CN114653372B - 一种高分散镍基催化剂的制备方法及其催化高温水煤气变换反应的应用 - Google Patents
一种高分散镍基催化剂的制备方法及其催化高温水煤气变换反应的应用 Download PDFInfo
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- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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Abstract
本发明公开了一种高分散镍基催化剂的制备方法及其催化高温水煤气变换反应的应用。该制备方法首先利用原位生长法合成花状镍铝水滑石，花状水滑石具有类阵列结构，比表面积大，分散作用好；水滑石经原位还原处理，层板部分崩塌，发生拓扑转变得到具有高分散性的负载型镍基催化剂，且金属载体强相互作用诱导形成的结构也有利于稳定小粒径的镍纳米颗粒。本发明制得的镍基催化剂具有活性组分高度分散、催化活性高、热稳定性好、碳氧键活化能力强、循环稳定性好、廉价无毒等特点，在催化高温水煤气变换反应中有着十分明显的性能优势。
Description
技术领域
本发明属于催化剂制备技术领域，具体涉及一种高分散镍基催化剂的制备方法及其催化高温水煤气变换反应的应用。
背景技术
水煤气变换反应主要应用在以煤、石油和天然气为原料的制氢工业和合成氨工业中，另外在合成气制醇、制烃催化过程中，低温水气变换反应通常用于甲醇重整制氢反应中大量CO的去除。
水煤气变换反应是放热反应，较低的反应温度有利于化学平衡，但反应温度过低则会影响反应速率，水煤气变换反应的正向反应是水合反应，逆向反应是一个加氢及脱水反应。
传统的水煤气变换反应催化工艺中，通常要采用两个绝热的转化阶段即高温段和低温段进行串联，使得最后得到的气体中一氧化碳的含量降低到0.2-0.4％。高温段(350-450℃)所使用的催化剂是铁铬系高温变换催化剂，低温段(190-250℃)所使用的是铜锌系低温变换催化剂。
铁系氧化物是高温水煤气变换反应最主要的催化剂之一，然而由于这一催化体系活性较底，必须在高温下进行操作，造成变换率降低，这样就限制了催化剂的应用。因此，如何设计出同时具有高催化活性和热稳定性的高温水煤气变换反应催化剂成为研究人员越来越需要关注的问题。
发明内容
本发明的目的是提供一种高分散镍基催化剂的制备方法，将制得的镍基催化剂应用于高温催化水煤气变换反应，其表现出高催化活性和稳定性。
所述的高分散镍基催化剂的制备方法为：首先通过原位生长法合成花状镍铝水滑石前驱体，然后原位还原得到负载型镍基催化剂。
所述的花状镍铝水滑石前驱体的制备步骤为：
(1)将酒石酸钠、硫酸铝、尿素溶解在去离子水中得到透明溶液，其中酒石酸钠、硫酸铝、尿素的浓度分别是0.01-0.1M、0.02-0.2M、0.1-1.0M；然后将溶液转移到聚四氟乙烯反应釜中，在150-200℃下密封反应4-12h；将得到的沉淀物用去离子水离心洗涤至上清液为中性；沉淀烘干研磨后放入石英舟中，在马弗炉中以5-10℃/min的升温速率升到500-600℃，保持5-10h，制得空心Al2O3微球；
(2)将硝酸镍、硝酸铵溶解在200-500mL去离子水中得到透明混合溶液，其中硝酸镍、硝酸铵的浓度分别是0.05-0.5M、0.1-1.0M；用碱溶液将混合溶液的pH值调至6-8；然后加入0.1-1.0g步骤(1)制得的空心Al2O3微球，在60-80℃下密封反应48-72h；最后将得到的沉淀物用去离子水洗至中性，烘干即得花状镍铝水滑石。
所述的原位还原的条件为：将花状镍铝水滑石研磨后，在30-50mL/min氢气气流中以5-10℃/min的升温速率升到400-600℃，保持4-6h，随后在氮气气流中缓慢降温到室温。
上述制得的高分散性镍基催化剂需密封保存。
上述制得的高分散性镍基催化剂应用于高温催化水煤气变换反应。反应完成后，分离出的催化剂经干燥后可重复循环使用。
本发明首先利用原位生长法合成花状镍铝水滑石，花状水滑石具有类阵列结构，比表面积大，分散作用好；水滑石经原位还原处理，层板部分崩塌，发生拓扑转变得到具有高分散性的负载型镍基催化剂，且金属载体强相互作用诱导形成的结构也有利于稳定小粒径的镍纳米颗粒。本发明制得的镍基催化剂具有活性组分高度分散、催化活性高、热稳定性好、碳氧键活化能力强、循环稳定性好、廉价无毒等特点，在催化高温水煤气变换反应中有着十分明显的性能优势。
附图说明
图1是实施例1所制备的花状镍铝水滑石前驱体的XRD图。
图2是实施例1所制备的花状镍铝水滑石前驱体的SEM图。
图3是实施例1所制备的花状镍铝水滑石前驱体的TEM图。
图4是实施例1所制备的高分散镍基催化剂的XRD图。
图5是实施例1所制备的高分散镍基催化剂的SEM图。
图6是实施例1所制备的高分散镍基催化剂的TEM图。
具体实施方式
实施例1
(1)室温条件下，称取18.7g硫酸铝，0.6g酒石酸钠，6.7g尿素，溶入200mL去离子水中形成透明溶液。然后将溶液倒入聚四氟乙烯反应釜中，置于180℃烘箱中密封反应4个小时后取出，将沉淀物离心洗涤，洗至中性，并置于60℃烘箱中干燥24小时。将干燥所得的固体粉末置于玛瑙研钵中研磨充分，然后置于马弗炉中以5℃/min的升温速率升到500℃，保持5个小时后自然冷却至室温，制得空心Al2O3微球。
(2)室温条件下，称取17.4g硝酸镍、28.8g硝酸铵溶解在500mL去离子水中得到透明的溶液，然后用0.4M氨水将溶液pH值缓慢调至7.0。称取0.5g步骤(1)制得的空心Al2O3微球置于上述溶液中超声分散，将得到的悬浊液置于500mL广口瓶中密封，然后在80℃下恒温水浴72h。将得到的沉淀物用去离子反复水洗至中性并60℃烘箱干燥12h，制得花状镍铝水滑石。
(3)将花状镍铝水滑石研磨后，置于气氛炉中进行原位共还原，在50mL/min氢气气流中以5℃/min的升温速率升到450℃，保持6个小时后在氮气气流中缓慢降温到室温，即得到高分散性镍基催化剂。
对上述催化剂进行水煤气变换反应的活性评价，催化反应条件为：温度范围：300-500℃；反应气氛：CO:6％，H2O:25％，Ar:69％；反应气流量：100mL/min。催化剂在空速为12000mL gcat -1h-1的条件下，300℃时CO转化率达到75.2％，在350℃时接近完全转化，在全温度段都远高于商业化催化剂。
对催化剂在350℃下进行水煤气变换反应的稳定性评价，发现其在100小时的性能测试中，显示出良好的稳定性，具有工业应用价值。
Claims (4)
1.一种高分散镍基催化剂的制备方法，其特征在于，所述方法首先通过原位生长法合成花状镍铝水滑石前驱体，然后原位还原得到负载型镍基催化剂；
所述的花状镍铝水滑石前驱体的制备步骤为：
（1）将酒石酸钠、硫酸铝、尿素溶解在去离子水中得到透明溶液，其中酒石酸钠、硫酸铝、尿素的浓度分别是0.01-0.1 M、0.02-0.2 M、0.1-1.0 M；然后将溶液转移到聚四氟乙烯反应釜中，在150-200 ºC下密封反应4-12 h；将得到的沉淀物用去离子水离心洗涤至上清液为中性；沉淀烘干研磨后放入石英舟中，在马弗炉中以5-10 ºC/min的升温速率升到500-600 ºC，保持5-10 h，制得空心Al2O3微球；
（2）将硝酸镍、硝酸铵溶解在200-500 mL去离子水中得到透明混合溶液，其中硝酸镍、硝酸铵的浓度分别是0.05-0.5 M、0.1-1.0 M；用碱溶液将混合溶液的pH值调至6-8；然后加入0.1-1.0 g 步骤（1）制得的空心Al2O3微球，在60-80 ºC下密封反应48-72 h；最后将得到的沉淀物用去离子水洗至中性，烘干即得花状镍铝水滑石。
2.根据权利要求1所述的制备方法，其特征在于，所述的原位还原的条件为：将花状镍铝水滑石研磨后，在30-50 mL/min氢气气流中以5-10 ºC/min的升温速率升到400-600 ºC，保持4-6 h，随后在氮气气流中缓慢降温到室温。
3.根据权利要求1或2所述的制备方法制备得到的高分散性镍基催化剂在高温催化水煤气变换反应中的应用。
4.根据权利要求3所述的应用，其特征在于，反应完成后，分离出的催化剂经干燥后可重复循环使用。
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