Tunde Victor Ojumu

Synthesis of zeolites Na-P1 from South African coal fly ash: effect of impeller design and agitation

South African fly ash has been shown to be a useful feedstock for the synthesis of some zeolites. The present study focuses on the effect of impeller design and agitation rates on the synthesis of zeolite Na-P1 which are critical to the commercialization of this product. The effects of three impeller designs (4-flat blade, Anchor and Archimedes screw impellers) and three agitation speeds (150, 200 and 300 rpm) were investigated using a modified previously reported synthesis conditions; 48 hours of ageing at 47 °C and static hydrothermal treatment at 140 °C for 48 hours. The experimental results demonstrated that the phase purity of zeolite Na-P1 was strongly affected by the agitation rate and the type of impeller used during the ageing step of the synthesis process. Although zeolite Na-P1 was synthesized with a space time yield (STY) of 15 ± 0.4 kg d−1m−3 and a product yield of 0.98±0.05 g zeolites/g fly ash for each impeller at different agitation speeds, zeolite formation was assessed to be fairly unsuccessful in some cases due the occurrence of undissolved mullite and/or the formation of impurities such as hydroxysodalite with the zeolitic product. This study also showed that a high crystalline zeolite Na-P1 can be synthesized from South African coal fly ash using a 4-flat blade impeller at an agitation rate of 200 rpm during the ageing step at 47 °C for 48 hours followed by static hydrothermal treatment at 140 °C for 48 hours.

Synthesis of zeolite A from coal fly ash using ultrasonic treatment – A replacement for fusion step

The synthesis of zeolites from fly ash has become an increasingly promising remedy to the crisis of coal fly ash production and disposal in South Africa. In recent studies, South African fly ash was proven to be a suitable feedstock for the synthesis of essential industrially used zeolite A. However, the process involves a costly energy intensive step whereby fly ash is fused at high temperatures, which may make the process economically unattractive on a large scale. The aim of this study is to investigate the possibility of replacing high temperature fusion with less energy intensive sonochemical treatment for the synthesis of zeolite A. Sonochemical treatment was first thought possible due to the violent cavitation caused by high intensity sonication. The results of the study showed that fusion can be replaced by 10 min of high intensity sonication. The incorporation of sonication also consequently reduced the crystallization temperature of the process making it possible to synthesize a pure phase zeolite A at lower temperatures and reduced times. This study effectively developed a novel process to replace the energy intensive fusion step with a short, easy and inexpensive treatment. Scale up of this synthesis approach may proffer a promising alternative option to the anticipated energy demand of the synthesis of fly ash-based zeolite with fusion method.

Waste Minimization Protocols for the Process of Synthesizing Zeolites from South African Coal Fly Ash

Production of a high value zeolite from fly ash has been shown to be an avenue for the utilization of South African fly ash which presently constitutes a huge disposal problem. The synthesis of zeolites Na-P1 and analcime on a micro-scale has been successful and preliminary investigation shows that scale-up synthesis is promising. However, the post-synthesis supernatant waste generated contains high levels of NaOH that may constitute a secondary disposal problem. A waste minimization protocol was developed to reduce the volume of waste generated with a view to enhancing the feasibility of the scale synthesis. Series of experiments were conducted in 100 mL jacketed batch reactors. Fly ash was reacted with 5 Mol NaOH on a 1:1 mass basis during the aging step, followed by hydrothermal treatment in which ultrapure water was added to the slurry. This study shows that by re-introducing the supernatant waste into the experiments in such a way that it supplies the required reagent (NaOH) for the zeolite synthesis, zeolite Na-P1 and analcime can be synthesized. It also shows that the synthesis process can be altered to allow up to 100% re-use of the supernatant waste to yield high value zeolitic products. This study effectively constructed two protocols for the minimization of waste generated during the synthesis of zeolites from South African coal fly ash. This result could be used to establish a basis for legal and environmental aspects involved in the commission of a full-scale plant synthesizing zeolites NaP1 and analcime.

The Effect of Total Iron Concentration and Iron Speciation on the Rate of Ferrous Iron Oxidation Kinetics of Leptospirillum ferriphilum in Continuous Tank Systems

In this study the results from a systematic study of the oxidation kinetics of Leptospirillum ferriphilum in continuous culture at total iron concentrations ranging from 2 to12 g/L are reported. In all experiments the steady-state concentrations of ferrous iron were small and comparable, and at least 97% of was as ferric. Surprisingly, the specific ferrous iron utilisation rate decreased with increasing total iron concentration, while yield coefficients increased. It was noted that the biomass concentration in the reactor (as measured by both CO2 uptake rate and cell counts) dramatically increased with increasing total iron concentrations, whereas it stayed more or less the same over a wide range of dilution rates at a given total iron concentration. The experimental data was re-analysed in terms of ferrous iron kinetics using Monod kinetics with a ferric inhibition term. The results confirm that the maximum specific iron utilisation rate is itself a function of ferric iron concentration, declining with increasing concentration. It thus appears that high concentrations of ferric iron stimulate microbial growth while at the same time inhibiting the rate of ferrous iron oxidation. It is postulated that these phenomena are related, i.e. that more growth occurs to reduce the load on the individual cell, possibly by sharing some metabolic functions.

The Effect of Aluminium and Magnesium Sulphate on the Rate of Ferrous Iron Oxidation by Leptospirillum ferriphilum in Continuous Culture

In heap bioleaching the dissolution of gangue minerals from igneous ore materials can lead to the build-up of considerable concentrations of Mg and Al sulphates in the recycled leach solution. This may interfere with microbial ferrous iron oxidation, which drives the oxidation of the target minerals. The kinetics of the oxidation process have been well studied for Leptospirillum and Acidithiobacillus species in tank systems. Although not directly comparable, kinetic parameters derived for tank systems do apply also for heap bioleach conditions. In the present study the effect of solution concentrations of Mg and Al as sulphate at individual concentrations of 0 to 10 g/L and combined concentrations 0 to 16 g/L each has been investigated in continuous culture using Leptospirillum ferriphilum. Increasing the concentrations of the salts increasingly depresses the rate of ferrous iron oxidation and also shifts the viable range more and more into the low potential region. Al significantly reduces the amount of carbon maintained in the reactor (assumed to be commensurate with biomass), whereas Mg actually enhances it at low concentrations. In both cases, however, the rate is always depressed. The results indicate that heap cultures are likely to perform sub-optimally in those operations where build-up of dissolved gangue minerals is not controlled.

Auto-hydrolysis of lignocellulosics under extremely low sulphuric acid and high temperature conditions in batch reactor

Batch reactors were employed to investigate the kinetics of cellulose hydrolysis under extremely low acid (ELA) and high temperature condition. The sawdust was pretreated by Autohydrolysis prior to the batch reaction. The maximum yield of glucose obtained from the batch reactor experiment was about 70% for the pretreated sawdust, this occurred at 210 and 220°C. The maximum glucose yield from the untreated sawdust was much lower at these temperatures, about 55%. The maximum yields of glucose from the lignocellulosics were obtained between 15th and 20th minutes after which gradual decrease was observed.

Bioavailability of High Molecular Weight Polycyclic Aromatic Hydrocarbons Using Renewable Resources

Petre M (ed): Environmental Biotechnology – New Approaches and Prospective Applications Rijeka, Croatia: InTech Online Publishers, 2013, pp 123-146, ISBN 978-953-51-0972-3

Charge transfer between biogenic jarosite derived Fe3 + and TiO2 enhances visible light photocatalytic activity of TiO2

In this work, we have shown that mining waste derived Fe3+ can be used to enhance the photocatalytic activity of TiO2. This will allow us to harness a waste product from the mines, and utilize it to enhance TiO2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO2 and biogenic jarosite. Evidence of FeOTi bonding in the TiO2/jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO2, biogenic jarosite and mechanically mixed sample of jarosite and TiO2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO2 and jarosite derived Fe3+ as was shown from the EELS and ELNEFS. Generation of OH was supported by photoluminesence (PL) experiments.

Distributional Fate of Elements during the Synthesis of Zeolites from South African Coal Fly Ash

The synthesis of zeolites from South African coal fly ash has been deemed a viable solution to the growing economical strain caused by the disposal of ash in the country. Two synthesis routes have been studied thus far namely the 2-step method and the fusion assisted process. Fly ash contains several elements originating from coal which is incorporated in the ash during combustion. It is vital to determine the final destination of these elements in order to unveil optimization opportunities for scale-up purposes. The aim of this study was to perform a material balance study on both synthesis routes to determine the distributional fate of these elements during the synthesis of zeolites. Zeolites were first synthesized by means of the two synthesis routes. The composition of all raw materials and products were determined after which an overall and elemental balance were performed. Results indicated that in the 2-step method almost all elements were concentrated in the solid zeolite product while during the fusion assisted route the elements mostly report to the solid waste. Toxic elements such as Pb, Hg, Al, As and Nb were found in both the supernatant waste and washing water resulting from each synthesis route. It has also been seen that large quantities of Si and Al are wasted in the supernatant waste. It is highly recommended that the opportunity to recycle this liquid waste be investigated for scale-up purposes. Results also indicate that efficiency whereby Si and Al are extracted from fused ash is exceptionally poor and should be optimized.

Kinetics of Microbial Ferrous-Iron Oxidation by Leptospirillum Ferriphilum: Effect of Ferric-Iron on Biomass Growth

The kinetics of microbial ferrous-iron oxidation have been well studied as it is a critical sub-process in bioleaching of sulphide minerals. Exhaustive studies in continuous culture have been carried out recently, investigating the effects of conditions relevant to heap bioleaching on the microbial ferrous-iron oxidation by Leptospirillum ferriphilum [1-3]. It was postulated that ferric-iron, which is known to be inhibitory, also acts as a stress stimulus, promoting microbial growth at higher total iron concentration. This paper investigates this phenomenon further, by comparing tests run with pure ferrous-iron feeds against those where the feed is partially oxidised to ferric at comparable concentrations. The findings clearly suggest that, contrary to reactor theory, it is indeed ferrous iron concentration in the reactor feed that determines biomass concentration and that ferric iron concentration has little effect on microbial growth. Further mathematical analysis shows that the phenomenon can be explained on the basis of the Pirt equation and the particular reaction conditions employed in the test work.