CN113289616A - 一种用于no氧化催化剂及其制备方法 - Google Patents
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Abstract
本发明涉及一种用于NO氧化催化剂,其特征在于,所述催化剂包括:载体和负载在载体上的活性组份,其中所述载体为γ‑氧化铝,所述活性组份是锰、铁、铜、钴、铬或铈的氧化物中的一种或几种;活性组分负载质量为载体质量的10‑25%。通过简单的浸渍法将活性组分负载到载体上,得到NO氧化催化剂。本催化剂在275℃较低的温度窗口,在有氧的条件下,NO转化率达最高到98.5%,并且具有良好的抗硫性。本方法制备的催化剂来源广泛,价格低廉,具有良好的工业应用潜力。
Description
技术领域
本发明属于工业催化剂技术及环境保护技术领域,具体涉及一种用于NO氧化催化剂及其制备方法,尤其是一种用于低温选择性氧化NO的金属氧化物负载型催化剂的制备方法及性质研究。
背景技术
化石燃料燃烧过程中排放出大量的氮氧化物,包括一氧化氮,二氧化氮和一氧化二氮等,会造成酸雨和光化学烟雾等环境问题。其中氮氧化物中90%为一氧化氮,因此一氧化氮的脱除已经成了热点问题。
NO脱硝方法主要有两种,一种是将NO还原成氮气,目前火电厂应用最广泛的是选择性催化还原(NH3-SCR)技术,但NH3-SCR安全性低,成本高,且具有严格的温度窗口。另一种方法是将NO氧化成高价态的氮氧化物,然后利用碱性、氧化性或还原性液体将其吸收,适用于中小型企业。利用氧化法脱除NO成本低,在低温范围内可以达到较高的脱除效率。
NO氧化法的核心是催化剂,按照活性组分的不同可分为贵金属与非贵金属催化剂两大类。其中,Pt、Pd、Ag等贵金属催化剂已经有了广泛研究,具有较好的脱硝效率,但是该类催化剂存在价格昂贵的问题,难以在工业中广泛使用。非贵金属价态多变且价格相对低廉,且具有较好的催化活性,因为,该类催化剂的制备引起了工业界的广泛关注。
中国专利文献CN107824192B公开发明了一种用于烟气脱硝的Sr2FeTaO6/氧化铝复合催化剂及其制备方法,该催化剂主要由碳酸锶、五氧化二钽和铁粒为原料制成Sr2FeTaO6,再涂覆在载体氧化铝小球表面制得。该催化剂具有反应窗口宽、环境友好、低温活性好等优点。但该脱硝方法为NH3-SCR法,安全性低,成本高,且会造成NH3泄露的问题。中国专利CN107376913A公开了一种可用于NO高效催化净化的γ-氧化铝基氧化铜纳米材料及其制备方法。该材料由γ相的Al2O3泡沫陶瓷及其表面原位生长的CuO纳米粒子组成。该催化剂制备成本低,催化效果较好,步骤简便,但其转化温度较高。因此开发低温高效、低成本的NO氧化催化剂具有重要意义。
发明内容
本发明的目的是提供一种用于NO氧化催化剂,该催化剂在较低温度下具有较高NO转化率的多元氧化物负载型催化剂,能够解决相关技术中在低温下转化率较低的问题,本发明的另一目的是提供上述催化剂的制备方法。
本发明的技术方案为:一种用于NO氧化催化剂,其特征在于,所述催化剂包括:载体和负载在载体上的活性组份,其中所述载体为γ-氧化铝,所述活性组份是锰、铁、铜、钴、铬或铈的氧化物中的一种或几种;活性组分负载质量为载体质量的10-25%。
优选所述的γ-氧化铝载体的平均孔径为9-12nm,孔容为0.30-0.50cm3/g,比表面积为130-150m2/g。
本发明还提供了一种制备上述的用于NO氧化催化剂的方法,具体步骤如下:
(1)制备活性组份溶液,将活性组分的可溶性盐溶解在溶剂中,制成活性组分溶液;其中,活性组分溶液中可溶性盐的浓度为0.1-0.3mol/L;所述活性组份是锰、铁、铜、钴、铬、铈的醋酸盐、硝酸盐或氯化盐中的一种或多种;
(2)将步骤(1)中制备的活性组分溶液加入γ-氧化铝载体中,超声处理,得到混合溶液;
(3)将步骤(2)得到的混合溶液置于旋蒸中加热蒸发,得到混合物;
(4)将步骤(3)得到的混合物经干燥、焙烧得到NO氧化催化剂。
优选步骤(1)中溶剂为乙醇或水。
优选步骤(2)中所述超声频率为20-60Hz,超声时间为1-1.5h。
优选步骤(3)中所述旋蒸温度为40-80℃。
优选步骤(4)中所述干燥温度为100-120℃,干燥时间为4-6h;所述焙烧温度为400-500℃,焙烧时间为3-4h。
本发明所述的一种用于NO氧化催化剂的应用方法,包括如下步骤:在150-400℃的烟气温度范围内,反应气体组成为:300ppmNO,5%O2,平衡气为N2,气体总流量100mL/min,空速为3.0-6.0h-1的条件下,利用NO氧化催化剂对NO进行氧化。
本发明制备的一种用于NO氧化催化剂的应用方法,包括如下步骤:在275℃的烟气温度范围下,反应气体组成为:300ppmNO,20ppmSO2,5%O2,平衡气为N2,气体总流量100mL/min,空速为6.0h-1的条件下,利用NO氧化催化剂对NO进行抗硫性测试。
本发明的有益效果在于,所述催化剂使用价格相对低廉的过渡金属氧化物和稀土金属氧化物作为催化剂的主要组分,使用简单且易重复的浸渍法制备,制备得到的催化剂在较低温度窗口下具有良好的NO转化率;该催化剂优异的稳定性、寿命长的特点,使其具有良好的工业应用潜力。
附图说明
图1所示为本发明实施例1-5制备的催化剂的XRD图;
图2所示为本发明实施例5于制备的催化剂的NO氧化性能图;
图3所示为本发明实施例5于制备的催化剂的抗硫性能图。
具体实施方式
下面通过附图和实施例对本发明的方案做进一步详述。
实施例1
量取18.4mL浓度为0.2mol/L的醋酸锰溶液,溶剂为水,加入1g未经其他处理的γ-氧化铝载体,所得混合物使用超声处理1h,超声频率为20Hz,置于旋蒸中80℃蒸干水分,然后在120℃烘箱中干燥4h,最后在空气气氛下于400℃焙烧4h。所得催化剂中活性组分含量相对于载体的质量分数为20%,记为Mn/Al2O3催化剂。其中,氧化铝载体的平均孔径为11.6nm,孔容为0.45cm3/g,比表面积为149.2m3/g。催化剂的XRD图见图1。
催化剂的活性评价在固定床反应器中进行,反应气体组成为:300ppmNO,5%O2,平衡气为N2,气体总流量100mL/min,反应空速为3.0h-1,测试的温度范围为150-400℃,在300℃时,达到最高NO转化率78.3%。
实施例2
量取18.4mL浓度为0.1mol/L的醋酸锰溶液和16.8mL浓度为0.1mol/L的氯化钴溶液,溶剂均为水,加入2g未经其他处理的γ-氧化铝载体,所得混合物使用超声处理1h,超声频率为40Hz,置于旋蒸中70℃蒸干水分,然后在100℃烘箱中干燥6h,最后在空气气氛下于450℃焙烧4h。所得催化剂中活性组分含量相对于载体的质量分数为10%,记为MnCo/Al2O3催化剂。其中,氧化铝载体的平均孔径为11.2nm,孔容为0.42cm3/g,比表面积为145.3m3/g。催化剂的XRD图见图1。
催化剂的活性评价在固定床反应器中进行,反应气体组成为:300ppmNO,5%O2,平衡气为N2,气体总流量100mL/min,反应空速为6.0h-1,测试的温度范围为150-400℃,在300℃时,达到最高NO转化率86.3%。
实施例3
量取18.2mL浓度为0.3mol/L的醋酸锰溶液和19.3mL浓度为0.2mol/L的硝酸铬溶液,溶剂均为乙醇,加入2g未经其他处理的γ-氧化铝载体,所得混合物使用超声处理1h,超声频率为50Hz,置于旋蒸中40℃蒸干水分,然后在110℃烘箱中干燥5h。最后在空气气氛下于400℃焙烧3h,所得催化剂中活性组分含量相对于载体的质量分数为25%,记为MnCr/Al2O3催化剂。其中,氧化铝载体的平均孔径为9.3nm,孔容为0.32cm3/g,比表面积为135.4m3/g。催化剂的XRD图见图1。
催化剂的活性评价在固定床反应器中进行,反应气体组成为:300ppmNO,5%O2,平衡气为N2,气体总流量100mL/min,反应空速为3.0h-1,测试的温度范围为150-400℃,在290℃时,达到最高NO转化率82.6%。
实施例4
量取11.7mL浓度为0.2mol/L的氯化铜溶液和6.3mL浓度为0.2mol/L的氯化钴溶液,溶剂均为乙醇,加入1.5g未经其他处理的γ-氧化铝载体,所得混合物使用超声处理1.5h,超声频率为30Hz,置于旋蒸中55℃蒸干水分,然后在100℃烘箱中干燥6h,最后在空气气氛下于500℃焙烧3h。所得催化剂中活性组分含量相对于载体的质量分数为15%,记为CoCu/Al2O3催化剂。其中,氧化铝载体的平均孔径为10.8nm,孔容为0.40cm3/g,比表面积为138.4m3/g。催化剂的XRD图见图1。
催化剂的活性评价在固定床反应器中进行,反应气体组成为:300ppmNO,5%O2,平衡气为N2,气体总流量100mL/min,反应空速为5.0h-1,测试的温度范围为150-400℃,在310℃时,达到最高NO转化率81.5%。
实施例5
量取12.4mL浓度为0.3mol/L的乙酸锰溶液、3.5mL浓度为0.1mol/L的硝酸铈溶液和7.5mL浓度为0.2mol/L的硝酸铁溶液,溶剂均为乙醇,加入2g未经其他处理的γ-氧化铝载体上,所得混合物使用超声处理1.5h,超声频率为60Hz,置于旋蒸中50℃蒸干水分,然后在120℃烘箱中干燥4h,最后在空气气氛下于400℃焙烧3h。所得催化剂中活性组分含量相对于载体的质量分数为16%,记为MnCeFe/Al2O3催化剂。其中,氧化铝载体的平均孔径为11.6nm,孔容为0.45cm3/g,比表面积为149.2m3/g。催化剂的XRD图见图1。
催化剂的活性评价在固定床反应器中进行,反应气体组成为:300ppmNO,5%O2,平衡气为N2,气体总流量100mL/min,反应空速为6.0h-1,测试的温度范围为150-400℃,在290℃时,达到最高NO转化率82.6%。所得结果见图2。
催化剂的抗硫性评价在固定反应器中进行,催化剂用量为0.1g,反应气体组成为:300ppmNO,5%O2,20ppmSO2,平衡气为N2,反应气体总流量为100mL/min,反应空速为6.0h-1,测试的温度为275℃,测试时间为10h。所得结果见图3。
Claims (7)
1.一种用于NO氧化催化剂,其特征在于,所述催化剂包括载体和负载在载体上的活性组份,其中所述载体为γ-氧化铝,所述活性组份是锰、铁、铜、钴、铬或铈的氧化物中的一种或几种;活性组分负载质量为载体质量的10-25%。
2.根据权利要求1所述的用于NO氧化催化剂,其特征在于,所述的γ-氧化铝载体的平均孔径为9-12nm,孔容为0.30-0.50cm3/g,比表面积为130-150m2/g。
3.一种制备如权利要求1所述的用于NO氧化催化剂的方法,具体步骤如下:
(1)制备活性组份溶液,将活性组分的可溶性盐溶解在溶剂中,制成活性组分溶液;其中,活性组分溶液中可溶性盐的浓度为0.1-0.3mol/L;所述活性组份是锰、铁、铜、钴、铬、铈的醋酸盐、硝酸盐或氯化盐中的一种或多种;
(2)将步骤(1)中制备的活性组分溶液加入γ-氧化铝载体中,超声处理,得到混合溶液;
(3)将步骤(2)得到的混合溶液置于旋蒸中加热蒸发,得到混合物;
(4)将步骤(3)得到的混合物经干燥、焙烧得到NO氧化催化剂。
4.根据权利要求3所述方法,其特征在于,步骤(1)中溶剂为乙醇或水。
5.根据权利要求3所述方法,其特征在于,步骤(2)中所述超声频率为20-60Hz,超声时间为1-1.5h。
6.根据权利要求3所述方法,其特征在于,步骤(3)中所述旋蒸温度为40-80℃。
7.根据权利要求3所述方法,其特征在于,步骤(4)中所述干燥温度为100-120℃,干燥时间为4-6h;所述焙烧温度为400-500℃,焙烧时间为3-4h。
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