羟基化氮化硼催化乙烷氧化脱氢制乙烯

引用本文: 石磊, 闫冰, 邵丹, 姜凡, 王东琪, 陆安慧. 羟基化氮化硼催化乙烷氧化脱氢制乙烯[J]. 催化学报, 2017, 38(2): 389-395. doi: 10.1016/S1872-2067(17)62786-4 shu

Citation: Lei Shi, Bing Yan, Dan Shao, Fan Jiang, Dongqi Wang, An-Hui Lu. Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst[J]. Chinese Journal of Catalysis, 2017, 38(2): 389-395. doi: 10.1016/S1872-2067(17)62786-4 shu

羟基化氮化硼催化乙烷氧化脱氢制乙烯

石磊 ^a, ,
闫冰 ^a, ,
邵丹 ^a, ,
姜凡 ^a, ,
王东琪 ^b, ,
陆安慧 ^a,

a 大连理工大学化化工学院, 精细化工国家重点实验室, 辽宁大连 116024;
b 中国科学院高能物理研究所多学科研究中心, 北京 100049
基金项目:
国家自然科学基金（21225312，U1462120，21473206）；长江学者奖励计划（批准号T2015036）.

摘要: 乙烯是最为重要的化工原料之一，目前其工业来源主要来自于烃类的水蒸汽裂解过程.该过程本质上是一个高温均相裂解过程，温度（>800℃）高，能耗大，碳排放严重.乙烷氧化脱氢制乙烯属于放热反应，反应温度低，速率快，无积碳等限制，是一条更富有竞争力的工艺路线.然而，常用的金属或金属氧化物催化剂容易导致乙烯深度氧化，从而降低了乙烯选择性.纳米碳材料在烃类氧化脱氢反应中展现出一定的催化活性，但容易被氧化，难以用于反应温度高的乙烷氧化脱氢反应.
本文报道了羟基化的氮化硼（BNOH）可高效催化乙烷氧化脱氢制乙烯.氮化硼边沿羟基官能团脱氢生成了动态活性位，从而引发了乙烷的脱氢反应.BNOH对乙烷氧化脱氢制乙烯显示出高选择性.当乙烷转化率在11%，乙烯选择性可高达95%；当乙烷转化率增加到40%，乙烯选择性保持在90%.重要的是，当乙烷转化率超过60%时，BNOH仍然可保持80%的乙烯选择性以及50%的乙烯收率.这些性能指标与现有工业乙烷水蒸气裂解过程运行性能相当.进一步优化反应条件，BNOH催化剂能够实现高达9.1 g_C2H4 g_cat^-1 h^-1的时空收率.经过200 h的氧化脱氢反应测试，BNOH催化剂活性和选择性基本恒定，表明其具有非常好的稳定性.X射线粉末衍射结果显示，反应前后BNOH催化剂的物相没有发生变化.透射电子显微镜测试证实，反应后BNOH催化剂的形貌和微观结构也没有明显改变.X射线光电子能谱结果显示，反应200 h后BNOH催化剂表面的氧含量仅从反应前的6.9 atom%微增到8.3 atom%.¹H固体核磁共振谱测试显示，反应200 h后，BNOH催化剂上羟基含量无明显改变.结合原位透射红外光谱和同位素示踪实验，初步确定了BNOH催化剂上引发乙烷氧化脱氢反应的活性中心.氮化硼边沿的氧官能团并不能引发乙烷的氧化脱氢反应，而羟基官能团才是氧化脱氢反应发生的活性位.在乙烷氧化脱氢条件下，分子氧脱除羟基官能团上的氢原子动态生成BNO^·和HO₂^·活性位.密度泛函理论计算表明，乙烷首先在BNO^·或HO₂^·位活化生成乙基自由基，这些中间物进一步与气相氧物种发生反应脱氢生成乙烯.动力学测试结果也验证了上述实验和理论结果.

关键词:

氮化硼
/ 羟基化
/ 乙烷
/ 氧化脱氢
/ 乙烯

English

Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst

a State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
b Center for Multi-disciplinary Research, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Received Date: 09 January 2017
Revised Date: 18 January 2017
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21225312, U1462120, 21473206) and Cheung Kong Scholars Programme of China (T2015036).

Abstract: Boron nitride containing hydroxyl groups efficiently catalysed oxidative dehydrogenation of ethane to ethylene, offering rather high selectivity (95%) but only small amount of CO₂ formation (0.4%) at a given ethane conversion of 11%. Even at high conversion level of 63%, the selectivity of ethylene retained at 80%, which is competitive with the energy-demanding industrialized steam cracking route. A long-term test for 200 h resulted in stable conversion and product selectivity, showing the excellent catalytic stability. Both experimental and computational studies have identified that the hydrogen abstraction of B-OH groups by molecular oxygen dynamically generated the active sites and triggered ethane dehydrogenation.

Key words:

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羟基化氮化硼催化乙烷氧化脱氢制乙烯

English

Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羟基化氮化硼催化乙烷氧化脱氢制乙烯

English

Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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