花状钼酸钴的制备及其好氧氧化脱硫性能

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

曹雪 李秀萍 江进 任铁强 赵荣祥

Xue CAO Xiuping LI Jin JIANG Tieqiang REN Rongxiang ZHAO

辽宁石油化工大学 石油化工学院，辽宁 抚顺 113001 浙江石油化工有限公司，浙江 舟山 316299

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China Zhejiang Petroleum and Chemical Co. Ltd. ，Zhoushan Zhejiang 316299，China

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。

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.

辽宁省自然科学基金指导计划项目(2019?ZD?0064)

10.12422/j.issn.1672-6952.2024.02.003