Ammonium and Lead Exchange in Clinoptilolite Zeolite Column
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AMMONIUM AND LEAD EXCHANGE IN CLINOPTILOLITE ZEOLITE COLUMN A THESIS SUBMITTED TO THE GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCES OF MIDDLE EAST TECHNICAL UNIVERSITY BY AHMAD DH. BAHAALLDDIN IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMICAL ENGINEERING DECEMBER 2010 Approval of the thesis: AMMONIUM AND LEAD EXCHANGE IN CLINOPTILOLITE ZEOLITE COLUMN submitted by AHMAD DH. BAHAALDDIN in partial fulfillment of the requirements for the degree of Master of Science in Chemical Engineering Department, Middle East Technical University by, Prof. Dr. Canan Özgen __________________ Dean, Graduate School of Natural and Applied Sciences Prof. Dr. Gürkan Karakaş __________________ Head of Department, Chemical Engineering Prof. Dr. Hayrettin Yücel __________________ Supervisor, Chemical Engineering, METU Examining Committee Members: Assoc. Prof. Dr. Halil Kalıpçılar __________________ Chemical Engineering Dept., METU Prof. Dr. Hayrettin Yücel __________________ Chemical Engineering Dept., METU Assoc. Prof. Dr. Naime Aslı Sezgi __________________ Chemical Engineering Dept., METU Assoc. Prof. Dr. İpek İmamoğlu __________________ Environmental Engineering Dept., METU Dr. Cevdet Öztin __________________ Chemical Engineering Dept., METU Date: December 17, 2010 I hereby declare that all information in this document has been obtained and presented in accordance with academic rules and ethical conduct. I also declare that, as required by these rules and conduct, I have fully cited and referenced all material and results that are not original to this work. Name, Last name: Ahmad Dh. Bahaalddin Signature: iii ABSTRACT AMMONIUM AND LEAD EXCHANGE IN CLINOPTILOLITE ZEOLITE COLUMN Bahaalddin, Ahmad Dh. M.Sc., Department of Chemical Engineering Supervisor: Prof. Dr. Hayrettin Yücel December 2010, 152 pages Wastewaters resulted from anthropogenic influence can encompass a wide range of potential contaminants and concentrations. There are numerous procedures that can be used to clear out wastewaters depending on the type and extent of contamination, however; disposal of pollutants from wastewaters in industrial scale is a difficult and costly problem. In this study, the use of ion exchange theory utilizing natural Turkish clinoptilolite zeolite from Gördes-Manisa as ion exchange resins in down-flow column mode is investigated. The clinoptilolite with particle size range of 0.25-0.50 mm is used in 2+ + the removal of lead Pb and ammonium NH4 ions from aqueous solutions. The aim of the study is to set up the conditions under which clinoptilolite may be used in an economical and efficient approach in the removal process. Experiments were divided into two sets: binary studies, and ternary studies, and the effects of iv conditioning clinoptilolite with NaCl solution, flow rate, and initial concentration of the solutions on the removal behavior were investigated. In binary studies, results showed that increasing the loading volumetric flow rate resulted in decreasing the breakthrough capacity and the column efficiency, while the total capacity remained constant. The maximum total capacity was determined as + 2+ 1.16 meq/g of zeolite for NH4 , and 1.1 meq/g of zeolite for Pb and these values were close to each other and to the sodium content of Na-form of pretreated clinoptilolite (1.16 meq/g of zeolite). In addition, by decreasing the initial contaminant concentration, an increase in breakthrough capacity and column efficiency was observed. 2+ + In ternary studies, the results showed that the removal of Pb and NH4 ions are dependent on the flow rate, in which at moderately low flow rate, a higher ion exchange capacity is yielded. That was explained as at higher flow rates, the retention time was insufficient for the ion exchange process to take place completely between clinoptilolite and lead and ammonium ions. Thus, a competition between 2+ + Pb and NH4 ions for the exchange sites on clinoptilolite was observed and this competition was in favor of lead ions. Consequently, it was observed that the clinoptilolite zeolite has affinity for both Pb2+ + and NH4 ions. However, the affinity of clinoptilolite for lead ions is higher than that for ammonium ions. Therefore, the cations selectivity for clinoptilolite according to + 2+ + their affinity is determined as the following sequence: NH4 > Pb > Na . Keywords: Clinoptilolite, Ion exchange, Pretreatment, Lead, Ammonium, Removal, Column, Multicomponent. v ÖZ KLİNOPTİLOLİT ZEOLİTİ KOLONUNDA AMONYUM VE KURŞUN DEĞİŞİMİ Bahaalddin, Ahmad Dh. Yüksek Lisans, Kimya Mühendisliği Bölümü Tez Danışmanı: Prof. Dr. Hayrettin Yücel Aralık 2010, 152 sayfa Antropojenik etkilerden kaynaklanan atıksular, geniş bir aralıkta potansiyel kirletici ve konsantrasyonları içerebilir. Kontaminasyonun tipine ve derecesine bağlı, atıksuların arıtması için kullanılabilecek çok sayıda prosedürleri vardır. Ancak, endüstriyel ölçüde atıksulardan kirleticileri bertaraf etmek zor ve pahalı bir sorundur. Bu çalışmada, iyon değiştirici olarak kullanılan Manisa-Gördes tipi doğal klinoplilolit zeolitinin aşağı-akışlı kolon operasyonu ile iyon değişimi incelenmiştir. 2+ + Kurşun Pb ve amonyum NH4 iyonlarının sulu çözeltilerden gidermesinde parçacık boyutu 0.25-0.5 mm arasında olan klinoptilolit kullanılmıştır. Bu çalışmanın amacı klinoptilolitin verimli ve etkili olarak ayırma proseslerinde kullanılabilmesi için koşulların belirlenmesidir. Deneyler ikili ve üçlü iyon değişim çalışması olarak iki kısma ayrılmıştır ve her iki çalışmada da; klinoptilolitin NaCl vi çözeltisi ile zenginleştirilmesinin, akış hızının, ve çözeltilerin başlangıç derişiminin atık giderimine etkileri incelenmiştir. İkili iyon değişim çalışmalarda, akış hızındaki artış salıverme kapasitesinin, ve kolon veriminin azalmasına neden olmuştur. Halbuki toplam kapasite sabit kalmıştır. + 2+ Maksimum toplam kapasite 1.16 meq/g zeolit, NH4 için, ve 1.1 meq/g zeolite, Pb için belirlenmiştir, ve bu değerler hem birbirlerine hem de Na-form klinoptilolitin sodyum içeriğine yakınmıştır (1.16 meq/g zeolite). Ayrıca başlangıçtaki kirletici maddenin konsantrasyonunu azaltarak, salıverme kapasitesinin ve kolon veriminin artışı gözlenmiştir. 2+ + Üçlü iyon değişim çalışmalarda, sonuçlar gösterdi ki kurşun Pb ve amonyum NH4 iyonların gideriminin akış hızına bağlıdır ve ılımlı düşük akış hızlarında daha yüksek iyon değişim kapasitesine ulaşılmıştır. Bu durumun yüksek akış hızlarında klinoptilolit ile kurşun ve amonyum iyonlarının tamamen yer değiştirmesi için gerekli olan alıkonma süresinin yetersiz olması ile açıklanmıştır. Nitekim 2+ + klinoptilolit üzerindeki değişim siteleri için Pb ve NH4 iyonları arasında bir rekabet gözlenmiştir ve bu çekişme kurşun iyonlarının lehine idi. Sonuç olarak, klinoptilolit zeolitinin hem kurşun hem de amonyum iyonlarına karşı çekiciliğinin olması gözlenmiştir. Fakat klinoptilolitin kurşun iyonuna olan çekiciliği amonyuma göre daha fazla olduğu gözlenmiştir. Bu nedenle klinoptilolitin seçicilik + 2+ + sırası NH4 > Pb > Na olarak belirlenmiştir. Anahtar Kelimeler: Klinoptilolit, İyon Değişimi, Pretreatment, Kurşun, Amonyum, Giderim, Kolon, Çok Bileşenli. vii To My Family... viii ACKNOWLEDGEMENTS First of all, I would like to express my deep sense of gratitude to my thesis supervisor Prof. Dr. Hayrettin Yücel for his permanent support, trust, precious advice and suggestions throughout this study. It was a great honor and pleasure to know him and to work with him. I am also grateful to Mrs. Kerime Güney in instrumental laboratory for her endless valuable assistance and care, supportive comments, and for her assist in all chemical analysis throughout my study. I am also grateful to all members and staff of the Department of Chemical Engineering in METU, for supporting me in my study and giving me chance to perform this thesis study. Many thanks go to Prof. Dr. Deniz Üner, Assoc. Prof. Dr. Halil Kalıpçılar, and Assoc. Prof. İpek İmamoğlu from Environmental Engineering Department, for giving me helpful suggestions and guidance in carrying out my thesis and for moral support. Many thanks go to my colleagues at Chemical Engineering Department who were beside me all the time and helped me in my difficult days. I wish to thank my dearest friends Murat Erdoğan, Wisam Abdallah, Baraa Abbas Ali (God bless his soul), Hale Ay, Dominic Deo, Duygu Yılmazer, Saltuk Pirgalıoğlu, Hakan Murat İşler, Bijen Kadaifci, and Gamzenur Özsin, for their continuous helps and support. I would like to express my great indebtedness to all my family, especially to my mother for her continuous support and encouragement. I like to convey many thanks to my father, my brother Safaaddin and my sister Mine, also to my uncle Sharaf and my aunts Mune and Salwa. I wouldn’t be able to succeed without your presence in my life. And finally, words are inadequate in offering my thanks to the one who doesn't want to be named but she knows who she is, and so do I. ix TABLE OF CONTENTS ABSTRACT……………………………………………………………………... iv ÖZ……………………………………………………………………………….. vi ACKNOWLEDGEMENTS…………………………………………………….. ix TABLE OF CONTENTS………………………………………………………... x LIST OF TABLES...…………………………………………………………….. xiii LIST OF FIGURES……………………………………………………………… xvi LIST OF SYMBOLS AND ABBREVIATIONS…...…………………………... xviii CHAPTERS 1. INTRODUCTION…………………………………………………………….. 1 2. THEORETICAL BACKGROUND…………………………………………... 3 2.1 Wastewater Treatment…………………………………………………….. 3 2.1.1 Lead Removal……………………………………………………….. 4 2.1.2 Ammonium Removal…………………..………………………….... 7 2.2 Natural Zeolites……………………………………………………………