Effect of hydrochloric acid treatment on catalytic performance of Ru/Ba-MgO catalyst template cotton fiber

doi:10.16085/j.issn.1000-6613.2023-0282

Abstract

Abstract:

The cotton fibers were pretreated with different concentrations of hydrochloric acid and then used as biological templates to prepare fibrous strip biomimetic Ru/Ba-MgO ammonia synthesis catalysts. The effect of cellulose hydrogen bonding in cotton fibers on Ru/Ba-MgO catalysts was investigated by characterization techniques such as XRD, FTIR, FE-SEM, EDS, BET, H₂-TPR and TG for cotton fibers, Ba-MgO carriers and Ru/Ba-MgO catalysts. The results showed that H⁺ in hydrochloric acid solution would break the intra-cellulose molecular hydrogen bonds in cotton fibers, which exposed a large number of highly reactive hydroxyl groups within the cellulose and enhanced the adsorption of Mg²⁺and Ba²⁺, and the specific surface area of the Ba-MgO carriers increased significantly and the pore size decreased significantly. Pretreatment of cotton fibers with suitable concentrations of hydrochloric acid can effectively regulate the particle size of the active component Ru in the catalyst and its dispersion, while the incorporation of co-catalyst Ba inhibited the production of RuO _x and improved the reduction performance of Ru/Ba-MgO catalyst, which ultimately led to the improvement of ammonia synthesis activity and thermal stability of Ru/Ba-MgO catalyst. When cotton fibers were pretreated with 3mol/L hydrochloric acid solution, the prepared Ru/Ba-MgO-3 catalyst had the best activity at 425℃, 10MPa and 10000h^-1 reaction conditions with an outlet ammonia volume concentration of 18.37%.

Key words: biotemplating, cellulose, synthetic ammonia, catalyst, support

摘要：

采用不同浓度的盐酸对棉纤维进行预处理，并以其为生物模板，制备具有纤维条状的仿生Ru/Ba-MgO氨合成催化剂。通过XRD、FTIR、FE-SEM、EDS、BET、H₂-TPR和TG等表征技术，分别对棉纤维、Ba-MgO载体和Ru/Ba-MgO催化剂进行分析，探讨了棉纤维中纤维素氢键对Ru/Ba-MgO催化剂的影响机理。结果表明，盐酸溶液中的H⁺会破坏棉纤维中纤维素分子内氢键，使得纤维素内大量高反应性的羟基暴露出来，增强了棉纤维对Mg²⁺，尤其是对Ba²⁺的吸附，以其为模板制备的Ba-MgO载体比表面积明显增加，孔径明显减小；棉纤维经过适宜浓度的盐酸预处理可以有效调控催化剂中活性组分Ru的颗粒尺寸及其分散度；助催化剂Ba的掺入抑制了RuO _x 的产生，改善了Ru/Ba-MgO催化剂的还原性能，最终使得Ru/Ba-MgO催化剂氨合成活性和热稳定性提高。当棉纤维经过3mol/L盐酸溶液预处理时，以其为模板制备的Ru/Ba-MgO-3催化剂在425℃、10MPa和10000h^-1反应条件下具有最佳的活性，其出口氨体积分数为18.37％。

关键词: 生物模板, 纤维素, 合成氨, 催化剂, 载体

CLC Number:

TQ426.81

DING Kang, HE Junqiao, CHEN Yuanjie, YANG Xiazhen, LIU Huazhang, HUO Chao. Effect of hydrochloric acid treatment on catalytic performance of Ru/Ba-MgO catalyst template cotton fiber[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 962-970.

丁康, 何军桥, 陈元捷, 杨霞珍, 刘化章, 霍超. Ru/Ba-MgO氨合成催化剂模板棉纤维的盐酸处理对催化性能的影响[J]. 化工进展, 2024, 43(2): 962-970.

Figures/Tables 19

References 21

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催化剂	C	O	Mg	Ba	Ru
Ru/Ba-MgO	1.26	43.42	52.02	0.95	2.35
Ru/Ba-MgO-1	2.01	40.38	52.96	2.51	2.14
Ru/Ba-MgO-2	3.02	41.02	51.07	3.01	1.88
Ru/Ba-MgO-3	2.23	42.90	48.95	3.95	1.97
Ru/Ba-MgO-4	2.47	39.42	52.34	3.82	1.95

催化剂	C	O	Mg	Ba	Ru
Ru/Ba-MgO	1.26	43.42	52.02	0.95	2.35
Ru/Ba-MgO-1	2.01	40.38	52.96	2.51	2.14
Ru/Ba-MgO-2	3.02	41.02	51.07	3.01	1.88
Ru/Ba-MgO-3	2.23	42.90	48.95	3.95	1.97
Ru/Ba-MgO-4	2.47	39.42	52.34	3.82	1.95

条件	C	O	Mg	Ba	Ru
评价前	2.23	42.90	48.95	3.95	1.97
评价后	1.69	42.48	49.88	3.93	2.02

条件	C	O	Mg	Ba	Ru
评价前	2.23	42.90	48.95	3.95	1.97
评价后	1.69	42.48	49.88	3.93	2.02

载体	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1	平均晶粒度/nm
Ba-MgO	33	31.22	0.26	18.7
Ba-MgO-1	34	27.41	0.23	17.3
Ba-MgO-2	39	23.39	0.23	16.4
Ba-MgO-3	47	19.69	0.23	14.9
Ba-MgO-4	44	23.78	0.26	15.9