等离子体与Cu-Pd/S-1催化剂协同催化甲烷转化制低碳烯烃

doi:10.16085/j.issn.1000-6613.2021-0258

化工进展 ›› 2022, Vol. 41 ›› Issue (1): 227-236.DOI: 10.16085/j.issn.1000-6613.2021-0258

等离子体与Cu-Pd/S-1催化剂协同催化甲烷转化制低碳烯烃

毕文菲(), 代成义(), 李雪梅, 贺建勋, 赵彬然, 马晓迅()

西北大学化工学院，国家碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710069

收稿日期:2021-02-04 修回日期:2021-03-08 出版日期:2022-01-05 发布日期:2022-01-24
通讯作者: 代成义,马晓迅
作者简介:毕文菲（1995—），女，硕士研究生，研究方向为非热等离子体条件下CH4转化。E-mail：1106380402@qq.com。

Synergistic catalysis of methane to light olefins by plasma and Cu-Pd/S-1 catalyst

BI Wenfei(), DAI Chengyi(), LI Xuemei, HE Jianxun, ZHAO Binran, MA Xiaoxun()

School of Chemical Engineering, Northwest University; International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources; Chemical Engineering Research Center of the Ministry of Education for Advance Use Technology of Shanbei Energy; Shaanxi Research Center of Engineering Technology for Clean Coal Conversion; Collaborative Innovation Center for Shanbei Energy and Chemical Industry Development, Xi’an 710069, Shaanxi, China

Received:2021-02-04 Revised:2021-03-08 Online:2022-01-05 Published:2022-01-24
Contact: DAI Chengyi,MA Xiaoxun

摘要/Abstract

摘要：

采用等体积浸渍法制备了Pd、Cu-Pd改性的S-1催化剂，利用介质阻挡放电（DBD）等离子体反应器研究了甲烷无氧转化制低碳烯烃（C₂~C₄⁼）的性能，重点关注了乙烯的产量。探讨了Ar的添加和特定输入能量（SIE）对甲烷转化率以及产物分布的影响。实验结果表明，等离子体与催化剂协同催化与仅使用等离子体相比性能更优异，使乙烯选择性提高了3.1倍，C₂~C₄⁼的选择性提高了2.7倍；与S-1相比，Pd/S-1具有更高的乙烯选择性，这是因为在S-1上负载金属Pd有助于乙炔原位加氢生成乙烯；适宜的Pd负载量有利于提高烯烃选择性，而过高的Pd负载量倾向于不饱和烃的连续加氢，导致了烷烃的生成；与单金属Pd改性相比，Cu-Pd双金属改性抑制了乙烯的进一步加氢，提高了乙烯的选择性。通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、高倍透射电子显微镜（HRTEM）、X射线粉末衍射（XRD）、X射线光电子能谱（XPS）对催化剂进行了表征分析。结果表明，Cu的加入使自身电子向Pd转移，增加了Pd电子密度；另外，Cu的存在提高了Pd的分散性。以2Cu-0.1Pd/S-1为催化剂时可以得到更优异的反应性能。

关键词: 甲烷, 加氢, 催化, 低碳烯烃, 介质阻挡放电（DBD）反应器

Abstract:

The Pd or Cu-Pd modified S-1 catalyst was prepared by an equivalent volume impregnation method. A dielectric barrier discharge (DBD) plasma reactor was used to study the nonoxidative conversion of methane to light olefins (C₂—C₄⁼), focusing on the production of ethylene. The effects of the Ar addition and specific input energy (SIE) on methane conversion and product distribution were investigated. The experimental results showed that the catalytic performance of plasma-catalyst cooperation was better than that of plasma-only mode. The selectivity of ethylene was increased by a factor of 3.1 and the selectivity of C₂—C₄⁼ was increased by a factor of 2.7. Compared with S-1, Pd/S-1 provided higher ethylene selectivity. This is because the metal Pd supported on S-1 promoted the in-situ hydrogenation of acetylene to ethylene. The suitable Pd loading was beneficial towards achieving higher olefins selectivity, while excessive Pd loading caused continuous hydrogenation of unsaturated hydrocarbons so that the production was alkanes. Compared with single metal Pd modification, Cu-Pd bimetal modification inhibited further hydrogenation of ethylene and improved the selectivity of ethylene. The catalysts were characterized by using SEM, TEM, HRTEM, XRD, XPS. The results showed that the addition of Cu transferred its own electrons to Pd, which increased the electron density of Pd. In addition, the presence of Cu improved the dispersibility of Pd. Better reaction performance were obtained with the 2Cu-0.1Pd/S-1 catalyst.

Key words: methane, hydrogenation, catalysis, light olefins, dielectric barrier discharge (DBD) reactor

中图分类号:

TE64

毕文菲, 代成义, 李雪梅, 贺建勋, 赵彬然, 马晓迅. 等离子体与Cu-Pd/S-1催化剂协同催化甲烷转化制低碳烯烃[J]. 化工进展, 2022, 41(1): 227-236.

BI Wenfei, DAI Chengyi, LI Xuemei, HE Jianxun, ZHAO Binran, MA Xiaoxun. Synergistic catalysis of methane to light olefins by plasma and Cu-Pd/S-1 catalyst[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 227-236.

图/表 14

图1 实验装置工艺流程示意图

图2 不同改性催化剂的XRD谱图

图3 不同催化剂的SEM图

图4 S-1的粒径分布图

图5 不同催化剂的TEM图

图6 不同催化剂的HRTEM和O、Si、Pd元素的EDS谱图

图7 0.1Pd/S-1和2Cu-0.1Pd/S-1的XPS谱图

表1 不同催化剂的XPS表面元素质量分数

催化剂	元素/%
催化剂	O	Si	C	Pd	Cu
0.1Pd/S-1	48.80	29.07	22.11	0.02	—
2Cu-0.1Pd/S-1	51.08	28.48	19.93	0.05	0.45

图8 仅使用等离子体时的产物分布（CH4流量为5mL·min-1，输入功率为5W，无催化剂）

图9 Ar的添加对甲烷转化率的影响（CH4流量为5mL·min-1，Ar流量为30mL·min-1，输入功率为5W，无催化剂）

图10 不同输入功率对反应体系的影响（CH4流量为5mL·min-1，Ar流量为30mL·min-1，无催化剂）

图11 不同Pd负载量对甲烷转化率和产物选择性的影响（CH4流量为5mL·min-1，Ar流量为30mL·min-1，输入功率为5W）

图12 0.1Pd/S-1和2Cu-0.1Pd/S-1催化剂的反应性能（CH4流量为5mL·min-1，Ar流量为30mL·min-1，输入功率为5W）

图13 0.1Pd/S-1和2Cu-0.1Pd/S-1催化剂加氢反应的可能机理

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等离子体与Cu-Pd/S-1催化剂协同催化甲烷转化制低碳烯烃

Synergistic catalysis of methane to light olefins by plasma and Cu-Pd/S-1 catalyst

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