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CN113522293A - 一种甲烷二氧化碳干重整制氢催化剂的制备方法和应用 - Google Patents

一种甲烷二氧化碳干重整制氢催化剂的制备方法和应用 Download PDF

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CN113522293A
CN113522293A CN202110761147.2A CN202110761147A CN113522293A CN 113522293 A CN113522293 A CN 113522293A CN 202110761147 A CN202110761147 A CN 202110761147A CN 113522293 A CN113522293 A CN 113522293A
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methane
carbon dioxide
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袁浩然
张军
李丹妮
王舒笑
顾菁
陈勇
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Guangzhou Institute of Energy Conversion of CAS
Southern Marine Science and Engineering Guangdong Laboratory Guangzhou
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Abstract

本发明公开了一种甲烷二氧化碳干重整制氢催化剂的制备方法，所述催化剂为Ni‑Cu‑Mg‑Al水滑石层状催化剂，以Ni、Cu为活性组分，以共沉淀法合成了Ni‑Cu‑Mg‑Al四元水滑石催化剂，通过煅烧和还原得到的层状结构催化剂具有较大的表面积、孔容和孔径，能够大幅度提高对CO2的吸附能力，从而提高催化剂的重整反应活性，具有较好的稳定性和抗积碳能力，对设备要求较低，无需对天然气中的CO2进行分离，甲烷的转化率可达89.4％，氢气收率可达89.6％，能够满足小型化甲烷制氢反应的需求。

Description

一种甲烷二氧化碳干重整制氢催化剂的制备方法和应用
技术领域：
本发明涉及催化剂制备技术领域，具体涉及一种甲烷二氧化碳干重整制氢催化剂的制备方法和应用。
背景技术：
氢燃料在航空领域已经有了长足的发展。氢气用作发动机燃料，可以优先减少汽油燃烧过程中一氧化碳和硫氮化物的排放；利用氢气和氧气燃烧，将化学能转化为电能供电，可大大提高供电站的发电能力，氢能已经逐渐应用于生活中的各个角落。因此，开发新型催化剂促进氢气制备效率具有重要的研究意义。
目前，甲烷制氢气技术主要包括蒸汽重整、二氧化碳干重整、部分氧化和催化裂解等。其中甲烷蒸汽重整制氢技术较为成熟，并得到了广泛的应用。专利CN105854885A公开了一种甲烷二氧化碳重整制备合成气的催化剂制备方法，以复合活性炭为载体，利用HNO3溶液对载体进行改性，以镍、铁、铜或锌为催化剂助剂，制备出一系列具有较高比表面积的催化剂，但制备过程所使用的硝酸溶液对容器具有一定腐蚀性，反应过程条件较为苛刻。专利CN106000444A公开了一种高分散镍基甲烷二氧化碳重整催化剂的制备方法，该催化剂具有较高的比表面积但由于3～7nm的Ni颗粒过小，容易在高温重整的过程中发生烧结，导致该催化剂在高温下的催化活性有所降低。因此，开发高活性、高稳定性、不易烧结的抗积碳催化剂仍是开展大规模甲烷二氧化碳重整制氢的关键问题。
发明内容：
本发明的目的是提供一种甲烷二氧化碳干重整制氢催化剂的制备方法和应用。
本发明是通过以下技术方案予以实现的：
一种甲烷二氧化碳干重整制氢催化剂的制备方法，所述催化剂为Ni-Cu-Mg-Al水滑石层状催化剂，以Ni、Cu为活性组分，该方法包括以下步骤，将Ni(NO3)2·6H2O、Cu(NO3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·6H2O金属离子总浓度为1mol/L的金属盐溶液，NaOH和Na2CO3配制碱溶液，其中，n[Na2CO3]＝0.5×n[Al3+]，n[NaOH]＝2×n[Al3++Ni2++Cu2++Mg2+]，将金属盐溶液和碱溶液这两种溶液同时缓慢滴加至超纯水中，控制溶液pH为8～10，上述溶液搅拌均匀后在65℃油浴锅中晶化12h，经洗涤、干燥、研磨、煅烧和还原后制得Ni-Cu-Mg-Al水滑石催化剂；所述煅烧是在300～600℃空气氛围中煅烧3h；所述还原是在氢气和氮气体积为7:3的混合气氛围中以2℃/min中的升温速率在400℃条件下还原4h。
优选地，n[Ni2++Cu2++Mg2+]：n[Al3+]＝3:1，Cu2+和Mg2+摩尔比为1:1，Ni2+的摩尔占Ni2+、Cu2+、Mg2+三者总摩尔的1/20～1/40。
优选地，金属盐溶液与碱溶液混合前在水中加入质量分数为0.1％的四丙基氢氧化铵表面活性剂，可以避免滴加速度过快引起团聚，提高了金属颗粒的分散性，提高了催化剂的抗积碳能力。
优选地，溶液pH为8.5～10。
优选地，所述干燥是在80℃真空干燥12h。
本发明还保护所述甲烷二氧化碳干重整制氢催化剂在甲烷二氧化碳干重整制氢的应用。
本发明的有益效果如下：
1.本发明以共沉淀法合成了Ni-Cu-Mg-Al四元水滑石催化剂，通过煅烧和还原使各金属具有良好的热稳定性。
2.本发明得到的层状结构的催化剂具有较大的表面积、孔容和孔径，能够大幅度提高对CO2的吸附能力，从而提高催化剂的重整反应活性。
总之，本发明制备工艺简便，得到的层状结构的催化剂具有较大的表面积、孔容和孔径，能够大幅度提高对CO2的吸附能力，从而提高催化剂的重整反应活性，同时具有较好的稳定性和抗积碳能力，对设备要求较低，无需对天然气中的CO2进行分离，甲烷的转化率可达89.4％，氢气收率可达89.6％，能够满足小型化甲烷制氢反应的需求。
附图说明：
图1是实施例2中煅烧后的Ni-Cu-Mg-Al-1/30的热重曲线图。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1
称取12gNaOH和1.98gNa2CO3配制碱溶液，以Ni、Cu、Mg摩尔比为1:9.5:9.5分别称取Ni(NO3)2·6H2O、Cu(NO3)2·6H2O、Mg(NO3)2·6H2O，然后称取Al(NO3)3·6H2O，n[Ni2++Cu2++Mg2 +]：n[Al3+]＝3:1，配制Ni、Cu、Mg、Al这四种金属离子的总摩尔浓度为1mol/L的金属盐溶液，将金属盐溶液和碱溶液同时滴入含有0.1g四苯基氢氧化铵的100mL超纯水中，搅拌均匀后于65℃油浴锅中以300rpm/min的速度晶化12h，然后过滤并用超纯水洗涤至中性，滤饼于80℃真空干燥箱中烘干过夜，研磨过筛即可得到Ni-Cu-Mg-Al-1/20。氧化态的前驱体在500℃空气氛围中煅烧3h后，在H2/N2(氢气和氮气体积为7:3)混合气氛中以2℃/min的升温速率在400℃还原3h，样品经研磨后及得到Ni-Cu-Mg-Al-1/20水滑石催化剂。得到的层状结构的催化剂具有较大的表面积、孔容和孔径，参见表1。
表1
Figure BDA0003149813540000041
对比例1：
参考实施例1，不同之处在于没有添加Cu(NO3)2·6H2O。
对比例2：
参考实施例1，不同之处在于没有添加Mg(NO3)2·6H2O。
对比例3：
参考实施例1，不同之处在于没有添加Al(NO3)2·6H2O。
对比例4：
参考实施例1，不同之处在于没有添加Al(NO3)2·6H2O，添加Fe(NO3)2·6H2O。
实施例2：
参考实施例1，不同之处在于Ni、Cu、Mg摩尔比为1:14.5:14.5。得到Ni-Cu-Mg-Al-1/30水滑石催化剂。得到的层状结构的催化剂具有较大的表面积、孔容和孔径，参见表1。煅烧后的Ni-Cu-Mg-Al-1/30的热重曲线图如图1，证明该催化剂具有较好的热稳定性。
实施例3：
参考实施例1，不同之处在于Ni、Cu、Mg摩尔比为1:19.5:19.5。得到Ni-Cu-Mg-Al-1/30水滑石催化剂。得到的层状结构的催化剂具有较大的表面积、孔容和孔径，参见表1。
实施例4：
参考实施例1，不同之处在于Ni、Cu、Mg摩尔比为1:14.5:14.5，煅烧温度为300℃。
实施例5：
参考实施例1，不同之处在于Ni、Cu、Mg摩尔比为1:14.5:14.5，煅烧温度为400℃。
实施例6：
参考实施例1，不同之处在于Ni、Cu、Mg摩尔比为1:14.5:14.5，煅烧温度为,600℃。
催化剂活性测试：
称取100mg实施例1-6和对比例1-3制备的催化剂放入固定床反应器石英管中，以20mL/min的流速同时通入CO2和CH4，反应测试温度设置为700℃，反应30h后开始检测气体组成，检测结果如表2。
表2
Figure BDA0003149813540000051
Figure BDA0003149813540000061
实施例1和对比例1-3对比可知，本发明Cu-Mg-Al组分间协同作用。

Claims (6)

1.一种甲烷二氧化碳干重整制氢催化剂的制备方法，其特征在于，所述催化剂为Ni-Cu-Mg-Al水滑石层状催化剂，以Ni、Cu为活性组分，以共沉淀法合成了Ni-Cu-Mg-Al四元水滑石催化剂，该方法包括以下步骤，称取Ni(NO3)2·6H2O、Cu(NO3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·6H2O配制金属离子总浓度为1mol/L的金属盐溶液，NaOH和Na2CO3配制碱溶液，其中，n[Na2CO3]＝0.5×n[Al3+]，n[NaOH]＝2×n[Al3++Ni2++Cu2++Mg2+]，将金属盐溶液和碱溶液同时缓慢滴加至超纯水中，控制溶液pH为8～10，上述溶液搅拌均匀后在65℃油浴锅中晶化12h，经洗涤、干燥、研磨、煅烧和还原后制得Ni-Cu-Mg-Al水滑石催化剂；所述煅烧是在300～600℃空气氛围中煅烧3h；所述还原是在氢气和氮气体积为7:3的混合气氛围中以2℃/min中的升温速率在400℃条件下还原4h。
2.根据权利要求1所述甲烷二氧化碳干重整制氢催化剂的制备方法，其特征在于，n[Ni2 ++Cu2++Mg2+]:n[Al3+]＝3:1，Cu2+和Mg2+摩尔比为1:1，Ni2+的摩尔占Ni2+、Cu2+、Mg2+三者总摩尔的1/20～1/40。
3.根据权利要求1或2所述甲烷二氧化碳干重整制氢催化剂的制备方法，其特征在于，金属盐溶液与碱溶液混合前在水中加入质量分数为0.1％的四丙基氢氧化铵表面活性剂。
4.根据权利要求1或2所述甲烷二氧化碳干重整制氢催化剂的制备方法，其特征在于，溶液pH为8.5～10。
5.根据权利要求1或2所述甲烷二氧化碳干重整制氢催化剂的制备方法，其特征在于，所述干燥是在80℃真空干燥12h。
6.权利要求所述甲烷二氧化碳干重整制氢催化剂的制备方法得到的催化剂在甲烷二氧化碳干重整制氢的应用。
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