1. Introduction Results Objectives Catalyst Synthesis Results Conclusions
Development of Zeolite Based Catalyst from Jordanian Zeolitic Tuff for Biodiesel Production from Waste Sunflower Oil
Noor Al- Jammal*, Zayed Al-Hamamre**
*Chemical Engineering Department, University of Jordan, Amman, Jordan
**Institute of Environmental Engineering, University of Pannonia, Veszprem, Hungary
The University of Jordan
Introduction
Objectives
Results
2) SEM Analysis
Efforts are being made all around the world to reduce the dependency on the depleting fossil fuels and to find environment friendly alternatives. Biodiesel is obtaining prominence as an alternative for petroleum based diesel due to environmental considerations. This study aims to develop a new heterogeneous catalytic system from raw Jordanian zeolitic tuff (RZT) for biodiesel production from waste vegetable oil. The new proposed catalytic system needs to be more environmentally friendly, economically visible and technically applicable with a minimum level of complexity in terms of preparation and use.
This research investigated the proficiency of a chemically treated Jordanian zeolitic tuff (TZT) as a heterogeneous catalyst for biodiesel production. Series of catalysts were prepared by methods. The prepared catalysts were then characterized by using X-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR), PH zero point of charge (PHzpc), scanning electron microscopy (SEM) and energy dispersive X-Ray (EDX) to obtain information about the structural, chemical and catalytic characteristics of zeolite materials as well as to study the availability of basic sites. In fact, the basicity was found as the critical factor for the choice of the suitable catalyst for the transesterification reaction. Many parameters which influence this basicity have been identified. The easiest of these parameters to act on are the aluminum (Al) content and the electronegativity of the cation.
The catalysts were then used for transesterification of waste sunflower vegetable oil in order to produce biodiesel. Among the different catalysts prepared, the 1- 4M KOH/TZT catalyst provided the maximum biodiesel yield of 96.7% at 50 °C reaction temperature, methanol to oil molar ratio of 11.5:1, agitation speed of 800 rpm, with catalyst having particle size of 350 µm and 2 hrs reaction time. The physicochemical properties of the produced biodiesel comply with the EN and ASTM standard specifications.
 Keywords: Biodiesel, Zeolite based catalyst, Impregnation, Transesterification’ A C B
Figure 2: Scanning electron micrographs of (A) RZT shows the associated materials covering RZT surface, (B) TZT image and (C) prepared catalyst
3) PHzpc Analysis
Table 2: PHZPC analysis
Figure 3 : PHZPC for the 1-4M* KOH loaded/TZT.
3) FTIR Analysis
This study aims to develop a new heterogeneous catalytic system from Jordanian zeolitic tuff for biodiesel production from waste vegetable oil.
Investigating the optimum operating parameters of the transesterification such as reaction time, wt.% KOH loading, molar ratio of oil to methanol, effect of catalyst concentration, spent catalyst efficiency, stirring speed, catalyst preparation time and particle size of catalyst.
Figure 4: (A)FT-IR spectra of raw zeolitic tuff (RZT) and treated zeolitic tuff (TZT),
(B) FT-IR spectra of raw zeolitic tuff (TZT) and series of modified treated zeolitic tuff catalyst(MTZT).
Catalyst Synthesis
4) XRD Analysis
The peaks intensity of the prepared catalysts decreased after increase K loading due to decrease in zeolite crystallinity, potassium species and secondary scattering of X-ray (Xie et al., 2006). 
The new phases of K species such as K2O phase (2θ =31°and 39°) were not observed, indicating good dispersion of K on catalyst surface (Ramos et al., 2008). Xie et al., (2006) had the same conclusion for KI loading on alumina. Therefore, K2O derived from KOH by impregnation step with heating and the Al–O–K groups were, most likely, the main reasons for the catalytic activity towards the reaction. The catalyst activity was correlated directly with its basicity
Figure 5: XRD patterns of the KOH loaded TZT, catalysts with various K+ loading.
5) Catalyst Performance
The biodiesel yield obtained using 1-4M*KOH/loaded TZT with 0.5 v/v MeOH/WVO (corresponding to 11.5:1 MeOH/Oil molar ratio) and 6.4 wt./wt. catalyst at 50 °C for fresh and waste vegetable oil is shown in Figure 6 as a function of time. Full conversion and highest yield of 97.6 % was achieved using the best catalyst
Figure 1 :Flow chart of transesterification reaction steps.
Results
XRF Analysis
All similar published work used high calcinations temperatures (500 to 900 ˚C) to create Potassium oxide K2O. But in this work the creation of the active site (K2O) was achieved in impregnation step which combined with heating at temperatures ranges between 80 to 100 ˚C only
Table 1 : Chemical composition of RZT, TZT and TZT loaded with KOH by XRF analysis.
Figure 6 :The effect of catalyst temperature and reaction time on the yield of Biodiesel (reaction time between 1 and 5 hr, amount of catalyst used was 6.4%, oil to methanol ratio 1:11.5, and reaction temperature 40, 50 and 60 °C.
Conclusions
The results obtained from characterization methods of the prepared series of zeolite catalyst suggest that 1-4M*KOH/TZT can be used as catalyst for biodiesel production.
The following points illustrate the main generated active sites:
Alkali metal supported on TZT: K2O derived from KOH by the impregnation method with heating and the surface Al–O–K groups were, probably, the main active sites.
Alkali metal exchanged TZT: Alkali cations K+, cation exchanges by K+, compensate the negative charge of the zeolite framework.
The Si/Al ratio for RZT, TZT and TZT loaded with KOH (catalyst) were found to be It was observed from Table 1 that concentrated hydrochloric acid has removed 25 wt. % to 30 wt.% (mass fraction) of other volcanic constituents (iron, aluminum, magnesium, calcium, and sodium oxides)