制备方法对粉煤灰合成沸石的种类及性能的影响

Effects of different preparation methods on the types and properties of zeolites synthesized from coal fly ash

  • 摘要: 针对如何将排放量巨大的固体废弃物粉煤灰合理资源化应用的问题,探索了不同合成方法对粉煤灰制备沸石的种类及性能的影响。考察了碱量、温度、时间等主要因素对合成沸石的种类及对氨氮吸附能力的影响。 研究表明,采用直接水热法在3.0 mol/L的NaOH溶液中100 ℃水热反应60 h可获得NaP型沸石;采用碱熔融水热法,在不添加任何结构导向剂,不外加硅、铝源,90 ℃水热反应12 h的最佳条件下获得了NaA-X沸石。合成的NaP型沸石为形貌不规则的颗粒聚集体,大小不一;合成的NaA-X沸石产物中同时含有典型的A型沸石立方体和X型沸石的八面体形貌,棱角分明,平均粒径约为3.5 μm。NaP型沸石和NaA-X沸石的比表面积为55.9和266.0 m2/g,分别是粉煤灰的21和100倍。NaP型沸石和NaA-X沸石的微孔比表面积为12.0和211.1 m2/g,分别是粉煤灰的17倍和301倍。两种合成沸石的孔容也远大于粉煤灰。氨氮吸附量为153.6 mmol/100 g和226.6 mmol/100 g,分别是粉煤灰的14和20倍。 2种合成沸石的热稳定性都符合工业要求,但直接水热法合成的NaP型沸石热稳定性要低于NaA-X沸石,且产物中含有不易反应的石英和莫来石,导致原料利用率较低。相反,碱熔融水热法合成的NaA-X沸石,有利于惰性晶相转化为活性组分,原料利用率高,产物纯度高,孔隙结构与氨氮吸附量均优于直接水热法的合成产物。

     

    Abstract: To reasonably utilize the large emissions of solid waste coal fly ash (CFA),different methods for zeolite syn- thesis from CFA were explored,focusing on the effects on the types and properties of as-prepared zeolites. The effects of alkali content,temperature and time on the types of synthetic zeolites and ammonia nitrogen adsorption capacity were investigated. The results showed that the NaP zeolite was synthesized via direct hydrothermal method at 100 ℃for 60 h in 3. 0 mol / L NaOH solution. While NaA-X composite zeolite was synthesized via the alkali fusion hydrother- mal method without structure-directing agent,silicon or aluminum source addition at 90 ℃ for 12 h. The synthesized NaP zeolite was a granular aggregate with irregular morphology and different sizes. The morphology of the synthesized NaA-X was characterized by typical cube blocks representing the zeolite A and octahedral ones representing the zeolite X. The particles were angular,with an average particle size of about 3. 5 μm. The specific surface area of NaP and NaA-X were 55. 9 and 266. 0 m2 / g,which were 21 times and 100 times those of fly ash,respectively. The micropore specific surface area of NaP and NaA-X were 12. 0 and 211. 1 m2 / g,which were 17 times and 301 times those of fly ash,respectively. The pore volumes of the two synthetic zeolites were also much larger than that of fly ash. The ammo- nia adsorption capacity were 153. 6 mmol / 100 g and 226. 6 mmol / 100 g,which were 14 times and 20 times those of fly ash,respectively. The thermal stability of the two synthetic zeolites was in line with industrial requirement,but the NaP zeolite synthesized by direct hydrothermal method was lower than that of NaA-X zeolite. Moreover,NaP zeolite contained unreacted quartz and mullite,resulting in low utilization of raw materials. On the contrary,NaA-X zeolite synthesized by alkali fusion hydrothermal method was beneficial to the conversion of inert crystal phase into active component,with the high utilization of raw materials,high product purity,and pore structure and ammonia nitrogen ad- sorption capacity were superior to the product synthesized by direct hydrothermal method.

     

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