基于高性能负载型钼基载氮体的化学链合成氨性能研究

doi:10.6023/A22010057

摘要/Abstract

化学链合成氨是一种新型的、环境友好的低压合成氨技术, 其借助于载氮体的传递作用实现固氮与释氮制氨的循环, 已受到产学界的广泛关注. 构建高效、绿色的载氮体是化学链合成氨技术的关键. 本工作通过一步热解法制备了负载型钼基载氮体, 并对其释氮、固氮及稳定性进行了研究. 结果表明: 在释氮阶段, 当热解制备温度为450 ℃时, 钼基载氮体的氢化产氨速率为最大, 可达20000 μmol•g^-1•h^-1; 固氮过程中, 氢气的引入加快了钼基载氮体从氮气中补充晶格氮的速率, 实现了载氮体的高效再生; 历经12次循环后, 负载型钼基载氮体(制备温度为600 ℃)的产氨速率基本稳定在1500 μmol•g^-1•h^-1. 本研究探索了负载型钼基载氮体化学链合成氨的可行性, 结果可为新型过渡金属基载氮体的开发及其化学链合成氨研究提供理论基础.

关键词: 化学链合成氨, 负载型钼基载氮体, 氨气, 释氮, 固氮

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

引用此文

张谭, 余钟亮, 余嘉祺, 万慧凝, 包成宇, 涂文强, 杨颂. 基于高性能负载型钼基载氮体的化学链合成氨性能研究[J]. 化学学报, 2022, 80(6): 788-796.

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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图/表 18

图1. ZSM-5载体材料的相关表征: (a) XRD图谱, (b) 扫描电镜图, (c) TG曲线

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

表1. 不同样品比表面积、平均孔径和孔体积汇总

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

图2. Mo2N/ZSM-5前驱体的热解曲线: (a) TG曲线, (b) DTG曲线

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

表2. 热解后负载型钼基载氮体中CHNS元素含量

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

图3. 不同热解温度下负载型钼基载氮体的XRD图谱

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

图4. γ-Mo2N/ZSM-5样品XPS分析: (a) 全谱, (b) Mo 3d 精细谱以及 (c) N 1s 精细谱

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

图5. 600 ℃下制备的负载型钼基载氮体(a)扫描电镜和(b)元素扫描图像

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

图6. 450 ℃热解所得样品在H2-TPR过程中NH3信号曲线

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

图7. 样品在不同温度下氢化产氨: (a) 氨产量随时间变化曲线及(b) 不同温度下产氨速率

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

表3. 金属氮化物氢化产氨速率

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

图8. 600 ℃下, 负载型钼基载氮体经历两个阶段后的XRD谱图: 热解后(红线)以及氢化后(蓝线)

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)

图9. 氢化后样品XPS分析: (a) Mo 3d 精细谱以及(b) N 1s 精细谱

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

图10. 负载型钼基载氮体释氮后的SEM和TEM图像: (a) SEM图, (b) 元素扫描图, (c) TEM图以及(d) 高分辨TEM图

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

图11. 600 ℃下, 负载型钼基载氮体经历三个阶段后的XRD谱图: 热解后(黑线), 氢化后(红线)以及再生后(蓝线)

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)

图12. 再生后样品XPS分析: (a) Mo 3d 精细谱以及(b) N 1s 精细谱

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

图 13. 负载型钼基载氮体固氮后的扫描电镜和透射电镜图像. (a)扫描电镜图像, (b)元素扫描, (c) TEM图以及(d)高分辨TEM图

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

表4. 热解、氢化和再生三个阶段后样品CHNS元素含量

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

图14. 600 ℃和0.1 MPa下12次循环测试. (a) 12次循环过程中产氨速率, (b) XRD 谱图, (c)扫描电镜图, (d)元素扫描

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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