Bogolowski Nicky, Sánchez Batalla Beatriz, Shin Baekkyoung, Drillet Jean-Francois
DECHEMA-Forschungsinstitut Theodor-Heuss-Allee 25 60486 Frankfurt a. M. Germany
RSC Adv. 2020 Mar 10;10(17):10285-10296. doi: 10.1039/d0ra00362j. eCollection 2020 Mar 6.
The syngas mixture of CO and H, from natural gas reforming, is currently an important feedstock supplier for the synthesis of numerous chemicals. In order to minimize fossil source dependency and reduce global warming, alternative processes to produce syngas, such as high-temperature co-electrolysis of HO and CO the internal reverse water-gas shift (RWGS) reaction, may be meaningful. In this study, the influence of the H : CO ratio on the activity, selectivity and stability of the as-prepared LaSrCrMnO (LSCrM) and NiSn as well as commercial Ni and Gd-doped CeO (GDC) powder materials for the reverse RWGS reaction was investigated in a tubular quartz glass reactor at 700 °C and 800 °C and ambient pressure. The highest conversion factor close to the maximum value of 50% for CO was yielded for the LSCrM, Ni and GDC samples by applying a 0.5 : 0.5 H : CO feed ratio at 800 °C. Similar activity was calculated for the NiSn alloy after normalization to the Ni mass content. Moreover, all the investigated catalysts exhibited higher selectivity for CO and HO products than Ni, with which CH molar concentrations up to 0.9% and 2.4% were collected at 800 °C and 700 °C, respectively. The influence of feed pressure on the carburisation process was inspected in a tubular Ni-Cr reactor. Under a carbon-rich gas mixture at 3 bar and 700 °C, large amounts of graphitic carbon were deposited solely on the Ni sample after 100 h of exposure time. After the exposure of the powder materials to 0.5 : 0.5 and 0.9 : 0.1 H : CO atmospheres for 300 h at 700 °C and 10 bar, traces of amorphous carbon were surprisingly detected only on NiSn powder Raman microscopy. Thus, because GDC ist not active for electrochemical H production, LSCrM or a mixture of both LSCrM and GDC materials appears to be the most promising candidate for Ni substitution in high-temperature HO/CO co-electrolysis.
来自天然气重整的一氧化碳和氢气合成气混合物,目前是众多化学品合成的重要原料供应商。为了尽量减少对化石能源的依赖并减少全球变暖,生产合成气的替代工艺,如高温共电解水和二氧化碳以及内部逆水煤气变换(RWGS)反应,可能具有重要意义。在本研究中,在管式石英玻璃反应器中,于700℃和800℃及常压下,研究了氢碳比(H∶CO)对所制备的镧锶铬锰氧(LSCrM)、镍锡以及商用镍和钆掺杂二氧化铈(GDC)粉末材料用于逆水煤气变换反应的活性、选择性和稳定性的影响。在800℃下,通过采用0.5∶0.5的氢碳进料比,LSCrM、镍和GDC样品的一氧化碳转化因子最高接近50%的最大值。将镍锡合金归一化为镍质量含量后计算出类似的活性。此外,所有研究的催化剂对一氧化碳和水产物的选择性均高于镍,在800℃和700℃下,镍分别收集到高达0.9%和2.4%的甲烷摩尔浓度。在管式镍铬反应器中考察了进料压力对渗碳过程的影响。在3巴和700℃的富碳气体混合物中,暴露100小时后,大量石墨碳仅沉积在镍样品上。在粉末材料于700℃和10巴下暴露于0.5∶0.5和0.9∶0.1的氢碳气氛300小时后,通过拉曼显微镜仅在镍锡粉末上意外检测到微量无定形碳。因此,由于GDC对电化学制氢不具有活性,LSCrM或LSCrM与GDC材料的混合物似乎是高温水电解/二氧化碳共电解中替代镍的最有前景的候选材料。