CN111215137A - 一种利用afv结构分子筛制备的低温scr蜂窝脱硝催化剂、其制备方法及应用 - Google Patents
一种利用afv结构分子筛制备的低温scr蜂窝脱硝催化剂、其制备方法及应用 Download PDFInfo
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Abstract
本发明涉及一种利用AFV结构分子筛制备的低温SCR蜂窝脱硝催化剂、其制备方法及应用。本发明利用具有AFV结构的MnAPO‑57分子筛负载金属元素作为活性组分,保证其具有较高的低温脱硝催化活性,避免活性位点的Mn与硫或水反应而失活,稳定性显著提高,使得其具有相对较好的抗水抗硫性;负载的金属元素与Mn元素协同作用,有效提高该催化剂的低温脱硝催化活性,使得脱硝过程中生成的硫铵盐更容易分解,有效减轻因硫铵盐粘附在催化剂表面而导致催化剂失活的现象,有效提高催化剂的抗硫性。该催化剂在100‑300℃的脱硝效率在80%以上,在500ppmSO2、10%H2O的条件下连续反应168h的脱硝效率基本不下降。
Description
技术领域
本发明属于大气污染治理技术和环保催化剂材料技术领域,尤其涉及一种利用AFV结构分子筛制备的低温SCR蜂窝脱硝催化剂、其制备方法及应用。
背景技术
氮氧化物(NOx)是造成酸雨、光化学烟雾、臭氧层破坏的主要大气污染物之一,对人体健康和生态环境产生严重的危害,如何有效控制和减少NOx的排放受到了各国研究者的广泛关注。
在众多氮氧化物污染控制技术中,选择性催化还原(SCR)技术是应用最广泛、技术最成熟的治理NOx的方法。而SCR技术的核心是脱硝催化剂的催化性能。
目前应用较为广泛的是钒钨钛催化剂(V2O5/W2O3/TiO2)。商用钒钨钛催化剂(V2O5/W2O3/TiO2)在中温段(300~450℃)脱硝催化性能较好,适合应用于中大型燃煤电厂的锅炉尾气处理。但是,在其他非电行业中,如钢铁、冶金、水泥、石化等,锅炉数量众多,燃煤烟气总量大,烟气温度偏低(100℃~ 280℃)。目前针对这类低温燃煤烟气脱硝技术仍未成熟,这使得中小型燃煤锅炉的烟气NOx减排形势十分严峻。有研究表明,锰的氧化物具有较高的低温脱硝催化活性。专利CN103464194A以TiO2与分子筛(ZSM-5)为载体,加入Fe、Mn及Ce的金属盐前驱体,混匀后挤出成型得到蜂窝催化剂,该催化剂具有较高的低温脱硝催化活性与抗水性。专利CN110280262A以TiO2-Al2O3为载体,浸渍法负载Mn与Fe,然后将浸渍后所得粉体Fe-Mn/TiO2-Al2O3涂覆在堇青石上,得到Fe-Mn/TiO2-Al2O3/堇青石蜂窝催化剂,该催化剂具有较高的低温脱硝催化活性。但是锰的氧化物在脱硝过程中容易跟烟气中的硫反应生成盐而快速失活,导致该系列催化剂的抗硫性较差。另外,在低温脱硝过程中生成硫铵盐粘附在催化剂表面,导致脱硝催化剂因催化活性位点被覆盖而逐渐失活。
因此,开发低温活性高、抗硫性好的低温脱硝催化剂是目前的一大难点,本发明为解决这一难题提供了一种有效的解决方法。专利US20140004035A 在2014年首次报道合成了具有AFV结构的分子筛,并将其用于长链烃类的催化裂化。但是目前尚无AFV结构分子筛在脱硝方面应用的相关报道。
发明内容
本发明所要解决的技术问题是,提供一种高效、抗水抗硫性能好的利用 AFV结构分子筛制备的SCR蜂窝脱硝催化剂、其制备方法及应用。
本发明解决上述技术问题的技术方案如下:一种利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂,其组分按重量份数计包括:10-35份活性组分和 50-80份载体;其中,所述活性组分为Me/MnAPO-57,Me为金属元素,载体为TiO2。
进一步,上述SCR蜂窝脱硝催化剂中还包括结构助剂。
进一步,在制备过程中,上述SCR蜂窝脱硝催化剂的原料包括10-35份活性组分、50-80份载体和成型助剂;所述成型助剂包括粘结剂、润滑剂、造孔剂、结构助剂和水;
其中,粘结剂的用量为活性组分和载体总重量的3-15%;润滑剂的用量为活性组分和载体总重量的1-5%;造孔剂的用量为活性组分和载体总重量的 0.5-5%;结构助剂的用量为活性组分和载体总重量的1-15%;水的用量为活性组分和载体总重量的20-50%。
更进一步,所述粘结剂为聚环氧乙烷(PEO)和羧甲基纤维素钠(CMC);其中,所述PEO为活性组分和载体总重量的2-10%,所述CMC为活性组分和载体总重量的1-5%;
所述润滑剂为乳酸;
所述造孔剂为木浆;
所述结构助剂为玻璃纤维,杆状,长度为0.1-0.5mm。
采用上述进一步方案的有益效果是,在制备过程中加入成型助剂,以协助完成催化剂的制备,但是在焙烧过程中,粘结剂、润滑剂、造孔剂均被除去,因此焙烧后的蜂窝催化剂中仅剩下活性组分、载体和结构助剂。
进一步,所述活性组分Me/MnAPO-57为MnAPO-57分子筛通过浸渍法负载Me所得;所述MnAPO-57分子筛通过水热合成法制备得到;其中,Mn占 SCR蜂窝脱硝催化剂的0.1-5wt%。
进一步,所述Me为Ce、Nd、La、Pr、Co、Ni或Zr金属元素中的一种或两种以上,每种金属元素占SCR蜂窝脱硝催化剂的0.1-5wt%。
进一步,所述载体TiO2为锐钛矿型TiO2,比表面积为85-95m2/g,粒径为0.5-50μm。
本发明的第二个目的在于提供上述利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂的制备方法,步骤如下:
(1)将至少一种含Me的前驱体溶解于去离子水中,配制成前驱体溶液;将MnAPO-57分子筛粉末加入前驱体溶液中,在20-90℃条件下搅拌反应 0.5-8h,经烘干、焙烧后,得活性组分Me/MnAPO-57粉末;
(2)取活性组分、载体和成型助剂混合均匀,得到塑性湿料泥团,陈腐6-24h;
(3)将步骤(2)得到的陈腐后塑性泥团在连续真空挤出机中进行炼泥,得到均匀致密的脱气泥段;将得到的脱气泥段在连续真空挤出机中进行挤出成型,得到整体蜂窝催化剂坯体;
(4)将步骤(3)的整体蜂窝催化剂坯体在恒温恒湿箱中干燥,烘干温度为20-100℃,湿度为20%-80%,烘干时间为12-24h;
(5)将烘干后的坯体转移至马弗炉中焙烧,焙烧温度为400-600℃,焙烧时间为2-8h,即得低温SCR蜂窝脱硝催化剂。
进一步,步骤(1)中,所述含Me的前驱体为含有Ce、Nd、La、Pr、Co、 Ni或Zr的硫酸盐、硝酸盐、草酸盐或乙酸盐中的一种或两种以上。
进一步,步骤(1)中的去离子水与MnAPO-57分子筛粉末的重量比为 (1-10):1。
本发明的第三个目的在于提供上述利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂在钢铁、冶金、水泥、石化等行业的低温烟气的脱硝过程中的应用。
本发明的有益效果是:
(1)本发明将具有AFV结构的MnAPO-57分子筛通过浸渍法负载活性金属元素Me得到的Me/MnAPO-57作为催化剂的活性组分。MnAPO-57分子筛中的Mn元素位于分子筛骨架上,与Al、P、O等元素通过桥键连接,受到分子筛体系的保护,既可以保证该产品具有较高的低温脱硝催化活性,又可以避免活性位点的Mn与硫或水反应而失活,稳定性显著提高,使得该催化剂具有相对较好的抗水、抗硫性。
(2)同时,活性金属元素的加入具有明显的助催化效果,活性金属元素与Mn元素协同作用,可以有效提高该催化剂的低温脱硝催化活性;而且活性金属元素的存在可以使得脱硝过程中生成的硫铵盐更容易分解,可有效减轻因硫铵盐粘附在催化剂表面而导致催化剂失活的现象,有效提高了催化剂的抗硫性。
(3)本发明将Me/MnAPO-57催化剂活性组分、载体与成型助剂混合后挤出成型,经烘干、焙烧后得到低温SCR蜂窝脱硝催化剂。该催化剂具有很好的低温脱硝催化活性与抗水、抗硫性,在100-300℃的脱硝效率在80%以上,在500ppmSO2、10%H2O的条件下连续反应168h的脱硝效率基本不下降,在钢铁、冶金、水泥、石化等行业具有很好的应用前景。
附图说明
图1为实施例2与对比例1、2制备的催化剂产品的脱硝催化活性的测试对比图;
图2为实施例2与对比例1、2制备的催化剂产品的脱硝催化稳定性的测试对比图。
具体实施方式
以下对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
本发明实施例中使用的MnAPO-57分子筛为实验室通过水热合成法自制产品。
实施例1
一种利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂,其组分按重量份数计包括:20份Ce/MnAPO-57粉末、70份TiO2粉体、6份PEO、4份CMC、 10份玻璃纤维、2份木浆、3份乳酸和30份去离子水。
上述利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂的制备方法,步骤如下:
(1)将0.2份乙酸铈溶解于100份去离子水中,配制成前驱体溶液;将20份MnAPO-57分子筛粉末加入前驱体溶液中,在60℃条件下搅拌反应 4h,经烘干、焙烧后,得活性组分Ce/MnAPO-57粉末;
(2)取Ce/MnAPO-57粉末、TiO2粉体、6份PEO、4份CMC、10份玻璃纤维和2份木浆混合均匀,再加入3份乳酸和30份去离子水,得到塑性湿料泥团,陈腐12h;
(3)将步骤(2)得到的陈腐后塑性泥团在连续真空挤出机中进行炼泥,得到均匀致密的脱气泥段;将得到的脱气泥段在连续真空挤出机中进行挤出成型,得到整体蜂窝催化剂坯体;
(4)将步骤(3)的整体蜂窝催化剂坯体在恒温恒湿箱中干燥,烘干温度为60℃,湿度为40%,烘干时间为24h;
(5)将烘干后的坯体转移至马弗炉中焙烧,焙烧温度为600℃,焙烧时间为4h,即得活性组分为Ce/MnAPO-57的低温SCR蜂窝脱硝催化剂。
实施例2
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为 Ce-Nd/MnAPO-57粉末,得到活性组分为Ce-Nd/MnAPO-57的低温SCR蜂窝脱硝催化剂。
实施例3
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为Ce-Pr /MnAPO-57粉末,得到活性组分为Ce-Pr/MnAPO-57的低温SCR蜂窝脱硝催化剂。
实施例4
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为Ce-Nd-Co /MnAPO-57粉末,得到活性组分为Ce-Nd-Co/MnAPO-57的低温SCR蜂窝脱硝催化剂。
实施例5
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为La /MnAPO-57粉末,得到活性组分为La/MnAPO-57的低温SCR蜂窝脱硝催化剂。
实施例6
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为La-Ni-Zr /MnAPO-57粉末,得到活性组分为La-Ni-Zr/MnAPO-57的低温SCR蜂窝脱硝催化剂。
对比例1
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为MnAPO-57 粉末,得到活性组分为MnAPO-57的低温SCR蜂窝脱硝催化剂。
对比例2
与实施例1相同,不同之处在于:将Ce/MnAPO-57粉末替换为 Mn-Ce-Nd/TiO2粉末,得到活性组分为Mn-Ce-Nd/TiO2的低温SCR蜂窝脱硝催化剂。
将实施例1-6和对比例1、2所得脱硝催化剂分别置于脱硝催化剂评价装置中,测试其在100-300℃范围内的脱硝催化活性。反应气体组成为:N2做平衡气,1000ppm NO、1000ppmNH3、500ppmSO2、10%H2O、10%O2、空速为6000h-1。测试结果见表1。
将实施例2和对比例1-2所得脱硝催化剂分别置于脱硝催化剂评价装置中,测试其在一定温度下的脱硝催化性能的稳定性,考察该催化剂的抗水、抗硫性能。反应温度为150℃,反应时间为168h,反应气体组成为:N2做平衡气,1000ppm NO、1000ppmNH3、500ppmSO2、10%H2O、10%O2、空速为6000h-1。测试结果见表1与图1、图2。
表1
催化剂编号 | 催化剂活性组分 | 反应窗口温度/℃ | T<sub>0h</sub>/% | T<sub>168h</sub>/% |
实施例1 | Ce/MnAPO-57 | 110~300 | / | / |
实施例2 | Ce-Nd/MnAPO-57 | 100~300 | 92.0 | 92.0 |
实施例3 | Ce-Pr/MnAPO-57 | 110~300 | / | / |
实施例4 | Ce-Nd-Co/MnAPO-57 | 110~300 | / | / |
实施例5 | La/MnAPO-57 | 120~300 | / | / |
实施例6 | La-Ni-Zr/MnAPO-57 | 110~300 | / | / |
对比例1 | MnAPO-57 | 120~300 | 87.5 | 83.8 |
对比例2 | Mn-Ce-Nd/TiO<sub>2</sub> | 110~300 | 91.6 | 65.9 |
注:(1)反应窗口温度是活性测试的脱硝效率在80%以上的温度区间;(2)T0h是稳定性测试在 150℃刚开始稳定反应时的脱硝效率,T168h是在150℃连续稳定反应168h的脱硝效率。
从表1、图1及图2可以看出,实施例2的产品具有较高的低温脱硝催化活性与稳定性,在100-300℃的脱硝效率在80%以上,在500ppmSO2、10%H2O 及150℃条件下连续反应168h,脱硝效率不下降,说明实施例2的产品具有较好的抗水抗硫性能。相比于对比例1,本发明通过浸渍法负载活性金属元素的Me/MnAPO-57作为活性组分,其低温脱硝催化活性得到很大提高。对比例2中,通过浸渍法制备的Mn-Ce-Nd/TiO2作为活性组分,虽然具有相对较高的低温脱硝催化活性,但是其稳定性差,抗水抗硫能力差。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂,其特征在于,其组分按重量份数计包括:10-35份活性组分和50-80份载体;其中,所述活性组分为Me/MnAPO-57,Me为金属元素,载体为TiO2。
2.根据权利要求1所述的SCR蜂窝脱硝催化剂,其特征在于,还包括结构助剂。
3.根据权利要求1或2所述的SCR蜂窝脱硝催化剂,其特征在于,其原料包括10-35份活性组分、50-80份载体和成型助剂;所述成型助剂包括粘结剂、润滑剂、造孔剂、结构助剂和水;
其中,粘结剂的用量为活性组分和载体总重量的3-15%;润滑剂的用量为活性组分和载体总重量的1-5%;造孔剂的用量为活性组分和载体总重量的0.5-5%;结构助剂的用量为活性组分和载体总重量的1-15%;水的用量为活性组分和载体总重量的20-50%。
4.根据权利要求3所述的SCR蜂窝脱硝催化剂,其特征在于,所述粘结剂为聚环氧乙烷和羧甲基纤维素钠;其中,所述聚环氧乙烷为活性组分和载体总重量的2-10%,所述羧甲基纤维素钠为活性组分和载体总重量的1-5%;
所述润滑剂为乳酸;
所述造孔剂为木浆;
所述结构助剂为玻璃纤维,杆状,长度为0.1-0.5mm。
5.根据权利要求1所述的SCR蜂窝脱硝催化剂,其特征在于,所述活性组分Me/MnAPO-57为MnAPO-57分子筛通过浸渍法负载Me所得;
所述MnAPO-57分子筛通过水热合成法制备得到;其中,Mn占SCR蜂窝脱硝催化剂的0.1-5wt%。
6.根据权利要求1或5所述的SCR蜂窝脱硝催化剂,其特征在于,所述Me为Ce、Nd、La、Pr、Co、Ni或Zr金属元素中的一种或两种以上,每种金属元素占SCR蜂窝脱硝催化剂的0.1-5wt%。
7.根据权利要求1所述的SCR蜂窝脱硝催化剂,其特征在于,所述载体TiO2为锐钛矿型TiO2,比表面积为85-95m2/g,粒径为0.5-50μm。
8.一种权利要求1-7任一项所述利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂的制备方法,其特征在于,步骤如下:
(1)将至少一种含Me的前驱体溶解于去离子水中,配制成前驱体溶液;将MnAPO-57分子筛粉末加入前驱体溶液中,在20-90℃条件下搅拌反应0.5-8h,经烘干、焙烧后,得活性组分Me/MnAPO-57粉末;
(2)取活性组分、载体和成型助剂混合均匀,得到塑性湿料泥团,陈腐6-24h;
(3)将步骤(2)得到的陈腐后塑性泥团在连续真空挤出机中进行炼泥,得到均匀致密的脱气泥段;将得到的脱气泥段在连续真空挤出机中进行挤出成型,得到整体蜂窝催化剂坯体;
(4)将步骤(3)的整体蜂窝催化剂坯体在恒温恒湿箱中干燥,烘干温度为20-100℃,湿度为20%-80%,烘干时间为12-24h;
(5)将烘干后的坯体转移至马弗炉中焙烧,焙烧温度为400-600℃,焙烧时间为2-8h,即得低温SCR蜂窝脱硝催化剂。
9.根据权利要求8所述的制备方法,其特征在于,步骤(1)中,所述含Me的前驱体为含有Ce、Nd、La、Pr、Co、Ni或Zr的硫酸盐、硝酸盐、草酸盐或乙酸盐中的一种或两种以上;
步骤(1)中的去离子水与MnAPO-57分子筛粉末的重量比为(1-10):1。
10.一种权利要求1-7任一项所述利用AFV结构分子筛制备的SCR蜂窝脱硝催化剂在低温烟气的脱硝过程中的应用。
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