(1. 桂林理工大学 化学与生物工程学院，广西有色金属隐伏矿床勘查及材料开发协同创新中心, 桂林 541004；
2. 广西壮族自治区环境应急与事故调查中心，南宁 530028；
3. 广西壮族自治区固体废物和化学品环境管理中心，南宁 530028)
摘 要: 以有色金属钨矿和铅锌矿尾矿为原料，分别采取酸浸后高温碱熔和无酸浸低温碱溶两种活化预处理，并以常规水热法(CH)和微波水热法(MH)合成ZSM-5分子筛，采用XRF、ICP-AES、FT-IR、XRD、SEM、BET和催化剂活性评价对所得产物进行表征分析。结果表明：合成产物为ZSM-5分子筛，其总比表面积在273.21~350.51 m2/g之间，MH法产物孔径较小；低温碱溶可以得到更高硅铝摩尔比n(SiO2)/n(Al2O3)的前驱液，导致产物形貌由类球形转变为六方棱柱形，并且产物粒径减小；高温碱熔合成产物对干化尾矿SiO2利用率更高，不过工艺复杂，能耗高；活化过程SiO2溶出率的影响因素程度由高到低的顺序为CaO、其他杂质、Fe2O3；合成相同结晶度的ZSM-5分子筛时，MH法所需时间仅为CH法的四分之一左右，并且合成产物粒径更小，表面更洁净，SiO2利用率更高；1 L反应釜工艺放大效应小，搅拌条件有利于合成体系的传质和传热，导致产物粒径减小，产物应用于脱硝反应的NO转化率可达94.31%。
关键字: 有色金属尾矿；预处理；ZSM-5分子筛；合成工艺
（1. Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal Deposits and Development of New Materials in Guangxi, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China;
2. Environmental Emergency and Accident Investigation Center of Guangxi Zhuang Autonomous Region, Nanning 530028, China;
3. Solid Waste and Chemical Environmental Management Center of Guangxi Zhuang Autonomous Region, Nanning 530028, China）
Abstract:The ZSM-5 molecular sieve was synthesized by conventional hydrothermal method (CH) and microwave hydrothermal method (MH), using non-ferrous metal tungsten ore and lead-zinc ore tailings as materials which were activated pretreatment by high-temperature alkali fusing after acid leaching and low-temperature alkali dissolving without acid leaching, respectively. The obtained products were characterizated by XRF, ICP-AES, FT-IR, XRD, SEM, BET and catalyst activity evaluation. The results show that, the synthesized product is ZSM-5 molecular sieve. BET shows that the total specific surface area of the product is between 273.21-350.51 m2/g, and the pore diameter of the product by the MH is small. Low-temperature alkali dissolution activate pretreatment can obtain higher n(SiO2)/n(Al2O3) liquid precursors, which leads to the transformation of the morphology of the product from a spherical shape to a hexagonal prism shape, and the particle size of the product decreases. The product synthesis by activation pretreatment with high-temperature alkali fusion has a higher utilization of the SiO2 of dried tailings, but the process is complicated and the energy consumption is high. The sequence of influence factors of SiO2 dissolution rate during activation from high to low are: CaO, Others, Fe2O3. The required time to synthesize ZSM-5 with the same crystallinity by MH method is only about a quarter of the that of CH method, and the product size by the MH method is smaller, the surface is cleaner, and the SiO2 utilization rate is also higher. The 1 L reactor has a small amplification effect, and the stirring conditions are conducive to the mass and heat transfer of the synthesis system, resulting in a decrease in the particle size of the product, and the NO conversion rate of the product applied to the denitration reaction can reach 94.31%.
Key words: non-ferrous metal tailings; pretreatment; ZSM-5 zeolite; synthesis technology
