Chemical Looping Ammonia Synthesis with High Performance Supported Molybdenum-based Nitrogen Carrier

doi:10.6023/A22010057

Abstract

Ammonia is not only a vital source of fertilizers production, but also a hydrogen carrier with high energy density, which has the potential to replace the traditional fossil fuels. However, the industrial route for ammonia production (Haber-Bosch process) is a highly energy-intensive process owing to the harsh operating conditions requirement. It is important to develop a novel ammonia synthesis process with mild operating conditions. Chemical looping ammonia synthesis (CLAS) is known to be an innovative and environmentally-friendly low-pressure ammonia synthesis technology, which separates the overall ammonia synthesis reaction into nitrogen release and replenish reactions facilitated with a nitrogen carrier (NC). NC with high efficiencies is the key to the the practical feasibility of CLAS technology. In this work, the supported molybdenum-based NCs were prepared with ammonium molybdate, hexamethylenetramine, and ZSM-5 zeolites through a facile pyrolysis method at different temperatures, and the performance of N-release, N-fixation, and the cyclic CLAS of NCs were studied in detail. The results indicate that the supported molybdenum-based NC pyrolyzed at 450 ℃ outperformed other NCs with an average NH₃ production rate of ca. 20000 μmol•g^-1•h^-1, which is two or three orders of magnitude higher than that of the known metal nitrides under similar conditions. Bulk and surface analyses of NCs indicated the migration of lattice nitrogen of NC during the direct hydrogenation step for NH₃ formation. At N-fixation stage, the nitrogen vacancy of molybdenum-based NC is expected to be recharged from N₂. However, the low kinetics is an important problem of NC nitridation. With the introduction of H₂, the nitridation kinetics of NC was significantly enhanced, improving the NC regeneration. During a 12-cycle test at 600 ℃ and atmospheric pressure, and the ammonia production rate was stabilized at ca. 1500 μmol•g^-1•h^-1 for each cycle. This article investigated the preliminary feasibility of the supported molybdenum-based nitride as NC during the process of CLAS and could provide a theoretical basis for the design and development of new types of NCs.

Key words: chemical looping ammonia synthesis, supported molybdenum-based nitrogen carrier, ammonia, nitrogen release, nitrogen fixation

Cite this article

Tan Zhang, Zhongliang Yu, Jiaqi Yu, Huining Wan, Chengyu Bao, Wenqiang Tu, Song Yang. Chemical Looping Ammonia Synthesis with High Performance Supported Molybdenum-based Nitrogen Carrier[J]. Acta Chimica Sinica, 2022, 80(6): 788-796.

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Fig. & Tab. 18

Figure 1. Characteristics of ZSM-5: (a) XRD pattern, (b) SEM image, (c) TG curve

样品名称^a	比表面积/(m²•g^-1)	平均孔径/nm	孔体积/(cm³•g^-1)
载体材料ZSM-5	338.7	2.5	0.09
热解后样品	134.2	3.7	0.03
12次循环后样品	159.8	2.9	0.02

Table 1. Summary of specific surface area, average pore diameter and pore volume of different samples

Figure 2. Pyrolysis curve of Mo2N/ZSM-5 precursor: (a) TG curve and (b) DTG curve

热解温度/℃	w_N/%	w_C/%	w_H/%	w_Mo/%	化学式
400	1.68	1.97	0.24	30.34	Mo₂N_0.76H_0.74C
450	1.60	1.58	0.21	33.84	Mo₂N_0.65H_0.58C_0.74
500	1.44	1.16	0.19	35.38	Mo₂N_0.55H_0.51C_0.52
550	1.39	0.82	0.20	33.47	Mo₂N_0.57H_0.58C_0.39
600	2.68	1.29	0.74	41.57	Mo₂N_0.88H_1.7C_0.5

Table 2. CHNS contents of ZSM-5-supported Mo-based nitrogen carriers after pyrolysis

Figure 3. XRD patterns of supported Mo-based nitrogen carriers at different pyrolysis temperatures

Figure 4. XPS analysis of γ-Mo2N/ZSM-5: (a) full spectrum, (b) high-resolution XPS spectra of Mo 3d and (c) high-resolution XPS spectra of N 1s

Figure 5. (a) SEM and (b) elemental mapping images of ZSM-5-supported Mo-based nitrogen carrier acquired at 600 ℃

Figure 6. NH3 signal during the H2-TPR of Mo-based nitrogen carrier pyrolyzed at 450 ℃

Figure 7. Ammonia yield of samples with H2 at different temperatures: (a) variation curve of ammonia production with time and (b) ammonia production rate at different temperatures

No.	Metal nitrides	Condition	Ammonia production rate/ (μmol•g^-1•h^-1)	Ref.
1	Fe-Mn-N	400 ℃	23	[19]
2	Co-Mn-N	400 ℃	46	[19]
3	Fe₃N	400 ℃	50	[43]
4	Mn₆N_2.58	550 ℃	62	[44]
5	Ta₃N₅	400 ℃	80	[45]
6	Sr₂N	550 ℃	88	[44]
7	Ca₃N₂	550 ℃	121	[44]
8	Re₃N	350 ℃	130	[43]
9	Li-Mn-N	400 ℃	261	[19]
10	Cu₃N	250 ℃	665	[45]
11	Zn₃N₂	400 ℃	852	[45]
12	Mo-N	450 ℃	20000	This work

Table 3. Summary of ammonia production rate of metal nitrides during hydrogenation

Figure 8. XRD patterns of ZSM-5-supported Mo-based nitrogen carrier at 600 ℃ under two stages: after pyrolysis (red line) and after hydrogenation (blue line)

Figure 9. XPS analysis of sample after hydrogenation: (a) high-resolution XPS spectra of Mo 3d and (b) high-resolution XPS spectra of N 1s

Figure 10. SEM and TEM images of ZSM-5-supported Mo-based nitrogen carrier after N-discharge: (a) SEM image, (b) elemental mapping image, (c) TEM image and (d) HRTEM image

Figure 11. XRD patterns of supported Mo-based nitrogen carriers at 600 ℃ under three stages: after pyrolysis (black line), after hydrogenation (red line) and after regeneration (blue line)

Figure 12. XPS analysis of sample after regeneration: (a) high-resolution XPS spectra of Mo 3d and (b) high-resolution XPS spectra of N 1s

Figure 13. SEM and TEM images of ZSM-5-supported Mo-based nitrogen carrier after N-charge. (a) SEM image, (b) elemental mapping, (c) TEM image and (d) HRTEM image

样品名称^a	w_N/%	w_C/%	w_H/%
热解后	2.67	1.29	0.74
氢化后	1.39	1.11	0.71
再生后	1.91	1.09	0.60

Table 4. CHNS contents of samples at three stages: after pyrolysis, after hydrogenation and after regeneration

Figure 14. Cyclic tests of NC sample at 600 ℃ and 0.1 MPa. (a) ammonia production rate during 12 cycles, (b) XRD patterns, (c) SEM image and (d) elemental mapping

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基于高性能负载型钼基载氮体的化学链合成氨性能研究