粉煤灰水热合成Y型沸石及其表征
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摘要
针对固体废弃物粉煤灰的资源化利用问题,探索合成Y型沸石的实验方法。以燃煤锅炉产生的粉煤灰为实验对象,经过筛分、研磨、高温煅烧和酸浸等预处理方法来提高硅铝含量。将预处理后的粉煤灰加碱煅烧后与氢氧化钠水溶液混合,水热合成Y型沸石。结果表明:粉煤灰经过750℃煅烧1.5 h可以去除约15%的碳;用4 mol·L~(-1)的盐酸在90℃下处理2 h,粉煤灰中的铁、钙和硫等杂质可以分别减少约63.1%、87.3%和79.6%;粉煤灰预处理后的质量减少约51%;预处理后的粉煤灰经过加碱熔融处理,其中的石英和莫来石晶相物质被完全破坏,生成了新的晶相物质;当预处理粉末/碱的质量比为1∶1.2时,熔融产物经过水热反应(温度95~105℃、时间12~24 h)可以生成纯度良好、形貌规则的八面棱柱体Y型沸石;粉煤灰合成Y型沸石的BET等效比表面积可达389.44 m~2·g~(-1),孔容为0.348 mL·g~(-1),并具有优良的热稳定性。粉煤灰经过适当处理,可以在不外加硅、铝化学试剂以及模板剂情况下水热合成结晶度良好的Y型沸石。
The experimental methods of synthesis of Y-type zeolite were studied in view of the utilization of solid waste of fly ash.The fly ash by coal fired boiler was used to improve the content of silicon and aluminum,after the pre-treatment methods such as screening,grinding,high temperature calcination and acid leaching.The fly ash,after the pre-treatment and alkali calcination,was mixed with Na OH aqueous solution to hydrothermally synthesize Y-type zeolite.The results show that about 15% of carbon in the fly ash can be removed after calcination at 750 ℃ for 1.5 h.By using 4 mol·L~(-1) hydrochloric acid treatment for 2 h at 90 ℃,the impurities such as iron,calcium and sulfur in fly ash can be reduced by about 63.1%,87.3% and 79.6%,respectively.The mass of the fly ash was reduced by about 51% after pre-treatment.The pre-treated fly ash is treated by alkali melting,in which the crystalline phases of quartz and mullite are completely destroyed and a new crystalline phase is formed.When the mass ratio of the pre-treated powder/alkali is 1 ∶ 1.2,the molten product can be converted to an eight-side prismatic Y-type zeolite with good purity and regular morphology through hydrothermal reaction treatment(95 to 105 ℃,12 to 24 h).The BET equivalent specific surface area of Y-type zeolite synthesized with fly ash can reach 389.44 m~2·g~(-1),while pore volume can reach 0.348 mL·g~(-1).And it has excellent thermal stability as well.Through this work,the Y-type zeolite with high crystallinity by hydrothermal synthesis without adding silicon,aluminum chemical reagents and templating agent can be synthesized if the fly ash is properly treated.
The experimental methods of synthesis of Y-type zeolite were studied in view of the utilization of solid waste of fly ash.The fly ash by coal fired boiler was used to improve the content of silicon and aluminum,after the pre-treatment methods such as screening,grinding,high temperature calcination and acid leaching.The fly ash,after the pre-treatment and alkali calcination,was mixed with Na OH aqueous solution to hydrothermally synthesize Y-type zeolite.The results show that about 15% of carbon in the fly ash can be removed after calcination at 750 ℃ for 1.5 h.By using 4 mol·L~(-1) hydrochloric acid treatment for 2 h at 90 ℃,the impurities such as iron,calcium and sulfur in fly ash can be reduced by about 63.1%,87.3% and 79.6%,respectively.The mass of the fly ash was reduced by about 51% after pre-treatment.The pre-treated fly ash is treated by alkali melting,in which the crystalline phases of quartz and mullite are completely destroyed and a new crystalline phase is formed.When the mass ratio of the pre-treated powder/alkali is 1 ∶ 1.2,the molten product can be converted to an eight-side prismatic Y-type zeolite with good purity and regular morphology through hydrothermal reaction treatment(95 to 105 ℃,12 to 24 h).The BET equivalent specific surface area of Y-type zeolite synthesized with fly ash can reach 389.44 m~2·g~(-1),while pore volume can reach 0.348 mL·g~(-1).And it has excellent thermal stability as well.Through this work,the Y-type zeolite with high crystallinity by hydrothermal synthesis without adding silicon,aluminum chemical reagents and templating agent can be synthesized if the fly ash is properly treated.
引文
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[2]KIM J K,LEE H D.Effects of step change of heating source on synthesis of zeolite 4A from coal fly ash[J].Journal of Industrial and Engineering Chemistry,2009,15(5):736-742
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[13]PURNOMO C W,SALIM C,HINODE H.Synthesis of pure Na-X and Na-A zeolite from bagasse fly ash[J].Microporous and Mesoporous Materials,2012,162:6-13
[14]OJHA K,PRADHAN N C,SAMANTA A N.Zeolite from fly ash:Synthesis and characterization[J].Bulletin of Materials Science,2004,27(6):555-564
[15]INADA M,TSUJIMOTO H,EGUCHI Y,et al.Microwave-assisted zeolite synthesis from coal fly ash in hydrothermal process[J].Fuel,2005,84(12/13):1482-1486
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[17]FUKUI K,KANAYAMA K,YAMAMOTO T,et al.Effects of microwave irradiation on the crystalline phase of zeolite synthesized from fly ash by hydrothermal treatment[J].Advanced Powder Technology,2007,18(4):381-393
[18]BELVISO C,CAVALCANTE F,LETTINO A,et al.Effects of ultrasonic treatment on zeolite synthesized from coal fly ash[J].Ultrasonics Sonochemistry,2011,18(2):661-668
[19]中国科学院大连化学物理研究所分子筛组.沸石分子筛[M].北京:科学出版社,1978:35-38
[20]王宇.低成本粉煤灰沸石的制备及其同步脱氨除磷试验研究[D].长沙:湖南大学,2011
[21]王春峰.利用粉煤灰合成沸石技术与吸附性能研究[D].南京:南京理工大学,2009
[22]户朝帅.粉煤灰沸石的合成及处理焦化废水的研究[D].昆明:昆明理工大学,2008
[23]WANG J Q,HUANG Y X,PAN Y,et al.New hydrothermal route for the synthesis of high purity nanoparticles of zeolite Y from kaolin and quartz[J].Microporous and Mesoporous Materials,2016,232:77-85
[24]单志超,刘思宇,李彩今,等.Y沸石的高温合成[J].物理化学学报,2011,27(4):959-964
[25]CHIYODA O,DAVIS M E.Hydrothermal conversion of Y-zeolite using alkaline-earth cations[J].Microporous and Mesoporous Materials,1999,32(3):257-264
[26]张婷,严红,王帆.纳米Y沸石合成及表征的研究[J].大连大学学报,2012,33(6):55-58
[27]裴仁彦,张耀日,霍志萍,等.高岭土微球原位合成纳米Y沸石[J].无机盐工业,2013,45(7):61-64
[28]徐芳芳.由粉煤灰制备Y型沸石分子筛的研究[D].沈阳:东北大学,2014
[29]王群,成岳,刘芳.利用粉煤灰制备Na Y分子筛及吸附性能研究[J].陶瓷学报,2009,30(3):345-348
[2]KIM J K,LEE H D.Effects of step change of heating source on synthesis of zeolite 4A from coal fly ash[J].Journal of Industrial and Engineering Chemistry,2009,15(5):736-742
[3]曾小强,叶亚平,王明文,等.粉煤灰分步溶出硅铝制备纯沸石分子筛的研究[J].硅酸盐通报,2007,26(1):19-24
[4]张晶晶,张雪峰,林忠,等.碱熔融法合成粉煤灰沸石[J].化工环保,2012,32(4):358-361
[5]PARK M,CHOI C L,LIM W T,et al.Molten-salt method for the synthesis of zeolitic materials:II.Characterization of zeolitic materials[J].Microporous and Mesoporous Materials,2000,37(1/2):91-98
[6]于艳卿,邹晓兰,李超峰,等.海水为溶剂合成纳米粉煤灰沸石及其性能表征[J].海洋科学,2012,36(1):49-53
[7]MOLINA A,POOLE C.A comparative study using two methods to produce zeolites from fly ash[J].Minerals Engineering,2004,17(2):167-173
[8]TANAKA H,SAKAI Y,HINO R.Formation of Na-A and-X zeolites from waste solutions in conversion of coal fly ash to zeolites[J].Materials Research Bulletin,2002,37(11):1873-1884
[9]FOTOVAT F,KAZEMIAN H,KAZEMEINI M.Synthesis of Na-A and faujasitic zeolites from high silicon fly ash[J].Materials Research Bulletin,2009,44(4):913-917
[10]AMRHEIN C,HAGHNIA G H,KIM T S,et al.Synthesis and properties of zeolites from coal fly ash[J].Environmental Science&Technology,1996,30(3):735-742
[11]LIN C F,HSI H C.Resource recovery of waste fly ash:Synthesis of zeolite-like materials[J].Environmental Science&Technology,1995,29(4):1109-1117
[12]INOUE K,TSUNEMATSU S,YAMADA H.Synthesis of A type zeolite from fly ash pretreated with solid sodium hydroxide[J].Journal of the Society of Inorganic Materials Japan,1995,2(255):108-114
[13]PURNOMO C W,SALIM C,HINODE H.Synthesis of pure Na-X and Na-A zeolite from bagasse fly ash[J].Microporous and Mesoporous Materials,2012,162:6-13
[14]OJHA K,PRADHAN N C,SAMANTA A N.Zeolite from fly ash:Synthesis and characterization[J].Bulletin of Materials Science,2004,27(6):555-564
[15]INADA M,TSUJIMOTO H,EGUCHI Y,et al.Microwave-assisted zeolite synthesis from coal fly ash in hydrothermal process[J].Fuel,2005,84(12/13):1482-1486
[16]TANAKA H,FUJII A,FUJIMOTO S,et al.Microwave-assisted two-step process for the synthesis of a single-phase Na-A zeolite from coal fly ash[J].Advanced Powder Technology,2008,19(1):83-94
[17]FUKUI K,KANAYAMA K,YAMAMOTO T,et al.Effects of microwave irradiation on the crystalline phase of zeolite synthesized from fly ash by hydrothermal treatment[J].Advanced Powder Technology,2007,18(4):381-393
[18]BELVISO C,CAVALCANTE F,LETTINO A,et al.Effects of ultrasonic treatment on zeolite synthesized from coal fly ash[J].Ultrasonics Sonochemistry,2011,18(2):661-668
[19]中国科学院大连化学物理研究所分子筛组.沸石分子筛[M].北京:科学出版社,1978:35-38
[20]王宇.低成本粉煤灰沸石的制备及其同步脱氨除磷试验研究[D].长沙:湖南大学,2011
[21]王春峰.利用粉煤灰合成沸石技术与吸附性能研究[D].南京:南京理工大学,2009
[22]户朝帅.粉煤灰沸石的合成及处理焦化废水的研究[D].昆明:昆明理工大学,2008
[23]WANG J Q,HUANG Y X,PAN Y,et al.New hydrothermal route for the synthesis of high purity nanoparticles of zeolite Y from kaolin and quartz[J].Microporous and Mesoporous Materials,2016,232:77-85
[24]单志超,刘思宇,李彩今,等.Y沸石的高温合成[J].物理化学学报,2011,27(4):959-964
[25]CHIYODA O,DAVIS M E.Hydrothermal conversion of Y-zeolite using alkaline-earth cations[J].Microporous and Mesoporous Materials,1999,32(3):257-264
[26]张婷,严红,王帆.纳米Y沸石合成及表征的研究[J].大连大学学报,2012,33(6):55-58
[27]裴仁彦,张耀日,霍志萍,等.高岭土微球原位合成纳米Y沸石[J].无机盐工业,2013,45(7):61-64
[28]徐芳芳.由粉煤灰制备Y型沸石分子筛的研究[D].沈阳:东北大学,2014
[29]王群,成岳,刘芳.利用粉煤灰制备Na Y分子筛及吸附性能研究[J].陶瓷学报,2009,30(3):345-348
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