Solid acid catalyzed cracking of waste oil-derived fatty acids is an attractive route to hydrocarbon fuels. HZSM-5 is an effective acid catalyst for fatty acid cracking; however, its microporous nature is susceptible to rapid deactivation by coking. We report the synthesis and application of hierarchical HZSM-5 (h-HZSM-5) in which silanization of pre-crystallized zeolite seeds is employed to introduce mesoporosity during the aggregation of growing crystallites. The resulting h-HZSM-5 comprises a disordered array of fused 10-20 nm crystallites and mesopores with a mean diameter of 13 nm, which maintain the high surface area and acidity of a conventional HZSM-5. Mesopores increase the yield of diesel range hydrocarbons obtained from oleic acid deoxygenation from ~20% to 65%, attributed to improved acid site accessibility within the hierarchical network.
Adsorption is one of the most efficient ways to remove heavy metal from wastewater. In this study, the adsorptive removal of hexavalent chromium, Cr (VI) from aqueous solution was investigated using natural zeolite, clinoptilolite, in the form of hollow fibre ceramic membrane (HFCM). The HFCM sample was prepared using phase inversion-based extrusion technique and followed by sintering process at different sintering temperatures in the range of 900-1050 °C. The fabricated HFCM was characterised using scanning electron microscopy (SEM), contact angle, water permeability, and mechanical strength for all HFCMs sintered at different temperatures. The adsorption and filtration test of Cr (VI) were performed using an in-house water permeation set up with a dead-end cross-flow permeation test. An asymmetric structure with sponge- and finger-like structures across the cross-section of HFCM was observed using SEM. Based on the characterisation data, 1050 °C was chosen to be the best sintering temperature as the water permeability and mechanical strength of this HFCM were 29.14 L/m2∙h and 50.92 MPa, respectively. The performance of the HFCM in adsorption/filtration was 44% of Cr (VI) removal at the Cr (VI) concentration of 40 mg/L and pH 4. In addition, the mathematical model was also performed in simulating the experimental data obtained from this study. All in all, the natural zeolite-based HFCM has a potential as a single-step Cr (VI) removal by membrane adsorption for the wastewater treatment.
Comparison studies in suspension and hybrid photocatalytic membrane reactor (HPMR) system was investigated by using Reactive Black 5 (RB5) as target pollutant under UVA light irradiation. To achieve this aim, hybrid TiO2/clinoptilolite (TCP) photocatalyst powder was prepared by solid-state dispersion (SSD) methods and embedded at the outer layer of dual layer hollow fiber (DLHF) membranes fabricated via single step co-spinning process. TiO2 and CP photocatalyst were also used as control samples. The samples were characterized by Scanning Electron Microscopy (SEM), Energy Dispersion of X-ray (EDX), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses. The result shows that TCP was actively functioned as photocatalyst in suspension system and 86% of RB5 photocatalytic degradation achieved within 60 min; however the additional step is required to separate the catalyst with treated water. In the HPMR system, even though the RB5 photocatalytic degradation exhibits lower efficiency however the rejection of RB5 was achieved up to 95% under UV irradiation due to the properties of photocatalytic membranes. The well dispersed of TCP at the outer layer of DLHF membrane have improved the surface affinity of DL-TCP membrane towards water, exhibit the highest pure water flux of 41.72 L/m2.h compared to DL-TiO2 membrane. In general, CP can help on improving photocatalytic activity of TiO2 in suspension, increased the RB5 removal and the permeability of DLHF membrane in HPMR system as well.
An aptasensor was developed on an interdigitated microelectrode (IDME) by current-volt sensing for the diagnosis of ulcerative colitis by detecting the biomarker lipocalin-2. Higher immobilization of the anti-lipocalin-2 aptamer as a probe was achieved by using sodium dodecyl benzenesulfonate-aided zeolite particles. FESEM and FETEM observations revealed that the size of the zeolite particles was <200 nm, and they displayed a uniform distribution and spherical shape. XPS analysis attested the occurrence of Si, Al, and O groups on the zeolite particles. Zeolite particles were immobilized on IDME by a (3-aminopropyl)-trimethoxysilane amine linker, and then, the aptamer as the probe was tethered on the zeolite particles through a biotin-streptavidin strategy assisted by a bifunctional aldehyde linker. Due to the high occupancy of the aptamer and the efficient electric transfer from zeolite particles, higher changes in current can be observed upon interaction of the aptamer with lipocalin-2. The lower detection of lipocalin-2 was noted as 10 pg/mL, with a linear range from 10 pg/mL to 1 μg/mL and a linear regression equation of y=8E-07x+8E-08; R² = 0.991. Control experiments with complementary aptamer and matrix metalloproteinase-9 indicate the specific detection of lipocalin-2. Furthermore, spiking lipocalin-2 in human serum does not interfere with the identification.
A new effective RF tar thermocatalytic treatment process with low energy intensive has been proposed to remove tar from biomass gasification. Toluene and naphthalene as biomass tar model compounds were removed via both thermal and catalytic treatment over a wide temperature range from 850 °C to 1200 °C and 450 °C to 900 °C, respectively at residence time of 0-0.7 s. Thermal characteristics of the new technique are also described in this paper. This study clearly clarified that toluene was much easier to be removed than naphthalene. Soot was found as the final product of thermal treatment of the tar model and completely removed during catalytic treatment. Radical reactions generated by RF non-thermal effect improve the tar removal. The study showed that Y-zeolite has better catalytic activity compared to dolomite on toluene and naphthalene removal due to its acidic nature and large surface area, even at lower reaction temperature of about 550 °C.
Catalytic cracking of crude palm oil (CPO) and used palm oil (UPO) were studied in a transport riser reactor for the production of biofuels at a reaction temperature of 450 degrees C, with residence time of 20s and catalyst-to-oil ratio (CTO) of 5 gg(-1). The effect of HZSM-5 (different Si/Al ratios), beta zeolite, SBA-15 and AlSBA-15 were studied as physically mixed additives with cracking catalyst Rare earth-Y (REY). REY catalyst alone gave 75.8 wt% conversion with 34.5 wt% of gasoline fraction yield using CPO, whereas with UPO, the conversion was 70.9 wt% with gasoline fraction yield of 33.0 wt%. HZSM-5, beta zeolite, SBA-15 and AlSBA-15 as additives with REY increased the conversion and the yield of organic liquid product. The transport riser reactor can be used for the continuous production of biofuels from cracking of CPO and UPO over REY catalyst.
Ammonia loss significantly reduces the urea-N use efficiency in crop production. Efforts to reduce this problem are mostly laboratory oriented. This paper reports the effects of urea amended with triple superphosphate (TSP) and zeolite (Clinoptilolite) on soil pH, nitrate, exchangeable ammonium, dry matter production, N uptake, fresh cob production, and urea-N uptake efficiency in maize (Zea mays) cultivation on an acid soil in actual field conditions. Urea-amended TSP and zeolite treatments and urea only (urea without additives) did not have long-term effect on soil pH and accumulation of soil exchangeable ammonium and nitrate. Treatments with higher amounts of TSP and zeolite significantly increased the dry matter (stem and leaf) production of Swan (test crop). All the treatments had no significant effect on urea-N concentration in the leaf and stem of the test crop. In terms of urea-N uptake in the leaf and stem tissues of Swan, only the treatment with the highest amount of TSP and zeolite significantly increased urea-N uptake in the leaf of the test crop. Irrespective of treatment, fresh cob production was statistically not different. However, all the treatments with additives improved urea-N uptake efficiency compared to urea without additives or amendment. This suggests that urea amended with TSP and zeolite has a potential of reducing ammonia loss from surface-applied urea.
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.
This study investigated the efficacy of using phosphate-modified zeolite (PZ) as an adsorbent for removing thorium from aqueous solutions. The effects of various factors such as contact time, adsorbent mass, initial thorium concentration, and pH value of the solution on the removal efficiency were analyzed using the batch technique to obtain optimum adsorption condition. The results revealed that the optimal conditions for thorium adsorption were a contact time of 24 h, 0.03 g of PZ adsorbent, pH 3, and a temperature of 25 °C. Isotherm and kinetics parameters of the thorium adsorption on PZ were also determined, with equilibrium studies showing that the experimental data followed the Langmuir isotherm model. The maximum adsorption capacity (Qo) for thorium was found to be 17.3 mg/g with the Langmuir isotherm coefficient of 0.09 L/mg. Using phosphate anions to modify natural zeolite increased its adsorption capacity. Furthermore, adsorption kinetics studies demonstrated that the adsorption of thorium onto PZ adsorbent fitted well with the pseudo-second-order model. The applicability of the PZ adsorbent in removing thorium from real radioactive waste was also investigated, and nearly complete thorium removal was achieved (> 99%) from the leached solution obtained from cracking and leaching processes of rare earth industrial residue under optimized conditions. This study elucidates the potential of PZ adsorbent for efficient removal of thorium from rare earth residue via adsorption, leading to a reduction in waste volume for ultimate disposition.
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.
The pyrolysis of oil palm mesocarp fiber (OPMF) was catalyzed with a steel slag-derived zeolite (FAU-SL) in a slow-heating fixed-bed reactor at 450 °C, 550 °C, and 600 °C. The catalytic pyrolysis of OPMF produced a maximum yield of 47 wt% bio-oil at 550 °C, and the crude pyrolysis vapor (CPV) of this process yielded crude pyrolysis oil with broad distribution of bulky oxygenated organic compounds. The bio-oil composition produced at 550 °C contained mainly light and stable acid-rich carbonyls at a relative abundance of 48.02% peak area and phenolic compounds at 12.03% peak area. The FAU-SL high mesoporosity and strong surface acidity caused the conversion of the bulky CPV molecules into mostly light acid-rich carbonyls and aromatics through secondary reactions. The secondary reactions mechanisms facilitated by FAU-SL reduced the distribution of the organic compounds in the bio-oil to mostly acid-rich carbonyls and aromatic in contrast to other common zeolite.
This study investigated the catalytic co-pyrolysis of sugarcane bagasse (SCB) and waste high-density polyethylene (HDPE) over faujasite-type zeolite derived from electric arc furnace slag (FAU-EAFS) in a fixed-bed reactor. The effects of reaction temperature, catalyst-to-feedstock ratio, and HDPE-to-SCB ratio on product fractional yields and chemical compositions were discussed. The co-pyrolysis of SCB and HDPE over FAU-EAFS increased the liquid yield and enhanced the quality of bio-oil. The maximum bio-oil (68.56 wt%) and hydrocarbon yield (74.55%) with minimum yield of oxygenated compounds (acid = 0.57% and ester = 0.67%) were achieved under the optimum experimental conditions of catalyst-to-feedstock ratio of 1:6, HDPE-to-SCB ratio of 40:60, and temperature of 500 °C. The oil produced by catalytic co-pyrolysis had higher calorific value than the oil produced by the pyrolysis of SCB alone.
Catalytic co-pyrolysis (CCP) of spent coffee ground (SCG) and cellulose over HZSM-5 and HY was characterized thermogravimetrically, and a catalytic pyrolysis of two samples was conducted using a tandem micro reactor that directly connected with gas chromatography-mass spectrometry. To access the more fundamental investigations on CCP, the effects of the zeolite pore structure, reaction temperature, in-situ/ex-situ reaction mode, catalyst to feedstock ratio, and the SCG and cellulose mixing ratio were experimentally evaluated. The temperature showing the highest thermal degradation rate of cellulose with SCG slightly delayed due to the interactions during the thermolysis of two samples. HZSM-5 in reference to HY produced more aromatic hydrocarbons from CCP. With respect to the reaction temperature, the formation of aromatic hydrocarbons increased with the pyrolytic temperature. Moreover, the in-situ/ex-situ reaction mode, catalyst/feedstock, and cellulose/SCG ratio were optimized to improve the aromatic hydrocarbon yield.
We present a novel synthesis strategy termed delayed linker addition (DLA) to synthesize hybrid zeolitic-imidazolate frameworks containing unsubstituted imidazolate linkers (Im) with SOD topology (hereafter termed Im/ZIF-8). Im linker incorporation can create larger voids and apertures, which are important properties for gas storage and separation. To date, there have been only a handful of reports of Im linkers incorporated into ZIF-8 frameworks, typically requiring arduous and complicated post synthesis approaches. DLA, as reported here, is a simple one-step synthesis strategy allowing high incorporation of Im linker into the ZIF-8 framework while still retaining its SOD topology. We fabricated mixed-matrix membranes (MMMs) with 6FDA-DAM polymer and Im/ZIF-8 obtained via DLA as a filler. The Im/ZIF-8-containing MMMs showed excellent performance for both propylene/propane and n-butane/i-butane separation, displaying permeability and ideal selectivity well above the polymer upper bound. Moreover, highly detailed molecular simulations shed light to the aperture size and flexibility response of Im/ZIF-8 and its improved diffusivity as compared to ZIF-8.
Availability of quality-certified water is pertinent to the production of food and pharmaceutical products. Adverse effects of manganese content of water on the corrosion of vessels and reactors necessitate that process water is scrutinized for allowable concentration levels before being applied in the production processes. In this research, optimization of the adsorption process conditions germane to the removal of manganese from biotreated palm oil mill effluent (BPOME) using zeolite 3A subsequent to a comparative adsorption with clinoptilolite was studied. A face-centered central composite design (FCCCD) of the response surface methodology (RSM) was adopted for the study. Analysis of variance (ANOVA) for response surface quadratic model revealed that the model was significant with dosage and agitation speed connoting the main significant process factors for the optimization. R(2) of 0.9478 yielded by the model was in agreement with predicted R(2). Langmuir and pseudo-second-order suggest the adsorption mechanism involved monolayer adsorption and cation exchanging.
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).
A 60-year-old man who presented with nasopharyngitis developed uncontrollable epistaxis following a punch biopsy of the nasopharynx. QuickClot was successfully used to arrest the haemorrhage under general anaesthesia after the usual methods employed to secure haemostasis failed. The haemostatic plug was successfully removed a week later after control of the infection. This case represents the first reported intranasal use of QuickClot. We describe our experience and a literature review on this haemostatic agent.
The effects of zeolite and zinc foliar applications on the biochemical characteristics of canola cultivars under different moisture regimes were investigated in a study conducted during the 2010 and 2011 growing seasons. The study was completed using a factorial split-plot experiment based on randomized complete block design (RCBD) with three replications at the Seed and Plant Improvement Institute (SPII), Karaj, Iran. The treatments were: irrigation (I): complete (I1) and restricted (I2); zeolite (Z): 0 (Z1) and 15 ton ha-1 (Z2) and Zn: 0, 0.1 and 0.2% concentrations of zinc sulfate (Zn1, Zn2, and Zn3) at the pod formation stage. These treatments were applied during the pod formation stage to the Licord, RGS003 and Opera cultivars. This study showed that although applying Z and Zn had positive effects on the quality of canola, the highest performance and the best results were obtained using a combination of Z and Zn. The combined application of Z and Zn decreased the proline and carbohydrate contents to 44.35 and 34.42%, respectively. Therefore, with the low cost of natural Z and moderate Zn intake, these treatments can be used to enhance the performance of canola, especially in regions frequently subjected to water stress.
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.
Nickel-based catalysts play an important role in the hydrogen-free deoxygenation for the production of biofuel. The yield and quality of the biofuel are critically affected by the physicochemical properties of NiO supported on nanosized zeolite Y (Y65, crystal size of 65 nm). Therefore, 10 wt% NiO supported on Y65 synthesized by using impregnation (IM) and deposition-precipitation (DP) methods were investigated. It was found that preparation methods have a significant effect on the deoxygenation of triolein. The initial rate of the DP method (14.8 goil·h-1) was 1.5 times higher than that of the IM method (9.6 goil·h-1). The DP-Y65 showed the best deoxygenation performance with a 80.0% conversion and a diesel selectivity of 93.7% at 380 °C within 1 h. The outstanding performance from the DP method was due to the smaller NiO particle size (3.57 ± 0.40 nm), high accessibility (H.F value of 0.084), and a higher Brönsted to Lewis acidity (B/L) ratio (0.29), which has improved the accessibility and deoxygenation ability of the catalyst. The NH4+ released from the decomposition of the urea during the DP process increased the B/L ratio of zeolite NaY. As a result, the pretreatment to convert Na-zeolite to H-zeolite in a conventional zeolite synthesis can be avoided. In this regard, the DP method offers a one-pot synthesis to produce smaller NiO-supported nanosized zeolite NaY with a high B/L ratio, and it managed to produce a higher yield with selectivity towards green diesel via deoxygenation under a hydrogen-free condition.