【作者】 刘杰；

【导师】 刘君腾； 杨汉功；

【作者基本信息】 北京化工大学 ， 化学工程（专业学位）， 2022， 硕士

【摘要】 工业上钼资源的回收主要来源于废催化剂及矿冶过程形成的废液和废渣,使用苯酐-尿素法合成铜酞菁颜料过程中,消耗大量钼酸铵催化剂,目前尚未有从铜酞菁废水中回收Mo(VI)的相关报道。铜酞菁废水酸性强、杂质多,体系中含Mo(VI)离子存在形态较为复杂。若能实现废水中Mo(VI)的分离富集,进而制备钼酸铵供合成反应使用,将节省企业生产环节的费用。本文选用离子交换法对铜酞菁废水中的Mo(VI)进行回收,选取合适的树脂,借助静态实验研究各因素对树脂吸附和解吸性能的影响,设计动态实验确定实际分离过程的操作参数,并对钼酸铵制备过程作初步研究,最后解释吸附过程的机理,为Mo(VI)回收提供理论支持。通过对比七种树脂的平衡吸附容量和解吸率,得出D301树脂更适合用于废水中Mo(VI)的分离。树脂用量为1m L、溶液p H为3.0时,对体积为200m L、浓度为1400mg/L的含Mo(VI)模拟液静态吸附效果较好;静态解吸实验得出较高浓度氨水对本体系饱和树脂的解吸效果较好。将200mg/L、p H=3.0的模拟液以20BV/h的流量通过高径比为2.2的吸附柱时动态吸附效果较好,使用10%的氨水在4BV/h流量条件下对饱和树脂的动态解吸效果较好。循环使用过程中,D301树脂的再生率均超过80%。解吸液结晶所得产品为多种钼酸铵的混合物。D301树脂吸附Mo(VI)过程的热力学特征为熵增大、自发进行且吸收热量,作用机理可用Langmuir等温式和准二级动力学理论解释,吸着阶段的速率为颗粒扩散步骤和液膜扩散步骤同时控制,动态吸附数据借助Thomas与Yoon-Nelson模型作计算得出的结果较佳。更多还原

【Abstract】 In industry,molybdenum is mainly recovered from spent catalysts and from waste liquids and residues formed in metallurgical processes.In the process of synthesizing copper phthalocyanine pigments by the phthalic anhydride-urea method,large amounts of ammonium molybdate catalyst is consumed.There are no reports on the recovery of Mo(Ⅵ)from copper phthalocyanine wastewater.Copper phthalocyanine wastewater has strong acidity and many impurities,and the existence of Mo(Ⅵ)ions in the system is relatively complex.If the separation and enrichment of Mo(Ⅵ)in the wastewater can be realized,and then ammonium molybdate can be prepared for the synthesis reaction,the cost of the production of the enterprise will be saved.In this paper,ion exchange is used to recover Mo(Ⅵ)in copper phthalocyanine wastewater,and the appropriate resin is selected.The effects of various factors on the adsorption and desorption properties of resins were studied by static experiments,and the operating parameters of the actual separation process are determined by dynamic experiments.The preparation process of ammonium molybdate is preliminarily studied,finally the mechanism of the adsorption process is analyzed to provide theoretical support for Mo(Ⅵ)recovery.By comparing the equilibrium adsorption capacity and desorption rate of the seven resins,it was concluded that D301 resin was more suitable for the separation of Mo(Ⅵ)in wastewater.When the resin dosage is 1m L and the p H of the solution is 3.0,the static adsorption effect of the simulated solution containing Mo(Ⅵ)with a volume of 200 m L and a concentration of 1400mg/L is better;the static desorption experiment shows that the higher concentration of ammonia has a better effect on the saturated resin.The dynamic adsorption effect was better when 200mg/L,p H=3.0simulated solution was passed through the adsorption column with a height-diameter ratio of 2.2 at a flow rate of 20BV/h,the desorption effect of10% ammonia on saturated resin is better under the condition of 4BV/h flow rate.The regeneration rate of D301 resin in the recycling process is over 80%.The product obtained from the crystallization of the desorbed solution is a mixture of various ammonium molybdates.The thermodynamic characteristics of the adsorption process of Mo(Ⅵ)by D301 resin are entropy-increasing,spontaneous and endothermic.The mechanism of process can be explained by Langmuir isotherm and pseudo-second-order kinetic theory.The rate of the adsorption process is controlled by liquid film diffusion and particle diffusion steps,and dynamic adsorption data were better fitted by Thomas and Yoon-Nelson models.更多还原