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Highly Durable C2 Hydrocarbon Production via the Oxidative Coupling of Methane Using a BaFe0.9Zr0.1O3−δ Mixed Ionic and Electronic Conducting Membrane and La2O3 Catalyst
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-03-08 , DOI: 10.1021/acscatal.0c04888 Georgios Dimitrakopoulos 1, 2, 3 , Bonjae Koo 1 , Bilge Yildiz 2, 3 , Ahmed F. Ghoniem 1
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-03-08 , DOI: 10.1021/acscatal.0c04888 Georgios Dimitrakopoulos 1, 2, 3 , Bonjae Koo 1 , Bilge Yildiz 2, 3 , Ahmed F. Ghoniem 1
Affiliation
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The oxidative coupling of methane (OCM) is an attractive technology for the production of ethane (C2H6) and ethylene (C2H4); and significant performance and efficiency gains as well as reduced carbon dioxide (CO2) emissions are expected when OCM takes place within mixed ionic and electronic conducting (MIEC) ceramic membrane reactors (CMRs). So far, research on OCM in CMRs has been limited to unstable and incompatible materials investigated under short-term measurements that hinder upscaling and commercial application. To this end, this work demonstrates long-term stable OCM performance enabled by a BaFe0.9Zr0.1O3−δ (BFZ91) perovskite utilized as the oxygen-ion MIEC membrane and lanthanum oxide (La2O3) used as the OCM catalyst. Experimental measurements conducted in the temperature (T) range of 750–900 °C and at inlet methane (CH4) mole fractions (
) of 0–30% revealed a highly stable performance during 23 days of continuous operation, which was further confirmed by material characterization. Under the aforementioned operating conditions, BFZ91 offers a high oxygen (O2) permeation flux (JO2) between 0.5−1.5 (μmol/cm2/s); CH4 conversion (CCH4) reached ∼35% while the selectivities to C2H6 (SC2H6) and C2H4 (SC2H4) were as high as ∼50% and ∼40%, respectively, showing a strong dependency on the operating conditions. Yields of C2H6 (YC2H6) and C2H4 (YC2H4) in the range of 1–5% and 1–7%, respectively, were measured, with more C2H4 being produced at higher T. In the absence of La2O3, CCH4 and C2 (C2H6 and C2H4) yields are lower confirming that BFZ91 does not promote CH4 oxidation, reforming, or coupling on its surface at high rates. The OCM performance of BFZ91 with La2O3 was also found to be stable under partial O2 consumption and pure CH4 conditions. Furthermore, a detailed analysis of the mixture composition allowed the identification of the primary reactions in the OCM chemistry. Our results reveal that within our reactor, CH4 full oxidation to CO2 and steam (H2O) happens simultaneously with CH4 oxidation to C2H6 and H2O (both on the La2O3 catalyst), but the production of the valuable C2H4 is primarily taking place through the C2H6 non-oxidative dehydrogenation in the gas phase; this reaction was not found to proceed on the La2O3 catalyst. Besides the promise of the investigated materials toward commercialization, the methods to study the OCM chemistry and the membrane catalyst coupling presented here are expected to promote further advances in the field of OCM.
中文翻译：
使用BaFe 0.9 Zr 0.1 O3 -δ混合离子和电子导电膜和La 2 O 3催化剂通过甲烷的氧化偶联产生高度耐用的C 2烃
甲烷的氧化偶联（OCM）是用于生产乙烷（C 2 H 6）和乙烯（C 2 H 4）的一种有吸引力的技术。当在混合离子和电子导电（MIEC）陶瓷膜反应器（CMR）中进行OCM时，预计会显着提高性能和效率，并减少二氧化碳（CO 2）排放。迄今为止，对CMR中OCM的研究仅限于在短期测量中研究的不稳定和不相容的材料，这阻碍了规模化和商业化应用。为此，这项工作证明了BaFe 0.9 Zr 0.1 O 3−δ可以实现长期稳定的OCM性能。（BFZ91）钙钛矿用作氧离子MIEC膜，氧化镧（La 2 O 3）用作OCM催化剂。在750–900°C的温度（T）范围内和入口甲烷（CH 4）的摩尔分数（）为0–30％的条件下进行的实验测量表明，连续运行23天的性能非常稳定，这一点得到了进一步的证实。材料表征。在上述操作条件下，BFZ91具有0.5-1.5（μmol/ cm 2 / s）的高氧（O 2）渗透通量（J O 2）；CH 4转换（C CH4）达到约35％，而对C 2 H 6（S C 2 H 6）和C 2 H 4（S C 2 H 4）的选择性分别高达〜50％和〜40％，显示出很强的依赖性在运行条件上。测量的C 2 H 6（Y C 2 H 6）和C 2 H 4（Y C 2 H 4）的产率分别在1–5％和1–7％范围内，其中C 2 H 4的含量更多更高的产量Ť。在没有La 2 O 3的情况下，C CH 4和C 2（C 2 H 6和C 2 H 4）的产率较低，这证实BFZ91不会促进CH 4在其表面高速率氧化，重整或偶联。在部分O 2消耗和纯CH 4条件下，还发现BFZ91与La 2 O 3的OCM性能稳定。此外，对混合物成分的详细分析可以确定OCM化学中的主要反应。我们的结果表明，在我们的反应堆中，CH4 CH 4氧化成C 2 H 6和H 2 O（均在La 2 O 3催化剂上）同时发生完全氧化为CO 2和蒸汽（H 2 O ），但是有价值的C 2 H 4的生产是主要通过气相中的C 2 H 6非氧化脱氢进行；未发现该反应在La 2 O 3上进行催化剂。除了被研究材料有望实现商业化以外，这里介绍的研究OCM化学方法和膜催化剂偶联的方法有望促进OCM领域的进一步发展。
更新日期：2021-03-19
) of 0–30% revealed a highly stable performance during 23 days of continuous operation, which was further confirmed by material characterization. Under the aforementioned operating conditions, BFZ91 offers a high oxygen (O2) permeation flux (JO2) between 0.5−1.5 (μmol/cm2/s); CH4 conversion (CCH4) reached ∼35% while the selectivities to C2H6 (SC2H6) and C2H4 (SC2H4) were as high as ∼50% and ∼40%, respectively, showing a strong dependency on the operating conditions. Yields of C2H6 (YC2H6) and C2H4 (YC2H4) in the range of 1–5% and 1–7%, respectively, were measured, with more C2H4 being produced at higher T. In the absence of La2O3, CCH4 and C2 (C2H6 and C2H4) yields are lower confirming that BFZ91 does not promote CH4 oxidation, reforming, or coupling on its surface at high rates. The OCM performance of BFZ91 with La2O3 was also found to be stable under partial O2 consumption and pure CH4 conditions. Furthermore, a detailed analysis of the mixture composition allowed the identification of the primary reactions in the OCM chemistry. Our results reveal that within our reactor, CH4 full oxidation to CO2 and steam (H2O) happens simultaneously with CH4 oxidation to C2H6 and H2O (both on the La2O3 catalyst), but the production of the valuable C2H4 is primarily taking place through the C2H6 non-oxidative dehydrogenation in the gas phase; this reaction was not found to proceed on the La2O3 catalyst. Besides the promise of the investigated materials toward commercialization, the methods to study the OCM chemistry and the membrane catalyst coupling presented here are expected to promote further advances in the field of OCM.
中文翻译：
使用BaFe 0.9 Zr 0.1 O3 -δ混合离子和电子导电膜和La 2 O 3催化剂通过甲烷的氧化偶联产生高度耐用的C 2烃
甲烷的氧化偶联（OCM）是用于生产乙烷（C 2 H 6）和乙烯（C 2 H 4）的一种有吸引力的技术。当在混合离子和电子导电（MIEC）陶瓷膜反应器（CMR）中进行OCM时，预计会显着提高性能和效率，并减少二氧化碳（CO 2）排放。迄今为止，对CMR中OCM的研究仅限于在短期测量中研究的不稳定和不相容的材料，这阻碍了规模化和商业化应用。为此，这项工作证明了BaFe 0.9 Zr 0.1 O 3−δ可以实现长期稳定的OCM性能。（BFZ91）钙钛矿用作氧离子MIEC膜，氧化镧（La 2 O 3）用作OCM催化剂。在750–900°C的温度（T）范围内和入口甲烷（CH 4）的摩尔分数（
）为0–30％的条件下进行的实验测量表明，连续运行23天的性能非常稳定，这一点得到了进一步的证实。材料表征。在上述操作条件下，BFZ91具有0.5-1.5（μmol/ cm 2 / s）的高氧（O 2）渗透通量（J O 2）；CH 4转换（C CH4）达到约35％，而对C 2 H 6（S C 2 H 6）和C 2 H 4（S C 2 H 4）的选择性分别高达〜50％和〜40％，显示出很强的依赖性在运行条件上。测量的C 2 H 6（Y C 2 H 6）和C 2 H 4（Y C 2 H 4）的产率分别在1–5％和1–7％范围内，其中C 2 H 4的含量更多更高的产量Ť。在没有La 2 O 3的情况下，C CH 4和C 2（C 2 H 6和C 2 H 4）的产率较低，这证实BFZ91不会促进CH 4在其表面高速率氧化，重整或偶联。在部分O 2消耗和纯CH 4条件下，还发现BFZ91与La 2 O 3的OCM性能稳定。此外，对混合物成分的详细分析可以确定OCM化学中的主要反应。我们的结果表明，在我们的反应堆中，CH4 CH 4氧化成C 2 H 6和H 2 O（均在La 2 O 3催化剂上）同时发生完全氧化为CO 2和蒸汽（H 2 O ），但是有价值的C 2 H 4的生产是主要通过气相中的C 2 H 6非氧化脱氢进行；未发现该反应在La 2 O 3上进行催化剂。除了被研究材料有望实现商业化以外，这里介绍的研究OCM化学方法和膜催化剂偶联的方法有望促进OCM领域的进一步发展。
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