雷尼镍的磷量子点改性及其催化加氢脱硫性能

doi:10.16085/j.issn.1000-6613.2023-0359

摘要/Abstract

摘要：

高硫燃油燃烧产生的排放会对环境造成巨大的破坏，严重影响人类的生存，开发高效的加氢脱硫催化剂至关重要。本文以雷尼镍为前体，首次使用磷量子点和商业红磷对非负载型（雷尼镍）催化剂进行改性，并系统探究了改性条件（改性温度、用量、反应温度）对催化剂加氢脱硫（DBT）性能的影响，采用BET比表面积测试、X射线衍射仪、扫面电子显微镜、透射电子显微镜、能量色散光谱和X射线光电子能谱等技术手段进行表征。结果发现，磷量子点改性催化剂的性能明显提升，改性催化剂孔径增大和磷量子点与镍的强相互作用是催化剂性能提升的主要原因。较大的孔径有利于DBT分子扩散，与磷量子点作用生成的带正电Ni ^δ⁺物种将有利于DBT的吸附，进而提高催化剂的加氢脱硫性能，并在最佳实验条件下得到了99.1%的DBT转化率。

关键词: 催化剂, 化学反应, 磷量子点, 改性, 加氢脱硫

Abstract:

The emission of high-sulfur fuel combustion will cause great damage to environment and seriously affect the living environment of human beings. It is very important to develop efficient hydrodesulfurization (HDS) catalysts. In this work, Phosphorus quantum dots and commercial red phosphorus were used for the first time to modify the unsupported catalyst (Raney nickel), and the influence of modification conditions (modification temperature, dosage, reaction temperature) on the performance of catalyst hydrodesulfurization (DBT) was systematically explored. The modified catalysts were characterized by BET, XRD, SEM, TEM, EDS and XPS, and their catalytic activity was evaluated for dibenzothiophene (DBT) hydrogenation. The results showed that the HDS performance of Rainey nickel modified with phosphorus quantum dots were greatly improved that could be attributed to the increased pore size of the modified catalyst and the strong interaction between phosphorus quantum dots and nickel. Large pore size was beneficial for the diffusion of DBT molecules, and the positively charged Ni ^δ⁺ generated by the interaction with phosphorus quantum dots facilitates the adsorption of DBT, thereby improving the hydrodesulfurization performance of the catalyst. DBT conversion rate of 99.1% was achieved under optimal experimental conditions.

Key words: catalyst, chemical reaction, phosphorus quantum dots, modification, hydrodesulfurization

中图分类号:

TE624.55

谷星朋, 马红钦, 刘嘉豪. 雷尼镍的磷量子点改性及其催化加氢脱硫性能[J]. 化工进展, 2024, 43(3): 1293-1301.

GU Xingpeng, MA Hongqin, LIU Jiahao. Modification of Rainey nickel with phosphorus quantum dots and its catalytic hydrodesulfurization performances[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1293-1301.

图/表 10

图1 红磷量子点制备过程

图2 磷量子点粒径的统计分布

图3 不同用量磷量子点改性催化剂的BET测试结果

表1 催化剂BET测试结果

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Ni	83.02	0.041	3.00
Ni-2	75.92	0.050	3.45
Ni-4	43.73	0.065	6.09
Ni-6	37.24	0.054	6.10
Ni-8	41.55	0.073	6.74
Ni-10	44.66	0.065	6.04

图4 改性催化剂的XRD结果

图5 不同磷源改性催化剂的SEM结果

图6 不同磷量子点溶液用量改性催化剂的SEM结果

图7 改性催化剂的EDS结果

图8 不同温度改性催化剂的XPS结果

图9 不同因素对加氢活性影响的测试结果

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