摘要
甲烷水汽重整反应是目前工业制氢的主要过程之一,其中提升Ni基催化剂的抗积炭和抗烧结能力以及降低重整操作温度是该工艺的关键。通过将Mo_(x)C与Ni/Al_(2)O_(3)机械混合制备了Mo_(x)C-Ni/Al_(2)O_(3)双功能催化剂(Mo_(x)C-NiAl),即Ni解离CH_(4),Mo_(x)C活化H_(2)O,同时耦合冷等离子体,系统地研究了Mo_(x)C助剂的加入对催化剂结构、等离子体放电性质(放电功率、有效电容)、催化性能的影响,并通过XRD、Raman、TEM等多种表征方法探究了催化剂的失活机制。研究表明,Mo_(x)C助剂的加入不仅有效促进金属Ni的再分散,提升催化剂的抗烧结能力,还提高了催化剂的有效电容和放电功率,有助于催化剂活性的提高。与传统Ni/Al_(2)O_(3)催化剂相比,无额外热源加热条件下,Mo_(2)C-Ni/Al_(2)O_(3)催化剂在输入电压70 V下可实现CH_(4)解离速率和H_(2)O活化速率的匹配,在反应时间29 h内CH_(4)转化率均保持在80%,展现出优异的催化稳定性。该研究工作实现了在冷等离子体和催化协同作用下CH_(4)、H_(2)O等分子的高效活化及速率匹配,为甲烷水蒸气高效重整制氢过程提供了一种可行途径。
Stream reforming of methane reaction is still one of the major procedures of industrial hydrogen production so far.The key to this process is to improve the coke-and sintering-resistant abilities of Ni-based catalysts and decrease the reforming operation temperature.The bifunctional Mo_(x)C-Ni/Al_(2)O_(3)catalysts(Mo_(x)C-NiAl)were prepared using Mo_(x)C physically mixed with Ni/Al_(2)O_(3),in which Ni dissociated CH_(4)and Mo_(x)C activated H_(2)O,and cold plasma was coupled,so as to systematically investigate the effects of Mo_(x)C promoter on catalyst structure,plasma discharge properties(discharge power and effective capacitance),and catalytic performance.Meanwhile,the deactivation mechanism of prepared catalysts was also studied by several characterization methods including XRD,Raman and TEM.The study reveals that the addition of Mo_(x)C promoter has not only effectively promoted the re-dispersed process of active Ni and the sintering-resistant ability of the catalyst,but also improved the effective capacitance and discharge power of the catalyst,which can help enhance the catalytic activity.Compared to conventional Ni/Al_(2)O_(3)catalyst,Mo_(2)C-Ni/Al_(2)O_(3)can achieve the matching of CH_(4)dissociation rate and H_(2)O activation rate at the input voltage of 70 V without additional heat source for heating,and the CH_(4)conversion rate can remain at 80%within 29 h,displaying excellent catalytic stability.This work has achieved efficient activation and rate matching of molecules such as CH_(4)and H_(2)O under the synergistic effect of cold plasma and catalysis,thus providing a feasible alternative for the efficient reforming hydrogen production process of methane water vapor.
作者
刁亚南
所聪
张晓
方健聪
石川
DIAO Ya′nan;SUO Cong;ZHANG Xiao;FANG Jiancong;SHI Chuan(State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)
出处
《石油学报（石油加工）》
EI
CAS
CSCD
北大核心
2023年第5期1025-1032,共8页
Acta Petrolei Sinica(Petroleum Processing Section)
基金
国家重点研发计划项目(2017YFA0700103,2021YFA1501102)
国家自然科学基金项目(21872014,21932002,21902018)
中央高校基础科研业务费项目(DUT22ZD212,DUT21RC(3)095,DUT20ZD205,DUT22LAB602)
兴辽英才计划项目(XLYC2008032)资助。
