Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal).
The removal of ammonium from aqueous solutions using zeolite NaY prepared from a local agricultural waste, rice husk ash waste was investigated and a naturally occurring zeolite mordenite in powdered and granulated forms was used as comparison. Zeolite NaY and mordenite were well characterized by powder X-ray diffraction (XRD), energy dispersive X-ray (EDX) analysis and the total cation exchange capacity (CEC). CEC of the zeolites were measured as 3.15, 1.46 and 1.34 meq g(-1) for zeolite Y, powdered mordenite and granular mordenite, respectively. Adsorption kinetics and equilibrium data for the removal of NH(4)(+) ions were examined by fitting the experimental data to various models. Kinetic studies showed that the adsorption followed a pseudo-second-order reaction. The equilibrium pattern fits well with the Langmuir isotherm compared to the other isotherms. The monolayer adsorption capacity for zeolite Y (42.37 mg/g) was found to be higher than that powdered mordenite (15.13 mg/g) and granular mordenite (14.56 mg/g). Thus, it can be concluded that the low cost and economical rice husk ash-synthesized zeolite NaY could be a better sorbent for ammonium removal due to its rapid adsorption rate and higher adsorption capacity compared to natural mordenite.
The synthesized zeolite NaY from rice husk ash (RHA) and the commercial zeolite NaY both modified with surfactants in amounts equal to 50%, 100% and 200% of their external cation exchange capacity (ECEC) were used to remove chromate and arsenate anions from aqueous solutions. While the unmodified zeolite Y had little or no affinity for the Cr(VI) and As(V) anionic species, the surfactant-modified zeolite Y (SMZY) showed significant ability to remove of these anions from the aqueous solutions. The highest chromates and arsenates adsorption efficiency was observed from solutions of pH values 3 and 8, respectively because of the dominance of the univalent species of both anions. The adsorption equilibrium data were best fitted with the Langmuir isotherm model with the highest removal capacities observed for the SMZY initially prepared considering the hexadecyltrimethyl ammonium (HDTMA) amount equal to the 100% of the ECEC of zeolite Y. Synthesized SMZY remove Cr(VI) and As(V) more than the corresponding commercial one due to its lower silica to alumina ratio. Thus, the HDTMA-covered modified zeolite Y synthesized using RHA can be used to remove Cr(VI) and As(V) from water.
Nanocrystalline aluminosilicate F-type zeolite (K-F, EDI-type structure) was synthesized in an organic template-free system
using rice husk ash (RHA) silica source and microwave energy. The morphology, crystallite size, chemical composition,
crystallographic and basicity properties of the nanocrystals were studied by using various characterization techniques.
The results showed that fully crystalline K-F zeolite (Si/Al ratio = 1.26) with flattened cuboid-like shaped could be
obtained within 2 min of crystallization which was considerably very fast. In addition, K-F zeolite nanocrystals was also
tested as a solid base catalyst in the microwave-enhanced Aldol condensation reaction of heptanal with benzaldehyde
and the six catalytic parameters were studied and optimized. The nanosized K-F zeolite crystals showed good catalytic
performance in the studied reaction with 77.1% heptanal conversion and 69.5% jasminaldehyde selectivity under optimum
reaction condition. The nanocatalyst was reusable and no significant loss in its catalytic reactivity was observed even
after five consecutive reaction cycles.
The performance of silver-loaded zeolite (HY and HZSM-5) catalysts in the oxidation of butyl acetate as a model volatile organic compound (VOC) was studied. The objective was to find a catalyst with superior activity, selectivity towards deep oxidation product and stability. The catalyst activity was measured under excess oxygen condition in a packed bed reactor operated at gas hourly space velocity (GHSV)=15,000-32,000 h(-1), reaction temperature between 150 and 500 degrees C and butyl acetate inlet concentration of 1000-4000 ppm. Both AgY and AgZSM-5 catalysts exhibited high activity in the oxidation of butyl acetate. Despite lower silver content, AgY showed better activity, attributed to better metal dispersion, surface characteristics and acidity, and its pore system. Total conversion of butyl acetate was achieved at above 400 degrees C. The oxidation of butyl acetate followed a simple power law model. The reaction orders, n and m were evaluated under differential mode by varying the VOC partial pressure between 0.004 and 0.018 atm and partial pressure of oxygen between 0.05 and 0.20 atm. The reaction rate was independent of oxygen concentration and single order with respect to VOC concentration. The activation energies were 19.78 kJ/mol for AgY and 32.26 kJ/mol for AgZSM-5, respectively.
The aim of this study is to identify the optimum thermal conversion of Chlorella vulgaris with neuro-evolutionary approach. A Progressive Depth Swarm-Evolution (PDSE) neuro-evolutionary approach is proposed to model the Thermogravimetric analysis (TGA) data of catalytic thermal degradation of Chlorella vulgaris. Results showed that the proposed method can generate predictions which are more accurate compared to other conventional approaches (>90% lower in Root Mean Square Error (RMSE) and Mean Bias Error (MBE)). In addition, Simulated Annealing is proposed to determine the optimal operating conditions for microalgae conversion from multiple trained ANN. The predicted optimum conditions were reaction temperature of 900.0 °C, heating rate of 5.0 °C/min with the presence of HZSM-5 zeolite catalyst to obtain 88.3% of Chlorella vulgaris conversion.
The catalytic cracking of waste cooking palm oil to biofuel was studied over different types of nano-crystalline zeolite catalysts in a fixed bed reactor. The effect of reaction temperature (400-500 °C), catalyst-to-oil ratio (6-14) and catalyst pore size of different nanocrystalline zeolites (0.54-0.80 nm) were studied over the conversion of waste cooking palm oil, yields of Organic Liquid Product (OLP) and gasoline fraction in the OLP following central composite design (CCD). The response surface methodology was used to determine the optimum value of the operating variables for maximum conversion as well as maximum yield of OLP and gasoline fraction, respectively. The optimum reaction temperature of 458 °C with oil/catalyst ratio=6 over the nanocrystalline zeolite Y with pore size of 0.67 nm gave 86.4 wt% oil conversion, 46.5 wt% OLP yield and 33.5 wt% gasoline fraction yield, respectively. The experimental results were in agreement with the simulated values within an experimental error of less than 5%.
Lubricant oils take significant part in current health and environmental considerations since they are an integral and indispensable component of modern technology. Antioxidants are probably the most important additives used in oils because oxidative deterioration plays a major role in oil degradation. Zeolite nanoparticles (NPs) have been proven as another option as green antioxidants in oil formulation. The anti-oxidative behavior of zeolite NPs is obvious; however, the phenomenon is still under investigation. Herein, a study of the effect of extra-framework cations stabilized on Linde Type L (LTL) zeolite NPs (ca. 20 nm) on inhibition of oxidation in palm oil-based lubricant oil is reported. Hydrophilic LTL zeolites with a Si/Al ratio of 3.2 containing four different inorganic cations (Li(+), Na(+), K(+), Ca(2+)) were applied. The oxidation of the lubricant oil was followed by visual observation, colorimetry, fourier transform infrared (FTIR) spectroscopy, (1)H NMR spectroscopy, total acid number (TAN), and rheology analyses. The effect of extra-framework cations to slow down the rate of oil oxidation and to control the viscosity of oil is demonstrated. The degradation rate of the lubricant oil samples is decreased considerably as the polarizability of cation is increased with the presence of zeolite NPs. More importantly, the microporous zeolite NPs have a great influence in halting the steps that lead to the polymerization of the oils and thus increasing the lifetime of oils.
The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.
Bionanocomposite films based on regenerated cellulose (RC) and incorporated with zeolite at different concentrations were fabricated by dissolving cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid using a simple green method. The interactions between the zeolite and the cellulose matrix were confirmed by Fourier transform infrared spectra. Mechanical properties of the nanocomposite films significantly improved as compared with the pure regenerated cellulose film, without the loss of extensibility. Zeolite incorporation enhanced the thermal stability and char yield of the nanocomposites. The scanning electron microscopy and transmission electron microscopy showed that zeolite was uniformly dispersed in the regenerated cellulose matrix. In vitro cytotoxicity test demonstrated that both RC and RC/zeolite nanocomposite films are cytocompatible. These results indicate that the prepared nanocomposites have potential applications in biodegradable packaging, membranes and biomedical areas.
Using the chemical reduction method, silver nanoparticles (Ag NPs) were effectively synthesized into the zeolite framework in the absence of any heat treatment. Zeolite, silver nitrate, and sodium borohydride were used as an inorganic solid support, a silver precursor, and a chemical reduction agent, respectively. Silver ions were introduced into the porous zeolite lattice by an ion-exchange path. After the reduction process, Ag NPs formed in the zeolite framework, with a mean diameter of about 2.12-3.11 nm. The most favorable experimental condition for the synthesis of Ag/zeolite nanocomposites (NCs) is described in terms of the initial concentration of AgNO(3). The Ag/zeolite NCs were characterized by ultraviolet-visible spectroscopy, powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray fluorescence, and Fourier transform infrared. The results show that Ag NPs form a spherical shape with uniform homogeneity in the particle size. The antibacterial activity of Ag NPs in zeolites was investigated against Gram-negative bacteria (ie, Escherichia coli and Shigella dysentriae) and Gram-positive bacteria (ie, Staphylococcus aureus and methicillin-resistant Staphylococcus aureus) by disk diffusion method using Mueller-Hinton agar at different sizes of Ag NPs. All of the synthesized Ag/zeolite NCs were found to have antibacterial activity. These results show that Ag NPs in the zeolite framework can be useful in different biological research and biomedical applications.
Three specific catalysts, namely ZIF-67 (zeolitic imidazolate framework-67), Co@NCF (Co@Nitrogen-Doped Carbon Framework), and 3D NCF (Three-Dimensional Nitrogen-Doped Carbon Framework), were prepared and studied for pulp and paper mill effluent degradation using heterogeneous activation of peroxymonosulfate (PMS). Numerous characterizations, including scanning electron microscopy (SEM), X-ray diffraction (XRD), and N2 adsorption, were used to characterize the properties of three different catalysts. 3D NCF is remarkably effective at heterogeneous activation of PMS to generate sulfate radicals to degrade pulp and paper mill effluent (PPME) compared to the other as-prepared catalysts. The catalytic activity reveals a sequence of 3D NCF > Co@NCF > ZIF-67.3D NCF could degrade organic pollutants in 30 min at an initial COD concentration of 1146 mg/L of PPME, 0.2 g/L catalysts, 2 g/L PMS, and 50 °C. Consequently, it was observed that the degradation of PPME using 3D NCF followed first-order kinetics, with an activation energy of 40.54 kJ mol-1. Overall, 3D NCF/PMS system reveals promising performance for PPME removal.
In this work, the novel imprinted zeolite (IZ) was synthesized, and its properties and performance in terms of adsorption of p-Cresol, which represent the protein-bounded uremic toxins in aqueous phase under phosphate buffer saline, were studied and compared with the synthesized zeolite-Y (ZeoY-S) and commercial CBV 100 zeolite-Y (ZeoY-C). The ZeoY-S was synthesized from sodium aluminate, NaOH, H2O and SiO2 under aging for 24 h at room temperature and hydrothermal condition for 24 h at 100 °C, with an initial composition of 10SiO2:Al2O3:4Na2O:180H2O. The ZeoY-S has been modified by using the imprinting technology to produce the IZ via the use of p-Cresol as a template. The p-Cresol successfully imprinted on the zeolite-Y was proved through the multipoint Brunauer-Emmett-Teller (BET) and the performance of IZ that was compared to ZeoY-S and ZeoY-C. Based on the BET results, it proves that the pore size of IZ is in accordance with the target compound, which is p-Cresol at 0.79 nm. This modification was able to adsorb p-Cresol 2.5 and 3.5 times higher than ZeoY-S and ZeoY-C can, respectively. Langmuir and Freundlich adsorption isotherm models, together with the pseudo-first and -second order and intra-particle diffusion kinetics models, were used to investigate the adsorption behavior of p-Cresol on the zeolites. The IZ has 4.30 times greater competitive molecules than ZeoY-S and the properties of IZ were not influenced by the content of other phenolic group uremic toxins as competitive molecules. It can be concluded that the micropores of zeolite as adsorbent can be modified using the imprinting technology in order to increase its sensitivity and selectivity towards p-Cresol.
White rice husk ash (RHA), an agriculture waste containing crystalline tridymite and alpha-cristobalite, was used as a silica source for zeolite Beta synthesis. The crystallization of zeolite Beta from RHA at 150 degrees C in the presence of tetraethylammonium hydroxide was monitored by XRD, FTIR and (29)Si MAS NMR techniques. It was found that zeolite Beta started to form after 12h and the complete crystallization of zeolite Beta phase was achieved after 2d. XRD, (29)Si MAS NMR and solid yield studies indicate that the transformation mechanism of silica present in RHA to zeolite Beta involves dissolution of the ash, formation of an amorphous aluminosilicate after 6h of crystallization, followed by dissolution in the mother liquor and final transformation to pure zeolite Beta crystals.
Improper use of urea may cause environmental pollution through NH3 volatilization and NO3 (-) leaching from urea. Clinoptilolite zeolite and compost could be used to control N loss from urea by controlling NH4 (+) and NO3 (-) release from urea. Soil incubation and leaching experiments were conducted to determine the effects of clinoptilolite zeolite and compost on controlling NH4 (+) and NO3 (-) losses from urea. Bekenu Series soil (Typic Paleudults) was incubated for 30, 60, and 90 days. A soil leaching experiment was conducted for 30 days. Urea amended with clinoptilolite zeolite and compost significantly reduced NH4 (+) and NO3 (-) release from urea (soil incubation study) compared with urea alone, thus reducing leaching of these ions. Ammonium and NO3 (-) leaching losses during the 30 days of the leaching experiment were highest in urea alone compared with urea with clinoptilolite zeolite and compost treatments. At 30 days of the leaching experiment, NH4 (+) retention in soil with urea amended with clinoptilolite zeolite and compost was better than that with urea alone. These observations were because of the high pH, CEC, and other chemical properties of clinoptilolite zeolite and compost. Urea can be amended with clinoptilolite zeolite and compost to improve NH4 (+) and NO3 (-) release from urea.
The surfaces of NaY zeolite particles were modified by the alkylsilylation of n-octadecyltrichlorosilane (OTS). Two kinds of modified NaY zeolites were prepared; one with its external surface partially and the other fully covered with alkylsilyl groups. Since the size of OTS is bigger than the pore diameter of NaY, it is attached on the external surface, leaving the internal pore accessible to adsorbate molecules. As a result of alkylsilylation, the adsorption properties of these sorbents were improved. The adsorption properties of these materials were tested by their reaction in a mixture of paraquat and blue dye. The results demonstrate that the alkysilylated NaY materials are capable of simultaneous adsorption of paraquat and blue dye. Paraquat was selectively adsorbed into the internal pore of the zeolite whereas the dye on the externally attached alkylsilyl groups of the sorbent; displaying the unique bimodal amphiphilic character of the alkylsilylated NaY zeolites.
Efficient management of P fertilizers ensures good yield of crops and adequate food supply. In the acid soil of the tropics, soluble P is fixed by Al and Fe. Exploitation of the high CEC and pH of Clinoptilolite zeolite (CZ) could mitigate low soil pH and P fixation in acid soils. This study was undertaken to determine the effects of amending a weathered acid soil with CZ on: (i) soil P availability and other related soil chemical properties, and (ii) nutrient concentration, nutrient uptake, above-ground biomass, agronomic efficiency, and yield of Zea mays L. on a tropical acidic soil. Triple superphosphate (TSP), Egypt Rock phosphate (ERP), and Christmas Island Rock phosphate (CIRP) were used as P sources. The treatments evaluated were: (i) soil alone, (ii) 100% recommended fertilizer rate (NPK), and (iii) 75% fertilizer rate + Clinoptilolite zeolite. Selected soil chemical properties and P availability were determined before and after field trials. Zea mays L. above-ground biomass, nutrient concentration, nutrient uptake, agronomic efficiency, and fresh cob yield were also determined. Results revealed that the effects of treatments with and without CZ treatments on soil pH, P fractions, soil acidity, dry matter production, yield of maize, nutrient uptake, and agronomic efficiency were similar. Hence, suggesting CZ inclusion in the fertilization program of Zea mays L is beneficial in terms of reducing excessive or unbalanced use of chemical fertilizers due to reduction of fertilizers usage by 25%.
Despite the extensive research into the catalytic uses of zeolite-based catalysts, these catalysts have a limited useful lifetime because of the deactivating effect of coke production. This study looks at the use of Cerium (Ce) loaded HZSM-5 zeolite catalysts in the hydrocarbon and oxygenated chemical conversion from Chlorella Vulgaris microalgae crude oil. Characterization of structure, morphology, and crystallinity was performed after the catalysts were manufactured using the impregnation technique. Soxhlet extraction was carried out to extract the crude oil of microalgae. Transesterification reaction was used to produce algal hydrolyzed oil (HO), and the resulting HO was put to use in a batch reactor at 300 °C, 1000 rpm, 7 bars of nitrogen pressure, a catalyst to the algal HO ratio of 15% (wt. %), and a retention time of 6 h. To determine which Ce-loaded HZSM-5 catalysts would be most effective in converting algal HO into non-oxygenated molecules (hydrocarbons), we conducted a series of tests. Liquid product characteristics were analyzed for elemental composition, higher heating value (HHV), atomic ratios of O/C and H/C, and degree of deoxygenation (DOD%). Results were categorized into three groups: product yield, chemical composition, and carbon number distribution. When Cerium was added to HZSM-5 zeolite at varying loading percentages, the zeolite's acid sites became more effective in facilitating the algal HO conversion. The results showed that 10%Ce/HZSM-5 had the greatest conversion of the algal HO, the yield of hydrocarbons, HHV, and DOD% (98.2%, 30%, 34.05 MJ/Kg, and 51.44%, respectively) among all the synthesized catalysts in this research. In conclusion, the physical changes seen in the textural characteristics may be attributed to Cerium-loading on the parent HZSM-5; nevertheless, there is no direct association between the physical features and the hydrocarbons yield (%). The primary impact of Cerium alteration of the parent HZSM-5 zeolite was to change the acidic sites required to boost the conversion (%) of the algal HO in the catalytic deoxygenation process, which in turn increased the hydrocarbons yield (%), which in turn increased the HHV and DOD%.
Due to their high lipid content, microalgae are one of the most significant sources of green hydrocarbons, which might help lessen the world's need for fossil fuels. Many zeolite-based catalysts are quickly deactivated by coke production and have a short lifetime. In this study, a bimetallic Lanthanum-Cerium (La-Ce)-modified HZSM-5 zeolite catalyst was synthesized through an impregnation method and was tested for the conversion of hydrolyzed oil into oxygen-free hydrocarbon fuels of high energy content. Initially, hydrolyzed oil (HO), the byproduct of the transesterification process, was obtained by the reaction of crude oil derived from Chlorella vulgaris microalgae and a methanol. Various catalysts were produced, screened, and evaluated for their ability to convert algal HO into hydrocarbons and other valuable compounds in a batch reactor. The performance of HZSM-5 was systematically tested in view of La-Ce loaded on conversion, yield, and selectivity. NH3-TPD analysis showed that the total acidity of the La-Ce-modified zeolites was lower than that of the pure HZSM-5 catalyst. TGA testing revealed that including the rare earth elements La and Ce in the HZSM-5 catalyst lowered the catalyst propensity for producing coke deposits. The acid sites necessary for algal HO conversion were improved by putting La and Ce into HZSM-5 zeolite at various loading percentages. The maximum hydrocarbon yield (42.963%), the highest HHV (34.362 MJ/Kg), and the highest DOD% (62.191%) were all achieved by the (7.5%La-2.5%Ce)/HZSM-5 catalyst, which was synthesized in this work. For comparison, the hydrocarbon yield for the parent HZSM-5 was 21.838%, the HHV was (33.230 MJ/Kg), and the DOD% was 44.235%. In conclusion, La and Ce-loading on the parent HZSM-5 may be responsible for the observed alterations in textural properties; nevertheless, there is no clear correlation between the physical features and the hydrocarbon yield (%). The principal effect of La and Ce modifying the parent HZSM-5 zeolite was to modify the acidic sites needed to enhance the conversion (%) of the algal HO during the catalytic deoxygenation process, which in turn raised the hydrocarbon yield (%) and increased the HHV and DOD%.
In this article, gelatin/copper activated faujasites (CAF) composite scaffolds were fabricated by lyophilisation technique for promoting partial thickness wound healing. The optimised scaffold with 0.5% (w/w) of CAF, G (0.5%), demonstrated pore size in the range of 10-350 μm. Agar disc diffusion tests verified the antibacterial role of G (0.5%) and further supported that bacterial lysis was due to copper released from the core of CAF embedded in the gelatin matrix. The change in morphology of bacteria as a function of CAF content in gelatin scaffold was studied using SEM analysis. The confocal images revealed the increase in mortality rate of bacteria with increase in concentration of incorporated CAF in gelatin matrix. Proficient oxygen supply to needy cells is a continuing hurdle faced by tissue engineering scaffolds. The dissolved oxygen measurements revealed that CAF embedded in the scaffold were capable of increasing oxygen supply and thereby promote cell proliferation. Also, G (0.5%) exhibited highest cell viability on NIH 3T3 fibroblast cells which was mainly attributed to the highly porous architecture and its ability to enhance oxygen supply to cells. In vivo studies conducted on Sprague Dawley rats revealed the ability of G (0.5%) to promote skin regeneration in 20 days. Thus, the obtained data suggest that G (0.5%) is an ideal candidate for wound healing applications.