杂原子掺杂生物质碳催化丙烷直接脱氢制丙烯

doi:10.15541/jim20220093

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1058-1064.DOI: 10.15541/jim20220093 CSTR: 32189.14.10.15541/jim20220093

杂原子掺杂生物质碳催化丙烷直接脱氢制丙烯

甘洪宇¹(), 冯燕¹, 杨德鸿¹, 田煜彬¹, 李阳¹, 邢涛², 李智²^,³, 赵学波¹, 代鹏程¹()

1.中国石油大学(华东) 新能源学院, 青岛 266580
2.山东能源集团有限公司新能源事业部, 济宁 273500
3.西安交通大学材料科学与工程学院, 西安 710049

收稿日期:2022-02-28 修回日期:2022-03-26 出版日期:2022-10-20 网络出版日期:2022-04-07
通讯作者: 代鹏程, 副教授. E-mail: dpcapple@upc.edu.cn
作者简介:甘洪宇(1998-), 男, 硕士研究生. E-mail: hongyugan@163.com
基金资助:
国家自然科学基金(51702365);山东省重点研发计划(2019GGX102056)

Heteroatom-doped Biochar for Direct Dehydrogenation of Propane to Propylene

GAN Hongyu¹(), FENG Yan¹, YANG Dehong¹, TIAN Yubin¹, LI Yang¹, XING Tao², LI Zhi²^,³, ZHAO Xuebo¹, DAI Pengcheng¹()

1. College of New Energy, China University of Petroleum (East China), Qingdao 266580, China
2. New Energy Division, Shandong Energy Group Co., Ltd., Jining 273500, China
3. School of Materials Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Received:2022-02-28 Revised:2022-03-26 Published:2022-10-20 Online:2022-04-07
Contact: DAI Pengcheng, associate professor. E-mail: dpcapple@upc.edu.cn
About author:GAN Hongyu (1998-), male, Master candidate. E-mail: hongyugan@163.com
Supported by:
National Natural Science Foundation of China(51702365);Key Research and Development Projects in Shandong Province(2019GGX102056)

摘要/Abstract

摘要：

碳材料以其低成本、良好的化学稳定性和热稳定性等优异特性被广泛应用于各种催化反应中。本研究利用来源广泛的天然脱脂棉为原材料, 通过原位气相掺杂的方法制备了N掺杂、B掺杂、BN共掺杂的生物质碳材料, 并将其应用在丙烷直接脱氢制丙烯反应中。研究发现, 与未掺杂的生物质碳相比, 杂原子掺杂的生物质碳均表现出更高的丙烷转化率和丙烯选择性, 而且N、B单独掺杂的生物质碳材料催化性能优于BN共掺杂的生物质碳材料, 其中N掺杂的生物质碳具有最优催化性能: 在600 ℃反应温度下, 丙烷转化率达到17.6%, 总烯烃收率达14.8%, 且经过12 h的脱氢反应后, 催化剂性能无明显的衰减。通过对这些碳材料的化学结构和催化性能的对比分析, 发现N掺杂和B掺杂使得碳材料表面的大量C-O基团转变为具有丙烷脱氢活性的C=O基团, 抑制反应过程中的C-C键断裂, 从而提高目标产物丙烯的选择性。生物质碳材料成本低廉且来源广泛, 以其作为催化剂可以极大地推动丙烷脱氢工业的发展。

关键词: 生物质碳, 杂原子掺杂, 直接脱氢, 丙烷, 丙烯

Abstract:

Carbon materials have been widely used in various catalytic reactions due to their excellent properties, such as low cost and good chemical/ thermal stability. In this study, nitrogen-doped, boron-doped, and boron-nitrogen co-doped biochars were prepared by in-situ gas-phase doping strategy using natural absorbent cotton as the raw materials. In the reaction of direct dehydrogenation of propane to propylene, the heteroatom-doped biochar showed higher propane conversion and propylene selectivity than the undoped biochar. It was also found that the catalytic performance of nitrogen and boron independently doped biochar was better than that of boron and nitrogen co-doped biochar. The nitrogen-doped biochar exhibited the best catalytic performance of which, at the reaction temperature of 600 ℃, the propane conversion reached 17.6%, and the olefins yield was 14.8%. After dehydrogenation reaction for 12 h, the catalyst’s performance exhibited no apparent declination. The characterization results revealed that nitrogen doping and boron doping in biochars could transform many C-O groups on the surface of biochar into C=O groups at an advantage of propane dehydrogenation activity, which inhibits the C-C bond breaking in the reaction process and improves the selectivity of propylene. Furthermore, duo to biochars rich in resources and low cost, they would promote the industrialization of direct dehydrogenation of propane.

Key words: biochar, heteroatom-doping, direct dehydrogenation, propane, propylene

中图分类号:

O643

甘洪宇, 冯燕, 杨德鸿, 田煜彬, 李阳, 邢涛, 李智, 赵学波, 代鹏程. 杂原子掺杂生物质碳催化丙烷直接脱氢制丙烯[J]. 无机材料学报, 2022, 37(10): 1058-1064.

GAN Hongyu, FENG Yan, YANG Dehong, TIAN Yubin, LI Yang, XING Tao, LI Zhi, ZHAO Xuebo, DAI Pengcheng. Heteroatom-doped Biochar for Direct Dehydrogenation of Propane to Propylene[J]. Journal of Inorganic Materials, 2022, 37(10): 1058-1064.

图/表 12

图1 样品B-BC、N-BC、BN-BC及BC的XRD谱图

Fig. 1 XRD patterns of samples B-BC, N-BC, BN-BC, and BC

图2 样品B-BC、N-BC、BN-BC及BC的XPS 全谱

Fig. 2 XPS survey spectra of samples B-BC, N-BC, BN-BC, and BC

表1 XPS对样品B-BC、N-BC、BN-BC及BC的组成分析(原子分数)

Table 1 Component analyses of samples B-BC, N-BC, BN-BC, and BC (atom fraction)

Sample	C/%	N/%	O/%	B/%
B-BC	82.6	-	16.57	0.83
N-BC	68.38	17.2	14.42	-
BN-BC	66.13	18.65	14.09	1.13
BC	83.76	-	16.24	-

图3 N-BC 样品的SEM(a, b)和TEM(c, d)照片

Fig. 3 SEM (a, b) and TEM (c, d) images of sample N-BC

图4 样品B-BC、N-BC、BN-BC及BC的N2吸附-脱附等温线(a)和孔径分布(b)

Fig. 4 N2 absorption/desorption isotherms (a) and DFT pore size distribution (b) of samples B-BC, N-BC, BN-BC, and BC

表2 样品的比表面积、孔体积及平均孔径

Table 2 Specific surface area, pore volume and average pore size of the samples

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	Pore diameter/nm
N-BC	1303	0.582	0.79-2.10
BN-BC	1226	0.535	0.62-4.50
B-BC	765	0.281	0.73-3.50
BC	497	0.191	0.62-0.87

图5 样品B-BC、N-BC、BN-BC及BC的拉曼光谱

Fig. 5 Raman spectra of samples B-BC, N-BC, BN-BC and BC

图6 不同催化剂在相同丙烷转化率(20%)下的产物分布(a)和相同温度(600 ℃)下丙烷转化率及烯烃收率(b)

Fig. 6 Product distribution at the same conversion (20%) (a) and conversion and olefins yield of propane (b) over different carbon catalysts at reaction temperatures of 600 ℃ The reaction conditions: 0.5 g catalyst, He-to-propane ratio = 3, GHSV = 3840 mL·g-1·h-1 Colorful figures are available on website

图7 样品BN-BC、B-BC、N-BC 及 BC的O1s精细谱图

Fig. 7 High-resolution O1s XPS spectra of samples BN-BC, B-BC, N-BC, and BC

图8 N-BC催化丙烷脱氢稳定性测试(a)和反应12 h内碳平衡数据(b)

Fig. 8 Stability test (a) and carbon balance during the catalytic test (b) of N-BC for direct dehydrogenation (DDH) reaction over 12 h GHSV = 3840 mL·g-1·h-1; TOS: Time on stream

图S1 BN-BC和B-BC的B1s精细图谱(a),BN-BC和N-BC的N 1s精细图谱(b)

Fig.S1 High-resolution B1s XPS spectra of BN-BC and B-BC (a), N1s XPS spectra of BN-BC and N-BC (b)

表S1 部分催化剂用于丙烷直接脱氢制丙烯的反应活性

Table S1 Catalytic performance of some catalysts for direct dehydrogenation of propane

Catalyst	T/℃	X% (C₃H₈)	Y% (Olefins)	Ref.
N-BC	600	17.6	14.8	This work
BN-BC	600	14.35	12.1	This work
B-BC	600	16.31	14.1	This work
BC	600	10.58	9.1	This work
5Cr₂O₃/SBA-15	580	18.0	14.8	[24]
PtSn/HZSM-5	590	22.9	11.2	[25]
CNTs	600	9.0	7.9	[11]
GC	600	6.5	6.1	[11]

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杂原子掺杂生物质碳催化丙烷直接脱氢制丙烯

Heteroatom-doped Biochar for Direct Dehydrogenation of Propane to Propylene

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