨气在下游SCO除氨催化剂的作用下催化氧化为N2和水。
7.根据权利要求6所述的一种W型火焰锅炉NOx超净排放的脱硝方法,其特征在于,SCR脱硝段前烟气中的氨氮比为0.8~1.2。
8.根据权利要求6所述的一种W型火焰锅炉NOx超净排放的脱硝方法,其特征在于,SCR脱硝段入口烟气中氨气含量为300~800ppm,二氧化硫含量为200~3000ppm,氧气含量为4~10%,NOx含量为300~800ppm,水蒸气含量1~10%,烟温为280~420℃,气体空速为2000~8000h-1。
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