Synthesis of zeolites from geological materials and industrial wastes for potential application in environmental problems

2.50
Hdl Handle:
http://hdl.handle.net/2436/39855
Title:
Synthesis of zeolites from geological materials and industrial wastes for potential application in environmental problems
Authors:
Rios Reyes, Carlos A.
Abstract:
Zeolites are among the least-known products for environmental pollution control, separation science and technology. Due to their unique porous properties, they are used in various applications in petrochemical cracking, ion-exchange and separation and removal of gases and solvents. The preparation of synthetic zeolites from chemical reagents is expensive. Therefore, in order to reduce costs, zeolite researchers are seeking cheaper aluminosilicate bearing raw materials, such as clay minerals, to produce synthetic zeolites. This research concerns the synthesis of zeolites and zeotypes derived from low-cost materials like kaolinite (KAO), natural clinker (NC) and fly ash (FA). The motivation for using these sources as the starting materials in zeolite synthesis is driven by factors, such as they are cheap and available in bulk quantities, are currently under-utilized, have high workability, and require less water (or solution) for activation. The raw materials were activated by two different routes: (1) classic alkaline hydrothermal synthesis and (2) alkaline fusion prior to hydrothermal synthesis. In the first method, the synthesis of zeolitic materials was carried out generally in alkaline media, although KAO or its calcination product, metakaolinite (MTK), was also activated in the presence or absence of structure directing agents (SDAs) and additional silica (precipitated SiO2), with the last one determining the SiO2/Al2O3 ratio of the reaction mixture and the time given for zeolitization. Synthesis in fluoride- and calcium-bearing media was also used to activate kaolinite. The process of synthesis was optimized by applying a wide range of experimental conditions with a wide range of reaction temperature, time, mineralizer concentration and solid/solution ratio. In the second approach, an alkaline fusion step was conducted prior to hydrothermal treatment, because it plays an important role in enhancing the hydrothermal conditions for zeolite synthesis. On the other hand, this approach was adopted because it can dissolve more aluminosilicates. The main synthesis products obtained after activation of KAO in NaOH solutions included zeolite LTA (LTA), sodalite (SOD), cancrinite (CAN), faujasite (FAU), zeolite Na-P1 (GIS), JBW-type zeolite (JBW), analcime (ANA), whereas the activation of KAO in KOH solutions produced chabazite (CHA), zeolite Barrer-KF, phillipsite (PHI) and K-feldspar. The hydrothermal conversion of kaolinite in fluoride media did not produce successful results, although traces of FAU, GIS, CHA, SOD and CAN crystallized. The activation of KAO in the system CaO-SiO2-Al2O3-H2O promoted the formation of different calcium silicate hydrate (C-S-H) phases, including hydrogarnet (HYD) and tobermorite (TOB). Following the fusion approach, the main zeolitic phases obtained using NaOH as mineralizer were LTA and CAN. The main as-synthesized zeolites obtained from NC by the conventional hydrothermal treatment method include PHI, SOD and CAN. Using the fusion approach, FAU and LTA were obtained with NaOH as an activator, whereas non-zeolitic material crystallized when KOH was used. The main as-synthesized zeolitic materials obtained by hydrothermal reaction of FA include PHI, zeolite Barrer-KF, CHA and SOD with traces of TOB, ANA, zeolite LTF (LTF) and herschelite (HER), appearing occasionally. By the fusion approach, FAU was obtained with NaOH as activator, whereas no zeolitic material crystallized using KOH. Experimental results indicate that the method, mineralizer, concentration and time have strong effects on the type and degree of crystallinity of the synthesis products. On the other hand, the type and chemical composition of the as-synthesized products are strongly dependent on the chemical composition of the starting material. The chemistry of zeolite synthesis was subject to perturbations caused by the presence of impurities in the raw materials, which may remain insoluble during crystallization and cause undesired species to nucleate, developing mixtures of different types of zeolites. However, other physicochemical factors may play a very important role in the thermodynamics and kinetics of zeolite formation. The raw materials have very high contents of SiO2 and Al2O3, with SiO2/Al2O3 ratios appropriate for the synthesis of low-Si zeolitic materials with high crystallinity and cation exchange capacity (CEC). However, although zeolites’ CEC represents a very important characteristic quality in the removal of undesired species from polluted effluents, it is not the deciding factor in determining zeolite performance during ion exchange processes, since numerous other factors also need to be considered. Finally, the potential application of the raw materials and their as-synthesized products as low-cost sorbents in the remediation of metal ions and ammonium from wastewater effluents was investigated. PHI showed a lower efficiency than FAU. Selectivity of FAU for metal removal was, in decreasing order, Fe>As>Pb>Zn>Cu>Ni>Cr. Based on these results, the use of these materials has the potential to provide improved methods for the treatment of contaminated effluents.
Advisors:
Williams, Craig D.; Roberts, Clive L.; Fullen, Michael A.
Publisher:
University of Wolverhampton
Issue Date:
2008
URI:
http://hdl.handle.net/2436/39855
Type:
Thesis or dissertation
Language:
en
Description:
A thesis submitted in partial fulfilment of the requirements of the University of Wolverhampton for the degree of Doctor of Philosophy
Appears in Collections:
E-Theses

Full metadata record

DC FieldValue Language
dc.contributor.advisorWilliams, Craig D.-
dc.contributor.advisorRoberts, Clive L.-
dc.contributor.advisorFullen, Michael A.-
dc.contributor.authorRios Reyes, Carlos A.-
dc.date.accessioned2008-10-29T11:38:37Z-
dc.date.available2008-10-29T11:38:37Z-
dc.date.issued2008-
dc.identifier.urihttp://hdl.handle.net/2436/39855-
dc.descriptionA thesis submitted in partial fulfilment of the requirements of the University of Wolverhampton for the degree of Doctor of Philosophyen
dc.description.abstractZeolites are among the least-known products for environmental pollution control, separation science and technology. Due to their unique porous properties, they are used in various applications in petrochemical cracking, ion-exchange and separation and removal of gases and solvents. The preparation of synthetic zeolites from chemical reagents is expensive. Therefore, in order to reduce costs, zeolite researchers are seeking cheaper aluminosilicate bearing raw materials, such as clay minerals, to produce synthetic zeolites. This research concerns the synthesis of zeolites and zeotypes derived from low-cost materials like kaolinite (KAO), natural clinker (NC) and fly ash (FA). The motivation for using these sources as the starting materials in zeolite synthesis is driven by factors, such as they are cheap and available in bulk quantities, are currently under-utilized, have high workability, and require less water (or solution) for activation. The raw materials were activated by two different routes: (1) classic alkaline hydrothermal synthesis and (2) alkaline fusion prior to hydrothermal synthesis. In the first method, the synthesis of zeolitic materials was carried out generally in alkaline media, although KAO or its calcination product, metakaolinite (MTK), was also activated in the presence or absence of structure directing agents (SDAs) and additional silica (precipitated SiO2), with the last one determining the SiO2/Al2O3 ratio of the reaction mixture and the time given for zeolitization. Synthesis in fluoride- and calcium-bearing media was also used to activate kaolinite. The process of synthesis was optimized by applying a wide range of experimental conditions with a wide range of reaction temperature, time, mineralizer concentration and solid/solution ratio. In the second approach, an alkaline fusion step was conducted prior to hydrothermal treatment, because it plays an important role in enhancing the hydrothermal conditions for zeolite synthesis. On the other hand, this approach was adopted because it can dissolve more aluminosilicates. The main synthesis products obtained after activation of KAO in NaOH solutions included zeolite LTA (LTA), sodalite (SOD), cancrinite (CAN), faujasite (FAU), zeolite Na-P1 (GIS), JBW-type zeolite (JBW), analcime (ANA), whereas the activation of KAO in KOH solutions produced chabazite (CHA), zeolite Barrer-KF, phillipsite (PHI) and K-feldspar. The hydrothermal conversion of kaolinite in fluoride media did not produce successful results, although traces of FAU, GIS, CHA, SOD and CAN crystallized. The activation of KAO in the system CaO-SiO2-Al2O3-H2O promoted the formation of different calcium silicate hydrate (C-S-H) phases, including hydrogarnet (HYD) and tobermorite (TOB). Following the fusion approach, the main zeolitic phases obtained using NaOH as mineralizer were LTA and CAN. The main as-synthesized zeolites obtained from NC by the conventional hydrothermal treatment method include PHI, SOD and CAN. Using the fusion approach, FAU and LTA were obtained with NaOH as an activator, whereas non-zeolitic material crystallized when KOH was used. The main as-synthesized zeolitic materials obtained by hydrothermal reaction of FA include PHI, zeolite Barrer-KF, CHA and SOD with traces of TOB, ANA, zeolite LTF (LTF) and herschelite (HER), appearing occasionally. By the fusion approach, FAU was obtained with NaOH as activator, whereas no zeolitic material crystallized using KOH. Experimental results indicate that the method, mineralizer, concentration and time have strong effects on the type and degree of crystallinity of the synthesis products. On the other hand, the type and chemical composition of the as-synthesized products are strongly dependent on the chemical composition of the starting material. The chemistry of zeolite synthesis was subject to perturbations caused by the presence of impurities in the raw materials, which may remain insoluble during crystallization and cause undesired species to nucleate, developing mixtures of different types of zeolites. However, other physicochemical factors may play a very important role in the thermodynamics and kinetics of zeolite formation. The raw materials have very high contents of SiO2 and Al2O3, with SiO2/Al2O3 ratios appropriate for the synthesis of low-Si zeolitic materials with high crystallinity and cation exchange capacity (CEC). However, although zeolites’ CEC represents a very important characteristic quality in the removal of undesired species from polluted effluents, it is not the deciding factor in determining zeolite performance during ion exchange processes, since numerous other factors also need to be considered. Finally, the potential application of the raw materials and their as-synthesized products as low-cost sorbents in the remediation of metal ions and ammonium from wastewater effluents was investigated. PHI showed a lower efficiency than FAU. Selectivity of FAU for metal removal was, in decreasing order, Fe>As>Pb>Zn>Cu>Ni>Cr. Based on these results, the use of these materials has the potential to provide improved methods for the treatment of contaminated effluents.en
dc.language.isoenen
dc.publisherUniversity of Wolverhamptonen
dc.subjectSynthesisen
dc.subjectZeolitesen
dc.subjectHydrothermal treatmenten
dc.subjectAlkaline fusionen
dc.subjectKaoliniteen
dc.subjectNatural clinkeren
dc.subjectFly ashen
dc.subjectEnvironmental impacten
dc.subjectWastewateren
dc.subjectWater treatmenten
dc.titleSynthesis of zeolites from geological materials and industrial wastes for potential application in environmental problemsen
dc.typeThesis or dissertationen
dc.publisher.departmentSchool of Applied Sciences, University of Wolverhampton-
dc.type.qualificationnamePhDen
dc.type.qualificationlevelDoctoralen
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