表面偶联甲基自由基实现低温高效甲烷氧化偶联

doi:10.1016/S1872-2067(20)63756-1

催化学报 ›› 2021, Vol. 42 ›› Issue (7): 1117-1125.DOI: 10.1016/S1872-2067(20)63756-1

表面偶联甲基自由基实现低温高效甲烷氧化偶联

邹世辉^a^,^†,^#(), 李志年^a^,†, 周秋月^a, 潘洋^b, 袁文涛^c, 贺磊^a, 王申亮^a, 文武^b, 刘娟娟^d, 王勇^c, 杜永华^e, 杨玖重^b, 肖丽萍^a, 小林久芳^f^,^&(), 范杰^a^,^*()

^a浙江大学化学系浙江省应用化学重点实验室, 浙江杭州310027, 中国
^b中国科学技术大学, 国家同步辐射重点实验室, 安徽合肥230029, 中国
^c浙江大学材料科学与工程学院, 浙江杭州310027, 中国
^d杭州电子大学, 材料与环境工程学院, 浙江杭州310036, 中国
^e布鲁克海文国家实验室, 国家同步辐射光源II, 纽约11973, 美国
^f京都工艺纤维大学化学与材料科学系, 京都606-8585, 日本

收稿日期:2021-01-04 接受日期:2021-01-09 出版日期:2021-07-18 发布日期:2021-01-19
通讯作者: 邹世辉,小林久芳,范杰
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(92045301);国家自然科学基金(91845203);国家自然科学基金(21802122);国家自然科学基金(21703050);中国科学院合肥大科学中心重点研发项目(2018HSC-KPRD002)

Surface coupling of methyl radicals for efficient low-temperature oxidative coupling of methane

Shihui Zou^a^,^†,^#(), Zhinian Li^a^,†, Qiuyue Zhou^a, Yang Pan^b, Wentao Yuan^c, Lei He^a, Shenliang Wang^a, Wu Wen^b, Juanjuan Liu^d, Yong Wang^c, Yonghua Du^e, Jiuzhong Yang^b, Liping Xiao^a, Hisayoshi Kobayashi^f^,^&(), Jie Fan^a^,^*()

^aKey Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310036, Zhejiang, China
^bNational Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, Anhui, China
^cSchool of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^dCollege of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310036, Zhejiang, China
^eNational Synchrotron Light Source II, Brookhaven National Laboratory Upton NY, 11973, USA
^fEmertus Professor of Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan

Received:2021-01-04 Accepted:2021-01-09 Online:2021-07-18 Published:2021-01-19
Contact: Shihui Zou,Hisayoshi Kobayashi,Jie Fan
About author:^* Tel/Fax: +86-571-87952338; E-mail: jfan@zju.edu.cn;
First author contact:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(92045301);National Natural Science Foundation of China(91845203);National Natural Science Foundation of China(21802122);National Natural Science Foundation of China(21703050);Key Program of Research and Development of Hefei Science Center, CAS(2018HSC-KPRD002)

摘要/Abstract

摘要：

天然气作为一种低碳清洁能源, 其储量大, 价格低, 被认为是最有前途的石油替代资源之一. 而以天然气的主要成分——甲烷为原料来生产高价值化学品被认为是石化工业中实现天然气取代石油为原料新化工路线的技术基础, 具有极为可观的社会经济价值. 目前甲烷的化学利用主要采用间接转化法, 即先从甲烷制合成气, 再由合成气制备各种化工原料和油品. 但该路线流程复杂, 能耗大, 生产成本高及投资大, 具有明显的局限性, 这促使着人们不断探索能量效率更高的甲烷直接转化技术.
甲烷氧化偶联(OCM)是最重要的甲烷直接转化技术之一. 自1982首次报道以来, 人们开发了1000多种OCM催化剂, 涉及元素超过68种, 但C₂烃类(乙烷和乙烯)的收率普遍低于30%, 尚未实现工业化. 传统研究认为, OCM反应遵循“多相-均相”催化反应机理, 甲烷在催化剂表面活化产生甲基自由基后, 在气相中进行偶联生成乙烷和乙烯等产物. 由于高温下甲基自由基很容易脱附到气相, 传统的OCM催化剂一般只在甲基自由基的产生这一步发挥作用. 而随后在气相中发生的甲基自由基均相反应并不受催化剂控制, 在热力学驱动下, 会倾向于深度氧化生成CO₂等副产物, 因此OCM反应中C₂的收率上限为25%-28%. 理论上来说, 只有当催化剂能够在甲基自由基偶联这一步发挥作用时, C₂物种的收率才可能打破上限, 但目前尚未有催化剂实现甲基自由基可控表面偶联.
本文提出并证实5wt% Na₂WO₄/SiO₂(5NaWSi)具有催化甲基自由基表面偶联的能力. 在低温下, 5NaWSi本身对于OCM没有催化活性, 但是它的加入能够显著提高La₂O₃催化剂的C₂选择性, 进而提高C₂收率, 使其在570 ºC的低温下即可达到10.9%的C₂收率. 在La₂O₃和5NaWSi之间加入一层甲基自由基淬灭剂——石英砂, 这种提升作用随即消失, 表明甲基自由基在5NaWSi上的表面偶联可能是C₂选择性和收率提升的主要原因. 本文进一步采用同步辐射光电离质谱技术原位检测了反应过程中的自由基中间体, 结果发现, La₂O₃表面产生的甲基自由基确实可以在5NaWSi表面进行偶联, 进而提高C₂的选择性和收率. 通过对5NaWSi的组成和结构进行分析, 发现5NaWSi中的Na₂WO₄纳米团簇可能是甲基自由基偶联的活性位点, 该位点不仅具有很强的甲基自由基吸附能力, 为甲基自由基表面偶联提供机会, 同时不会深度氧化C₂物种, 有效地提高了C₂选择性. 以此为基础建立理论模型, 我们通过DFT计算对甲基自由基在5NaWSi表面的偶联机制进行了研究. 结果表明, 5NaWSi对甲基自由基具有很强的吸附能力, 而吸附后的甲基自由基更倾向于偶联生成C₂产物, 而不是β-H消除生成HCHO等副产物, 表明5NaWSi确实是很好的甲基自由基表面偶联催化剂. 甲基自由基表面偶联的证实为OCM催化剂的开发开辟了新方向. 从双功能催化剂设计的角度出发, 将OCM反应分解成甲烷活化和甲基自由基偶联这两个部分, 并分别针对这两个部分来筛选和优化催化剂, 将有望突破C₂收率上限, 进而推进OCM的工业化进程.

关键词: 甲烷氧化偶联, 双功能催化, 甲基自由基, 表面偶联, La₂O₃, Na₂WO₄/SiO₂

Abstract:

Selective coupling of methyl radicals to produce C₂ species (C₂H₄ and C₂H₆) is a key challenge for oxidative coupling of methane (OCM). In traditional OCM reaction systems, homogeneous transformation of methyl radicals in O₂-containing gases are uncontrollable, resulting in limited C₂ selectivity and yield. Herein, we demonstrate that methyl radicals generated by La₂O₃ at low reaction temperature can selectively couple on the surface of 5 wt% Na₂WO₄/SiO₂. The controllable surface coupling against overoxidation barely changes the activity of La₂O₃ but boosts the C₂ selectivity by three times and achieves a C₂ yield as high as 10.9% at bed temperature of only 570 °C. Structure-property studies suggest that Na₂WO₄ nanoclusters are the active sites for methyl radical coupling. The strong CH₃· affinity of these sites can even endow some methane combustion catalysts with OCM activity. The findings of the surface coupling of methyl radicals open a new direction to develop OCM catalyst. The bifunctional OCM catalyst system, which composes of a methane activation center and a CH₃· coupling center, may deliver promising OCM performance at reaction temperatures below the ignition temperature of C₂H₆ and C₂H₄ (~600 °C) and is therefore more controllable, safer, and certainly more attractive as an actual process.

Key words: Oxidative coupling of methane, Bifunctional catalysis, Methyl radicals, Surface coupling, La₂O₃, Na₂WO₄/SiO₂

邹世辉, 李志年, 周秋月, 潘洋, 袁文涛, 贺磊, 王申亮, 文武, 刘娟娟, 王勇, 杜永华, 杨玖重, 肖丽萍, 小林久芳, 范杰. 表面偶联甲基自由基实现低温高效甲烷氧化偶联[J]. 催化学报, 2021, 42(7): 1117-1125.

Shihui Zou, Zhinian Li, Qiuyue Zhou, Yang Pan, Wentao Yuan, Lei He, Shenliang Wang, Wu Wen, Juanjuan Liu, Yong Wang, Yonghua Du, Jiuzhong Yang, Liping Xiao, Hisayoshi Kobayashi, Jie Fan. Surface coupling of methyl radicals for efficient low-temperature oxidative coupling of methane[J]. Chinese Journal of Catalysis, 2021, 42(7): 1117-1125.

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图/表 4

Fig. 1. Catalytic performances of La2O3-5NaWSi and reference catalysts in OCM reaction. (a) C2 yield as a function of reaction temperature; (b) CH4 conversion, C2 selectivity and C2 yield at 571 ± 6 °C; (c) A stability test of La2O3-5NaWSi at 570 °C, CH4:O2:N2 = 3:1:2.6, total gas flow rate 66 mL min-1; (d) Integrated SVUV-PIMS peak intensity of gas-phase methyl radicals, ethylene and CO2 during OCM reaction catalyzed by various catalysts at 600 °C; (e) C2 yield as a function of reaction temperature over various catalysts (GHSV 20,000 mL h-1 gcat-1); (f) Schematic illustration of reaction process of OCM over La2O3-5NaWSi.

Fig. 2. The structure and property of 5NaWSi. (a) The difference in C2 yield (ΔC2 yield) between composite catalysts and pure La2O3 at 570 °C; (b) XRD patterns for various catalysts; (c) The W L3-edge XANES spectra; (d) EXAFS-derived Fourier transforms of Na2WO4/SiO2 with different mass loading; Catalytic performance of deep oxidation of (e) ethane and (f) ethylene (C2Hx:O2:N2 = 1:6:5, x = 4 or 6, gas flow rate 66 mL min-1). The red dash lines indicate the ignition temperature at 50% conversion. HAADF-STEM images of (g) 2NaWSi, (h) 5NaWSi and (i) 10NaWSi.

Fig. 3. DFT calculations for CH3· coupling over various catalyst models. (a) The energy profiles; (b) the corresponding configurations for CH3· coupling over (WO3)8 via L-H mechanism and E-R mechanisms; (c) The energy profiles for CH3· coupling; (d) the configurations for CH3? adsorption over various catalyst models. Other configurations are shown in Fig. S9. (e) The energy profile and (f) the corresponding configurations for the β-H elimination of W-O-CH3 over (WO3)8. Yellow: Si, red: O, blue: W, purple: Na, gray: C, and white: H. (WO3)2, (WO3)6, and (WO3)8 abbreviate Si48O112H30Na2(WO3)2, Si48O112H26Na6(WO3)6, and [Si12O28H6Na2(WO3)2]4, respectively.

Fig. 4. Catalytic performance of transition metal oxides and their mixture with 5NaWSi at 755 ± 15 °C for OCM reaction. CH4:O2:N2 = 3:1:2.6, total gas flow rate 66 mL min-1.

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表面偶联甲基自由基实现低温高效甲烷氧化偶联

Surface coupling of methyl radicals for efficient low-temperature oxidative coupling of methane

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