静电纺丝法制备硼掺杂氧化硅纳米纤维用于低碳烷烃氧化脱氢制烯烃

doi:10.1016/S1872-2067(21)63809-3

催化学报 ›› 2021, Vol. 42 ›› Issue (10): 1782-1789.DOI: 10.1016/S1872-2067(21)63809-3

静电纺丝法制备硼掺杂氧化硅纳米纤维用于低碳烷烃氧化脱氢制烯烃

闫冰, 陆文多, 盛健, 李文翠, 丁鼎, 陆安慧()

大连理工大学化工学院, 辽宁省低碳资源高值化利用重点实验室, 精细化工国家重点实验室, 辽宁大连116024

收稿日期:2021-02-26 接受日期:2021-03-05 出版日期:2021-10-18 发布日期:2021-06-20
通讯作者: 陆安慧
作者简介:*电话: (0411)84986112; 电子信箱: anhuilu@dlut.edu.cn
基金资助:
国家自然科学基金重点项目(21733002);国家重点研发计划(2018YFA0209404);大连科技创新基金(2020JJ26GX030)

Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes

Bing Yan, Wen-Duo Lu, Jian Sheng, Wen-Cui Li, Ding Ding, An-Hui Lu()

State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2021-02-26 Accepted:2021-03-05 Online:2021-10-18 Published:2021-06-20
Contact: An-Hui Lu
Supported by:
State Key Program of the National Natural Science Foundation of China(21733002);the National Key Research and Development Program of China(2018YFA0209404);the Science and Technology Innovation Fund of Dalian(2020JJ26GX030)

摘要/Abstract

摘要：

乙烯和丙烯等低碳烯烃是重要的基础有机化工产品, 广泛应用于化工生产的各个领域. 相比于其他工艺, 低碳烷烃氧化脱氢制烯烃工艺具有不受热力学平衡限制、无积炭等特点而被广泛研究. 近年发现六方氮化硼(h-BN)、硼化硅(SiB₆)和磷酸硼(BPO₄)等非金属硼基催化剂能够高效催化烷烃氧化脱氢反应, 并抑制产物烯烃的过度氧化, 表现出高的催化活性和烯烃选择性. 大量的研究表明, 硼基催化剂活性起源于催化剂表面的“BO”物种(如B-O和B-OH等基团). 氧化硼(B₂O₃)作为一种氧化气氛中化学性质稳定的含硼化合物, 兼具丰富的“BO”位点, 在反应条件下可形成多种结构以适用不同的化学环境, 为制备高效的烷烃氧化脱氢催化剂提供了可能. 在之前的研究中, 多将B₂O₃浸渍在常规的TiO₂, SiO₂, Al₂O₃等三维多孔载体上用于氧化脱氢反应. 考虑到B₂O₃结构的灵活性和易于成键特性, 需开发更为有效的合成策略, 以提升B₂O₃催化剂在氧化脱氢反应中的活性和稳定性.
本文采用静电纺丝技术合成了直径为100~150 nm的多孔掺硼二氧化硅纳米纤维(PBSN)用于低碳烷烃氧化脱氢反应. 静电纺丝法合成的催化剂中硼物种在开放的氧化硅纤维骨架上均匀分散且稳定固载. 一维纳米纤维结构不仅有利于扩散, 且赋予催化剂在高重时空速(WHSV)条件下优异的烷烃氧化脱氢反应活性. 在乙烷氧化脱氢反应中, 当乙烷的转化率达到44.3%时, 乙烯的选择性和产率分别为84%和44.2 μmol g_cat^-1 s^-1. 而在丙烷脱氢反应中, 当丙烷转化率为19.2%时, 总烯烃选择性及丙烯产率分别为90%和76.6 μmol g_cat^-1 s^-1. 在温度为545^oC, 丙烷WHSV高达84.6 h^-1的条件下, 催化剂保持长时间稳定. 与其他负载型氧化硼催化剂相比, PBSN催化剂具有更高的烯烃选择性和稳定性. 研究表明, 在氧化硅负载B₂O₃催化剂催化丙烷氧化脱氢反应中, 载体中Si-OH基团的存在可能会降低丙烯的选择性. 瞬态分析和动力学实验表明, 硼基催化剂催化烷烃氧化脱氢反应过程中O₂的活化受到烷烃的影响. 本文不仅为高效硼基催化剂的合成提供了新思路, 也为深入理解该类催化剂上烷烃氧化脱氢反应过程提供了实验支撑.

关键词: 静电纺丝, 纳米纤维, 硼基催化剂, 氧化脱氢, 低碳烷烃

Abstract:

The discovery of the high activity and selectivity of boron-based catalysts for oxidative dehydrogenation (ODH) of alkanes to olefins has attracted significant attention in the exploration of a new method for the synthesis of highly active and selective catalysts. Herein, we describe the synthesis of porous boron-doped silica nanofibers (PBSNs) 100-150 nm in diameter by electrospinning and the study of their catalytic performance. The electrospinning synthesis of the catalyst ensures the uniform dispersion and stability of the boron species on the open silica fiber framework. The one-dimensional nanofibers with open pore structures not only prevented diffusion limitation but also guaranteed high catalytic activity at high weight hourly space velocity (WHSV) in the ODH of alkanes. Compared to other supported boron oxide catalysts, PBSN catalysts showed higher olefin selectivity and stability. The presence of Si-OH groups in silica-supported boron catalysts may cause low propylene selectivity during the ODH of propane. When the ODH conversion of ethane reached 44.3%, the selectivity and productivity of ethylene were 84% and 44.2% g_cat^-1 s^-1, respectively. In the case of propane ODH, the conversion, selectivity of olefins, and productivity of propylene are 19.2%, 90%, and 76.6 μmol g_cat^-1 s^-1, respectively. No significant variations in the conversion and product selectivity occurred during 20 h of operation at a high WHSV of 84.6 h^-1. Transient analysis and kinetic experiments indicated that the activation of O₂ was influenced by alkanes during the ODH reaction.

Key words: Electrospinning, Nanofibers, Boron-based catalyst, Oxidative dehydrogenation, Light alkanes

闫冰, 陆文多, 盛健, 李文翠, 丁鼎, 陆安慧. 静电纺丝法制备硼掺杂氧化硅纳米纤维用于低碳烷烃氧化脱氢制烯烃[J]. 催化学报, 2021, 42(10): 1782-1789.

Bing Yan, Wen-Duo Lu, Jian Sheng, Wen-Cui Li, Ding Ding, An-Hui Lu. Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes[J]. Chinese Journal of Catalysis, 2021, 42(10): 1782-1789.

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图/表 9

Fig. 1. SEM images (a,b), TEM image (c), and STEM-EDX mapping (d) of PBSN-3 catalyst.

Fig. 2. Structural characterization of the PBSN catalysts. (a) N2 sorption isotherms (curves for PBSN-1 and PBSN-2 were vertically shifted respectively by 70 and 30 cm3 g-1); (b) pore size distributions; (c) XRD patterns; (d) FTIR spectra.

Fig. 3. ODH of light alkanes over the PBSN-3 catalyst. (a) Dependence of ethane conversion and product selectivity on reaction temperature; (b) stability test of ethane over PBSN-3 and B2O3/gel catalysts at similar initial conversion rates; (c) dependence of propane conversion and product selectivity on reaction temperature; (d) stability test of propane at 545 °C; gas feed, 16.7 vol% C2H6, 25 vol% O2, and N2 balance; WHSV of C2H6, 12.8 h-1; 25 vol% C3H8, 25 vol% O2, and N2 balance; WHSV of C3H8, 84.6 h-1.

Fig. 4. Dependence of propylene selectivity on propane conversion over PBSN-3 and B2O3/gel catalysts. Reaction conditions: 25 vol% C3H8, 25 vol% O2, and N2 balance; 520 °C, WHSV of C3H8, 16.9-169.2 h-1.

Fig. 5. SEM (a,b) and TEM (c,d) images of spent PBSN-3 catalyst.

Table 1 Elemental analysis results of PBSN-3 from XPS.

Catalyst	Elemental composition (at%)
Catalyst	B	Si	O
Fresh	3.0	36.5	60.5
Spent	2.9	37.9	59.2

Fig. 6. 11B MAS NMR spectra with a 14.1 T magnet of fresh (a) and spent (b) PBSN-3 catalysts.

Fig. 7. Mass spectra of H2O and C2H4 species upon pulsing (a) C2H6 and (b) C2H6/O2 onto the PBSN-3 catalyst at 600 °C.

Fig. 8. Effect of the partial pressure of light alkanes and oxygen on alkanes consumption rate in the ODH reaction (a and b for ethane, c, and d for propane) over the PBSN-3 catalyst. Reaction conditions: gas feed, (a) 0.7 vol%-12.6 vol% C2H6 and 25 vol% O2, (b) 4.6 vol%-14.1 vol% O2 and 16.7 vol% C2H6, (c) 1.8 vol%-16.7 vol% C3H8 and 25 vol% O2, (d) 1.8 vol%-16.7 vol% O2 and 25 vol% C3H8, and N2 balance; temperature, (a,b) 540 °C and (c,d) 590 °C.

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静电纺丝法制备硼掺杂氧化硅纳米纤维用于低碳烷烃氧化脱氢制烯烃

Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes

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