Heteroatom-doped Biochar for Direct Dehydrogenation of Propane to Propylene

doi:10.15541/jim20220093

Abstract

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

CLC Number:

O643

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.

Figures/Tables 12

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

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

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	-

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

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

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

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

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

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

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

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

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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