有机酸在超声作用下对废FCC催化剂中有害金属脱除的影响  

Effect of Organic Acids on Ultrasonication-assisted Removal of Harmful Metals from Spent FCC Catalysts

作　　者：余裕森 黎氏琼春 王天 张利波[1,2] YU Yusen;LE Thiquynhxuan;WANG Tian;ZHANG Libo(State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,Kunming University of Science and Technology,Kunming 650093,China;Faculty of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China)

机构地区：[1]昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室,昆明650093 [2]昆明理工大学冶金与能源工程学院,昆明650093

出　　处：《材料导报》2023年第8期193-200,共8页Materials Reports

基　　金：云南省科技厅“智汇云南”计划(202103AM140006);云南省基础研究计划项目(202201AU070088,202101BE070001-023);昆明理工大学高层次人才科研平台建设资助(141120200029);昆明理工大学分析测试基金(2020T20204104)。

摘　　要：有害金属Fe、V、Ni是石油流化催化裂化(FCC)催化剂中毒的根源,导致FCC催化剂的活性降低。针对现有废FCC催化剂再生工艺存在有害金属脱除率低、废剂颗粒的微观形貌和分子筛骨架易被破坏、废剂无法回用等问题,以有机酸为浸出剂,提出超声协同有机酸脱除废催化剂中有害金属的强化处理工艺。本研究以保留废FCC催化剂的球状颗粒结构和Y型分子筛骨架结构为前提,研究在超声作用下氧化预处理、有机酸种类、反应温度、时间以及超声功率对废FCC催化剂中有害金属脱除的影响。实验结果表明,在超声作用下,不同有机酸对有害金属的脱除效果从弱到强的顺序为乙酸、EDTA、草酸+乙酸、草酸,而废剂微观结构被破坏的程度也增加。在草酸和乙酸的混合液为浸出剂、超声功率为250 W、浸出温度为70℃、浸出时间为30 min的条件下,V、Fe、Ni脱除率分别高达40.7%、27.5%和17.2%,且浸出后的FCC催化剂球状结构和分子筛骨架结构完整。与常规浸出相比,超声浸出对有害金属的脱除起到强化作用,V、Fe、Ni的浸出率分别提高了19.9%、13.1%和7.7%。The main causes of poisoning of fluid catalytic cracking(FCC)catalysts in the petroleum industry are harmful metals,such as Fe,V and Ni,which reduce the activity of the FCC catalysts.The existing regeneration processes of spent FCC catalysts have problems,such as low metal removal rate,incomplete microstructure,and damaged zeolite Y framework,resulting in the inability of spent FCC catalysts to be reused.An effective method combining organic acids as a leaching agent and ultrasonic radiation was developed in this study to improve the removal effect of harmful metals in spent FCC catalyst without destroying the zeolite Y framework and particle microstructure.The effects of oxidation pretreatment,organic acid type,leaching temperature,leaching time,and ultrasonic power on the zeolite Y framework,particle microstructure,and harmful metal removal were investigated.The experimental results show that the removal effects of different organic acids on harmful metals under ultrasound are in the order from weak to strong as follows:acetic acid,EDTA,oxalic acid+acetic acid,oxalic acid,and the destruction of the microstructure of the spent catalyst particle increases in this order.After leaching in a mixture of oxalic acid and acetic acid for 30 min at 70℃with an ultrasonic power of 250 W,a regenerated catalyst with a complete particle structure and zeolite Y framework was obtained,with the removal rates of V,Fe and Ni 40.7%,27.5%and 17.2%,respectively.Compared to conventional leaching,ultrasonic leaching exhibited a strengthening effect on removing harmful metals,and the leaching rates of V,Fe and Ni increased by 19.9%,13.1%and 7.7%,respectively,during the ultrasonic leaching process.

关 键 词：废FCC催化剂 有机酸 有害金属 超声 脱除 

分 类 号：X742[环境科学与工程—环境工程] TB559[理学—物理]