• Hydrothermal synthesis of hydrogarnet and tobermorite at 175 °C from kaolinite and metakaolinite in the CaO–Al2O3–SiO2–H2O system: A comparative study.

      Rios, Carlos A.; Williams, Craig D.; Fullen, Michael A. (Amsterdam: Elsevier, 2009)
      The hydrothermal synthesis of hydrogarnet and tobermorite from kaolinite and metakaolinite was examined at 175 °C for 24 h in the CaO–Al2O3–SiO2–H2O (CASH) system, which is important in cement science and especially in cement chemistry and is closely related to the pozzolanic reaction, the CaO-aggregate reaction and the glass fibre reinforcement of hardened cement. Starting mixtures were prepared with molar ratios Al/(Si + Al) = 0.10–0.13 and Ca/(Si + Al) = 1.00–7.00. The hydration products were characterized by X-ray diffraction, scanning electron microscopy, Fourier transformed infrared spectroscopy, Magic Angle Spinning Nuclear Magnetic Resonance and thermogravimetric analysis in order to elucidate their mineral chemistry and microstructure. Results reveal that several poorly crystalline materials were formed, with un-reacted Ca(OH)2 appearing at shorter reaction times. Hydrogarnet always tended to form more rapidly than tobermorite. It was transformed into aluminium-substituted tobermorite with curing time. CaO is present in the further reaction with SiO2 forming calcium silicate hydrates, and released Al3+ ions were inserted into tobermorite.
    • Nucleation and growth history of zeolite LTA synthesized from kaolinite by two different methods.

      Rios, Carlos A.; Williams, Craig D.; Fullen, Michael A. (Amsterdam: Elsevier, 2009)
      The synthesis of zeolite Linde Type A (LTA) from kaolinite by two different routes: (1) conventional hydrothermal alkaline activation and (2) alkaline fusion prior to hydrothermal reaction, as well as its nucleation and growth history, were investigated. Using the first method, co-crystallization of sodalite and cancrinite, probably via an unstable zeolite LTA intermediate, was observed during treatment of kaolinite in NaOH solutions. The addition of a SiO2 source promoted the co-precipitation of several zeolite phases, including zeolites LTA, X and P, with traces of sodalite and cancrinite. By fusion with NaOH followed by hydrothermal reaction, kaolinite was converted into zeolite LTA. Synthesized materials appeared stable thermodynamically under the experimental conditions. The synthesis products have been characterized by X-ray diffraction, scanning electron microscopy and Fourier Transform Infrared Spectroscopy.
    • Synthesis of Zeolites and Zeotypes by Hydrothermal transformation of Kaolinite and Metakaolinite.

      Rios, Carlos A.; Williams, Craig D.; Maple, Martin J. (Bucaramanga, Colombia: Universidad de Pamplona, 2007)
      The synthesis of zeolitic materials by hydrothermal transformation of kaolinite and metakaolinite in NaOH solutions of various concentrations was investigated between 100 and 200 degrees C, over different reaction times, using in some cases precipitated SiO2 or organic templates. Materials were obtained, including clathrasils: cancrinite (CAN), sodalite (SOD), and Linde Type A (LTA), faujasite (FAU), NaP1 (GIS), analcime (ANA) and nepheline hydrate I (JBW) zeolites. In general, co-crystallization of CAN and SOD, likely via an unstable LTA zeolite intermediate, was observed after dissolution of kaolinite at low temperature; although the feldspathoids tend to be unstable at high temperature. LTA zeolite was synthesized after metakaolinite reaction, with minor amount of FAU zeolite, ANA and SOD. Solids were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA).
    • Synthesis of zeolites from geological materials and industrial wastes for potential application in environmental problems

      Williams, Craig D.; Roberts, Clive L.; Fullen, Michael A.; Rios Reyes, Carlos A. (University of WolverhamptonSchool of Applied Sciences, University of Wolverhampton, 2008)
      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.