CN116078393A - 一种过渡金属负载型高熵氧化物低温甲烷干重整催化剂及其制备方法与应用 - Google Patents
一种过渡金属负载型高熵氧化物低温甲烷干重整催化剂及其制备方法与应用 Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 30
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
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Abstract
本发明提供了一种过渡金属负载型高熵氧化物低温甲烷干重整催化剂及其制备方法与应用。本发明制备的催化剂在较低温度下(600℃)对甲烷有强烈的催化裂解作用，并且增强了CO2的吸附的解离，使得催化剂上不易产生积碳，同时高熵氧化物载体的熵稳定性抑制了过渡金属的迁移，有效地延长催化剂的寿命和保持高催化活性。所采用原料价廉易得，制备方法简单，对设备要求低，适合大规模生产。
Description
技术领域
本发明属于催化材料领域，特别涉及一种过渡金属负载型高熵氧化物低温甲烷干重整催化剂及其制备方法与应用。
背景技术
甲烷干重整(DRM)被认为是一种很有潜力的反应，它能够以污水处理厂、垃圾填埋场、农业废弃物发酵等产生的CH4，和燃料燃烧产生的CO2为原料来生产合成气，能够在有效地处理两大温室气体的同时，生产出工业原料。
过渡金属因其具有价格低廉，储量丰富易得，且催化能力强等优点，常被用于制作DRM催化剂。然而过渡金属催化剂存在的问题，一是在DRM过程中容易产生大量积碳，导致催化剂活性位点被堵塞甚至于失活，二是容易发生团聚，造成催化能力下降。
含五种或五种以上金属元素的单相氧化物通常被归类为高熵氧化物。高熵氧化物的熵稳定性有助于这类催化剂在高温反应中长期保持稳定的催化性能，因此具有较大的潜力。然而现有的高熵氧化物催化剂主要应用于电催化领域，在DRM中过度稳定，催化性能十分有限。
可见，不论是常用的过渡金属催化剂还是具有潜力的高熵氧化物催化剂，对于DRM还有待进一步改善。
发明内容
本发明的目的在于克服现有DRM过渡金属催化剂稳定性差，寿命较短与高熵氧化物催化剂选择性差，催化效果不理想的缺点与不足，提供一种用于低温甲烷干重整的溶出过渡金属-负载型高熵氧化物催化剂，该方法制备得到的溶出过渡金属-负载型高熵氧化物催化剂同时结合了过渡金属催化剂催化能力强与高熵氧化物催化剂稳定性高的优点，具有长时间保持高选择性，高催化能力的优点。
本发明的另一目的在于，提供上述催化剂的制备方法。
本发明的再一目的在于，提供上述催化剂的应用。
本发明的目的通过下述技术方案实现：
一种过渡金属负载型高熵氧化物低温甲烷干重整催化剂的制备方法，包括如下步骤：
(1)配制金属盐溶液；
(2)配制碱性溶液；
(3)将碱性溶液加入金属盐溶液中，过滤、干燥得到沉淀物；
(4)将步骤(3)得到的沉淀物煅烧，再放入还原气氛中还原即得到过渡金属负载型高熵氧化物低温甲烷干重整催化剂。
步骤(1)所述的金属盐为过渡金属或非过渡金属的金属盐。
步骤(1)所述的金属盐为至少6种不同金属的金属盐。
所述的过渡金属盐包括锰，铁，镍，钴，铜的硝酸盐、乙酸盐或氯盐中的至少一种。
所述的非过渡金属盐包括镁，钇，锆，镧，铈，铒的硝酸盐或乙酸盐中的至少一种。
所述的金属盐为六水硝酸镍、六水硝酸镁、乙酸钇水合物、五水硝酸锆、六水硝酸铈和六水硝酸铒。
步骤(1)所述的配制的具体步骤为：将金属盐溶于水中搅拌得到金属盐溶液。
步骤(2)所述的配制的具体步骤为：将碱溶于水中搅拌得到碱性溶液。
步骤(2)所述的碱为碳酸钠，碳酸钾，氢氧化钠或氢氧化钾中的至少一种。
步骤(3)所述的加入的具体步骤为：将碱性溶液在2h内逐滴加入前驱体盐溶液中并搅拌，之后继续搅拌2h。
步骤(3)所述的过滤为抽滤。
步骤(3)所述的干燥为使用鼓风干燥箱干燥。
步骤(4)所述的煅烧为700～1000℃下煅烧0.5～2h；优选为900℃下煅烧1h。
步骤(4)所述的还原气氛为100mL/min速率的H2/N2，H2:N2为10：90。
步骤(4)所述的还原为700～1000℃下还原0.5～2h；优选为900℃下还原1h。
上述制备方法制备得到的过渡金属负载型高熵氧化物低温甲烷干重整催化剂。
上述过渡金属负载型高熵氧化物低温甲烷干重整催化剂在催化甲烷干重整中的应用。
所述的催化甲烷干重整的反应温度为550～650℃；优选为600℃。
本发明相对于现有技术具有如下的优点及效果：
本发明制备的催化剂在较低温度下(600℃)对甲烷有强烈的催化裂解作用，并且增强了CO2的吸附的解离，使得催化剂上不易产生积碳，同时高熵氧化物载体的熵稳定性抑制了过渡金属的迁移，有效地延长催化剂的寿命和保持高催化活性。所采用原料价廉易得，制备方法简单，对设备要求低，适合大规模生产。
附图说明
图1是实施例1制备得到的Ni/(CeZrMgYEr)O2-x的XRD图。
图2是实施例1制备得到的Ni/(CeZrMgYEr)O2-x的TEM图。
图3是实施例1制备得到的Ni/(CeZrMgYEr)O2-x的EDX图
图4是实施例1制备得到的Ni/(CeZrMgYEr)O2-x的XPS图。
图5是本发明制备得到的溶出过渡金属-负载型高熵氧化物催化剂的CO2-TPD图。
图6是本发明制备得到的溶出过渡金属-负载型高熵氧化物催化剂的催化活性测试转化率结果图。
图7是本发明制备得到的溶出过渡金属-负载型高熵氧化物催化剂的催化活性测试H2/CO结果图。
图8是实施例1制备得到的Ni/(CeZrMgYEr)O2-x的连续50h催化活性测试结果图。
图9是实施例1制备得到的Ni/(CeZrMgYEr)O2-x的连续50h催化活性测试后TG分析结果图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
下面实施方案中若未注明具体试验条件，则通常按照常规试验条件或按照试剂公司所建议的试验条件。所使用的材料、试剂等，若无特殊说明，均为从商业途径得到的试剂和材料。
实施例1 Ni/(CeZrMgYEr)O2-x的制备
(1)将1.45g六水硝酸镍，0.51g六水硝酸镁，0.53g乙酸钇水合物，0.86g五水硝酸锆，0.87g六水硝酸铈，0.92g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)将2.1g无水碳酸钾溶于100ml去离子水中，搅拌30min，形成碱性溶液。
(3)将碱性溶液在2h内逐滴加入前驱体盐溶液中，搅拌，逐渐形成稳定的悬浊液，待所有碱性溶液全部滴入前驱体盐溶液并搅拌满2h后，继续搅拌2h。随后使用循环水式真空泵抽滤，滤渣用100ml去离子水洗涤3次，然后放入105℃鼓风干燥箱中干燥12h，得到沉淀物；
(4)将步骤(3)得到的沉淀物放入马弗炉中在900℃中煅烧1h。在管式炉中以100ml/min的速率通入10％H2/N2(H2:N2为10：90)维持加热管的还原性气氛，管式炉维持900℃，取1g步骤(3)中煅烧后的沉淀物，放入管式炉中还原1h，即得过渡金属负载型高熵氧化物低温甲烷干重整催化剂Ni/(CeZrMgYEr)O2-x，之后对得到的催化剂进行XRD/TEM/EDX/XPS表征测试，结果如图1～4所示。
实施例2 Fe/(CeZrMgYEr)O2-x的制备
(1)将2.02g九水硝酸镍，0.51g六水硝酸镁，0.53g乙酸钇水合物，0.86g五水硝酸锆，0.87g六水硝酸铈，0.92g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Fe/(CeZrMgYEr)O2-x。
实施例3 Co/(CeZrMgYEr)O2-x的制备
(1)将1.46g六水硝酸钴，0.51g六水硝酸镁，0.53g乙酸钇水合物，0.86g五水硝酸锆，0.87g六水硝酸铈，0.92g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Co/(CeZrMgYEr)O2-x。
实施例4 Ni/(CeZrMgYLa)O2-x
(1)将1.45g六水硝酸镍，0.51g六水硝酸镁，0.53g乙酸钇水合物，0.86g五水硝酸锆，0.87g六水硝酸铈，0.87g六水硝酸镧溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(CeZrMgYLa)O2-x。
实施例5 Ni/(Ce0.1Zr0.4Mg0.2Y0.2Er0.1)O2-x的制备
(1)：将1.45g六水硝酸镍，0.26g六水硝酸镁，0.27g乙酸钇水合物，0.86g五水硝酸锆，0.22g六水硝酸铈，0.46g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(Ce0.1Zr0.4Mg0.2Y0.2Er0.1)O2-x。
实施例6 Ni/(Ce0.25Zr0.25Mg0.2Y0.2Er0.1)O2-x的制备
(1)将1.45g六水硝酸镍，0.26g六水硝酸镁，0.27g乙酸钇水合物，0.54g五水硝酸锆，0.54g六水硝酸铈，0.46g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(Ce0.25Zr0.25Mg0.2Y0.2Er0.1)O2-x。
实施例7 Ni/(Ce0.4Zr0.1Mg0.2Y0.2Er0.1)O2-x的制备
(1)将1.45g六水硝酸镍，0.26g六水硝酸镁，0.27g乙酸钇水合物，0.21g五水硝酸锆，0.87g六水硝酸铈，0.46g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(Ce0.4Zr0.1Mg0.2Y0.2Er0.1)O2-x。
实施例8 Ni/(Ce0.25Zr0.25Mg0.3Y0.1Er0.1)O2-x的制备
(1)将1.45g六水硝酸镍，0.77g六水硝酸镁，0.27g乙酸钇水合物，0.54g五水硝酸锆，0.54g六水硝酸铈，0.46g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(Ce0.25Zr0.25Mg0.3Y0.1Er0.1)O2-x。
实施例9 Ni/(Ce0.25Zr0.25Mg0.1Y0.3Er0.1)O2-x的制备
(1)将1.45g六水硝酸镍，0.26g六水硝酸镁，0.80g乙酸钇水合物，0.54g五水硝酸锆，0.54g六水硝酸铈，0.46g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(Ce0.25Zr0.25Mg0.1Y0.3Er0.1)O2-x。
实施例10 Ni/(Ce0.25Zr0.25Mg0.1Y0.1Er0.3)O2-x的制备
(1)将1.45g六水硝酸镍，0.26g六水硝酸镁，0.27g乙酸钇水合物，0.54g五水硝酸锆，0.54g六水硝酸铈，1.38g六水硝酸铒溶于100ml的去离子水中，搅拌30min，形成前驱体盐溶液。
(2)参照实施例1步骤(2)～(4)的方法制备得到Ni/(Ce0.25Zr0.25Mg0.1Y0.1Er0.3)O2-x。
实施例11过渡金属负载型高熵氧化物的CO2吸附特性研究
在AutoChem1 II 2920设备上对实施例1和实施例8～10进行CO2程序升温脱附(CO2-TPD)实验。将约50mg新鲜的样品置于U型石英形管中，在300℃和氩气流量为20mL·min-1的条件下预处理30min，然后冷却至50℃。然后将气体切换至10％CO2/N2(50mL·min-1)以吸附CO2 1h。在氩气流(50mL·min-1)下进行吹扫1h后，将样品加热至800℃(10℃·min-1)。用热导检测器(TCD)记录解吸的CO2。实验结果记录如图5所示。其中，实施例1的CO2吸附量高于其他实施例许多，证明了实施例1具有优异的CO2吸附能力。
实施例12过渡金属负载型高熵氧化物的催化活性研究
在直石英管(长度350mm，内径＝12mm)中加入0.6g实施例1中制备得到的催化剂，用石英棉固定在管子中间位置。原料气(36％CH4，21％CO2，7％O2，以N2平衡)以140mL·min-1的总流速通过催化剂。将石英管放入温度恒定为600℃的管式炉中反应。开始反应后的1h收集产生的气体，每次收集2min，并通过GC(Agilent)分析反应器流出物中气体产物的浓度。
对样品进行CH4和CO2转化率，以及H2/CO值的计算，并将计算结果进行统计，如图6。
CH4转化率根据下式计算：
其中，CCH4为CH4转化率，NCH4,入为CH4通入量，NCH4,出为气相检测的反应后CH4剩余量。
CO2转化率根据下式计算：
其中，CCO2为CO2转化率，NCO2,入为CO2通入量，NCO2,出为气相检测的反应后CO2剩余量。
H2/CO值根据下式计算：
其中，NH2,出为气相检测的反应后H2产生量，NCO,出为气相检测的反应后CO产生量。
对实施例2～10制备得到的催化剂进行相同测试。
实验结果如图6～7所示，实施例1的CH4和CO2转化率与其他实施例相比为最高。其中，CO2转化率与CH4转化率相比较低的原因是气氛中的O2与CO2在反应中是竞争关系，O2的转化取代了部分CO2转化。并且，实施例1的H2/CO与其他实施例相比最接近1，说明几乎没有副反应发生。以上证明了实施例1具有优异的催化性能。
实施例13过渡金属负载型高熵氧化物的循环效果研究
循环实验设置与实施例12的催化活性实验保持一致，开始反应后1h开始收集产气，此后每1h收集一次，连续收集50次，实验结果统计于图8。
如图8所示，CH4转化率在前28h内都比较稳定，在50％以上，最高转化率更是达到了54.5％，而之后便缓慢下降，在第50h时降到最低值，但仍然有40.4％的转化率。而CO2转化率却相对比较平稳，在50h内几乎都维持在10％～15％之间。CH4转化率和CO2转化率在50h保持在相对稳定的水平，证明了实施例1的稳定性较高。并且，反应前期的副反应较少，产物以H2和CO为主，因此H2/CO值接近1.00。
如图9所示，经过50h的连续反应后，实施例1中只产生了5.52wt％的积碳，说明实施例1能够有效地抑制反应中积碳的产生。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种过渡金属负载型高熵氧化物低温甲烷干重整催化剂的制备方法，其特征在于包括如下步骤：
(1)配制金属盐溶液；
(2)配制碱性溶液；
(3)将碱性溶液加入金属盐溶液中，过滤、干燥得到沉淀物；
(4)将步骤(3)得到的沉淀物煅烧，再放入还原气氛中还原即得到过渡金属负载型高熵氧化物低温甲烷干重整催化剂。
2.根据权利要求1所述的制备方法，其特征在于
步骤(1)所述的金属盐为过渡金属或非过渡金属的金属盐；
步骤(1)所述的金属盐为至少6种不同金属的金属盐。
3.根据权利要求2所述的制备方法，其特征在于：
所述的过渡金属盐包括锰，铁，镍，钴，铜的硝酸盐、乙酸盐或氯盐中的至少一种；
所述的非过渡金属盐包括镁，钇，锆，镧，铈，铒的硝酸盐或乙酸盐中的至少一种。
4.根据权利要求1所述的制备方法，其特征在于：
步骤(2)所述的碱为碳酸钠，碳酸钾，氢氧化钠或氢氧化钾中的至少一种。
5.根据权利要求1所述的制备方法，其特征在于：
步骤(1)所述的配制的具体步骤为：
将金属盐溶于水中搅拌得到金属盐溶液。
6.根据权利要求1所述的制备方法，其特征在于：
步骤(2)所述的配制的具体步骤为：
将碱溶于水中搅拌得到碱性溶液。
7.根据权利要求1所述的制备方法，其特征在于：
步骤(3)所述的加入的具体步骤为：
将碱性溶液在2h内逐滴加入前驱体盐溶液中并搅拌，之后继续搅拌2h；
步骤(3)所述的过滤为抽滤；
步骤(3)所述的干燥为使用鼓风干燥箱干燥。
8.根据权利要求1所述的制备方法，其特征在于：
步骤(4)所述的煅烧为700～1000℃下煅烧0.5～2h；
步骤(4)所述的还原气氛为100mL/min速率的H2/N2，H2:N2为10：90；
步骤(4)所述的还原为700～1000℃下还原0.5～2h。
9.权利要求1～8任一所述的制备方法制备得到的过渡金属负载型高熵氧化物低温甲烷干重整催化剂。
10.权利要求9所述的过渡金属负载型高熵氧化物低温甲烷干重整催化剂在催化甲烷干重整中的应用。
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| CN115261921A (zh) * | 2022-07-20 | 2022-11-01 | 昆明理工大学 | FeCoNiMnCr高熵合金/高熵氧化物异质相催化剂及其制备方法和应用 |
| CN115518649A (zh) * | 2022-09-15 | 2022-12-27 | 三峡大学 | (CoCuZnMnMg)3O4高熵氧化物的制备方法 |
| CN115555030A (zh) * | 2022-10-28 | 2023-01-03 | 吉林大学 | 具有受阻路易斯对的多孔层状高熵氧化物制备方法及应用 |
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| CN117019168A (zh) * | 2023-06-29 | 2023-11-10 | 华南农业大学 | 一种高稳定性的过渡金属高熵载氧体及其制备方法与应用 |
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