Preparation of Flower⁃Like Cobalt Molybdate and Its Aerobic Oxidation Desulfurization Performance

doi:10.12422/j.issn.1672-6952.2024.02.003

Abstract

Abstract:

Aerobic oxidative desulfurization is a safe and environmentally friendly desulfurization method, but oxygen usually needs to be activated under harsh conditions, the synthesis of efficient catalyst is an effective way to improve desulfurization activity. In this work, flower?like cobalt molybdate with large specific surface area was synthesized by one?step hydrothermal method using cobalt chloride and ammonium molybdate as raw materials. In addition, urea is used as precipitation agent and structure control agent. The morphology and structure of the CoMoO₄ were characterized by FT?IR, XRD, SEM, XPS and N₂ adsorption desorption techniques. Dibenzothiophene in simulated oil was removed using CoMoO₄ as catalyst and molecular oxygen as oxidant. The effects of reaction temperature, the flow of oxygen, the amount of CoMoO₄ and the type of sulfur compounds on the desulfurization rate were investigated. In addition, the recycling performance of flower?like CoMoO₄ was studied. The experiment shows that the desulfurization rate can reach 98.2% under the optimal reaction conditions. The catalyst can be reused for 5 times without significant reduction in oxidative desulfurization activity. The formation of superoxide radical in the oxidation desulfurization process resulting in high desulfurization activity.

Key words: Cobalt molybdate, Oxidative desulfurization, Flower?like, Specific surface area, Superoxide radical

摘要：

有氧氧化脱硫是一种安全环保的脱硫方法，但是氧气常需要在较为苛刻的条件下才能被激活，合成高效的有氧氧化脱硫催化剂是提高脱硫活性的有效途径。以氯化钴、钼酸铵为原料，以尿素为沉淀剂和结构控制剂，采用一步水热法合成了大比表面积的花状钼酸钴(CoMoO₄)。通过FT?IR、XRD、SEM、XPS和N₂?吸附脱附技术确定了催化剂的形貌和结构特征；以CoMoO₄为催化剂、氧气为氧化剂，氧化脱除模拟油中的二苯并噻吩，考察了温度、氧气流量、催化剂质量以及硫化物类型对氧化脱硫的影响；此外，研究了花状CoMoO₄的循环使用性能。结果表明，在最适宜的反应条件下，脱硫率达到98.2%；催化剂循环使用5次后，氧化脱硫活性无明显降低，超氧自由基的形成提高了脱硫活性。

关键词: CoMoO₄, 氧化脱硫, 花状, 比表面积, 超氧自由基

CLC Number:

TE624

Xue CAO, Xiuping LI, Jin JIANG, Tieqiang REN, Rongxiang ZHAO. Preparation of Flower⁃Like Cobalt Molybdate and Its Aerobic Oxidation Desulfurization Performance[J]. Journal of Liaoning Petrochemical University, 2024, 44(2): 14-21.

曹雪, 李秀萍, 江进, 任铁强, 赵荣祥. 花状钼酸钴的制备及其好氧氧化脱硫性能[J]. 辽宁石油化工大学学报, 2024, 44(2): 14-21.

Figures/Tables 14

Fig.1 FT?IR spectra of flower?like CoMoO4

Fig.2 XRD spectrum of flower?like CoMoO4

Fig.3 SEM of flower?like CoMoO4

Fig.4 N2 adsorption desorption curve and pore size distribution of flower?like CoMoO4

Fig.5 XPS analysis results of flower?like CoMoO4

Fig.6 The influence of reaction temperature on desulfurization rate

Fig.7 The influence of oxygen flow rate on desulfurization rate

Fig.8 The influence of the amount of flower?like CoMoO4 on desulfurization rate

Fig.9 The influence of sulfide types on desulfurization rate

Fig.10 Recycling performance of flower?like CoMoO4

Fig.11 Infrared spectra of fresh flower?like CoMoO4 and recycled flower?like CoMoO4

Fig.12 Infrared spectra of dibenzothiophene and its product

Fig.13 Results of free radical capture experiment

Fig.14 Reaction mechanism of oxidative desulfurization

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