The atmosphere security and regulation of climate change are being continuously highlighted as a pressing issue. The crisis of climate change owing to the anthropogenic carbon dioxide emission has led many governments at federal and provincial levels to promulgate policies to address this concern. Among them is regulating the carbon dioxide emission from major industrial sources such as power plants, petrochemical industries, cement plants, and other industries that depend on the combustion of fossil fuels for energy to operate. In view of this, various CO2 capture and sequestration technologies have been investigated and presented. From this review, adsorption of CO2 on porous solid materials has been gaining increasing attention due to its cost-effectiveness, ease of application, and comparably low energy demand. Despite the myriad of advanced materials such as zeolites, carbons-based, metal-organic frameworks, mesoporous silicas, and polymers being researched, research on activated carbons (ACs) continue to be in the mainstream. Therefore, this review is endeavored to elucidate the adsorption properties of CO2 on activated carbons derived from different sources. Selective adsorption based on pore size/shape and surface chemistry is investigated. Accordingly, the effect of surface modifications of the ACs with NH3, amines, and metal oxides on adsorption performance toward CO2 is evaluated. The adsorption performance of the activated carbons under humid conditions is also reviewed. Finally, activated carbon-based composite has been surveyed and recommended as a feasible strategy to improve AC adsorption properties toward CO2. The activated carbon surface in the graphical abstract is nitrogen rich modified using ammonia through thermal treatment. The values of CO2 emissions by sources are taken from (Yoro and Daramola 2020).
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.
Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.
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.
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.
A feasible and cost-effective process for utilization of toluene and heavy reformate is the conversion of its streams by transalkylation reaction into highly valuable xylenes. The process is usually catalysed by zeolites and the challenges to overcome in transalkylation of heavy reformate with toluene over zeolites are their selectivity, activity, long-term stability, and coke formation. Current study aimed to investigate xylenes production by transalkylation reaction on the synthesized metal-doped zeolite catalysts and to characterize prepared catalysts by FTIR, SEM, EDS and BET analysis. Toluene/heavy reformate modelled mixture was utilized as a feed. For the first time Beta and ZSM-5 catalysts with 10% (w/w) cerium and 0.1% (w/w) palladium were synthesized by calcination and wet impregnation method. Catalytic tests were performed by continuous-flow gas/solid catalytic fixed bed reactor at atmospheric pressure, 2 h-1 and 5 h-1 and 250, 300, 350 and 400 °C. Experimental results revealed that the highest heavy reformate conversion (98.94%) and toluene conversion (9.82%) were obtained over H-ZSM-5, at 400 °C and 2 h-1 WHSV. The highest xylene selectivity (11.53) was achieved over H-ZSM-5, and the highest p-xylene percentage (62.40%), using Ce-ZSM-5 catalyst. ZSM-5 catalysts showed more resistance to coke deposition than Beta zeolites. The present study delivers novel approach and catalysts, which have immense potential for developing safer and inexpensive transalkylation process in industry.
A new heterogeneous catalyst for sonocatalytic degradation of amaranth dye in water was synthesized by introducing titania into the pores of zeolite (NaY) through ion exchange method while Fe (III) was immobilized on the encapsulated titanium via impregnation method. XRD results could not detect any peaks for titanium oxide or Fe(2)O(3) due to its low loading. The UV-vis analysis proved a blue shift toward shorter wavelength after the loading of Ti into NaY while a red shift was detected after the loading of Fe into the encapsulated titanium. Different reaction variables such as TiO(2) content, amount of Fe, pH values, amount of hydrogen peroxide, catalyst loading and the initial dye concentration were studied to estimate their effect on the decolorization efficiency of amaranth. The maximum decolorization efficiency achieved was 97.5% at a solution pH of 2.5, catalyst dosage of 2 g/L, 20 mmol/100 mL of H(2)O(2) and initial dye concentration of 10 mg/L. The new heterogeneous catalyst Fe/Ti-NaY was a promising catalyst for this reaction and showed minimum Fe leaching at the end of the reaction.
This study focused on improving the producer gas quality using radio frequency (RF) tar thermocatalytic treatment reactor. The producer gas containing tar, particles and water was directly passed at a particular flow rate into the RF reactor at various temperatures for catalytic and thermal treatments. Thermal treatment generates higher heating value of 5.76 MJ Nm(-3) at 1200°C. Catalytic treatments using both dolomite and Y-zeolite provide high tar and particles conversion efficiencies of about 97% on average. The result also showed that light poly-aromatic hydrocarbons especially naphthalene and aromatic compounds particularly benzene and toluene were still found even at higher reaction temperatures. Low energy intensive RF tar thermocatalytic treatment was found to be effective for upgrading the producer gas quality to meet the end user requirements and increasing its energy content.
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.
One of the most crucial attributes of synthetic organic chemistry is to design organic reactions under the facets of green chemistry for the sustainable production of chemicals. Thus, due to the intensified environmental and safety concern, the need for new technologies for conducting chemical transformation has grown. In this regard, there is enormous interest in the use of heterogeneous catalysts as they generally avoid the generation of waste, require fewer toxic reagents, as well as entail easier separation and recycling of the catalyst. α,β-Unsaturated acids have been widely used in various industrial applications and have been identified as one of the most promising chemicals obtained via the Knoevenagel condensation reaction. This review aims to discuss the most pertinent heterogeneous catalytic systems such as zeolites, mesoporous silica, ionic liquids, metal oxides, and graphitic carbon nitride-based catalysts in the Knoevenagel reaction. Ultimately, this review focuses not only on the catalyst but also provides an overall idea and guide for the preparation of new catalysts with outstanding properties by looking at the chemical and engineering aspects such as the reaction conditions and the mechanisms.
The study explored the characteristics and effectiveness of modified TiO2 nanotubes with zeolite as a composite photocatalyst (MTNZC) for the degradation of triclocarban (TCC) from the aqueous solution. MTNZC samples have been produced via electrochemical anodisation (ECA) followed by electrophoretic deposition (EPD). Three independent factors selected include MTNZC size (0.5-1 cm2), pH (3-10), and irradiation time (10-60 min). The observation revealed that the surface of Ti substrate by the 40 V of anodisation and 3 h of calcination was covered with the array ordered, smooth and optimum elongated nanotubes with average tube length was approximately 5.1 μm. EDS analysis proved the presence of Si, Mg, Al, and Na on MTNZC due to the chemical composition present in the zeolite. The average crystallite size of TiO₂ nanotubes increased from 2.07 to 3.95 nm by increasing anodisation voltage (10, 40, and 60 V) followed by 450 °C of calcination for 1, 3, and 6 h, respectively. The optimisation by RSM shows the F-value (36.12), the p-value of all responses were less than 0.0001, and the 95% confidence level of the model by all the responses indicated the model was significant. The R2 in the range of 0.9433-0.9906 showed the suitability of the model to represent the actual relationship among the parameters. The photocatalytic degradation rate of TCC from the first and the fifth cycles were 94.2 and 77.4%, indicating the applicability of MTNZC to be used for several cycles.
The current work aimed to investigate the degradation of the triclocarban (TCC) in aqueous solution using a modified zeolite/TiO2 composite (MZTC) synthesized by applying the electrochemical anodization (ECA). The synthesis process was conducted at different voltages (10, 40, and 60) V in 1 h and using electrophoresis deposition (EPD) in doping zeolite. The MZTC was covered with the array ordered, smooth and optimum elongated nanotubes with 5.1 μm of the length, 120.3 nm of the inner diameter 14.5 nm of the wall thickness with pure titanium and crystalline titania as determined by FESEM/EDS, and XRD. The kinetic study by following Langmuir-Hinshelwood(L-H) model and pseudo first order, the significant constant rate was obtained at pH 11 which was 0.079 ppm/min, 0.75 cm2 of MZTC catalyst loading size achieved 0.076 ppm/min and 5 ppm of TCC initial concentration reached 0.162 ppm/min. The high-performance liquid chromatography (HPLC) analysis for mechanism study of TCC photocatalytic degradation revealed eleven intermediate products after the whole process of photocatalysis. In regard of toxicology assessment by the bacteria which is Photobacterium phosphoreum, the obtained concentration of TCC at minute 60 was less satisfied with remained 0.36 ppm of TCC was detected indicates that the concentration was above allowable level. Where the allowable level of TCC in stream is 0.1 ppm.
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 behaviours of butyl acetate in air have been studied over silver-loaded Y (Si/Al=40) and ZSM-5 (Si/Al=140) zeolites. The silver metal was loaded into the zeolites by ion exchange (IE) and impregnation (IM) methods. The adsorption study was mainly conducted at a gas hourly space velocity (GHSV) of 13,000 h(-1) with the organic concentration of 1000 ppm while the desorption step was carried out at a GHSV of 5000 h(-1). The impregnated silver-loaded adsorbents showed lower uptake capacity and shorter breakthrough time by about 10 min, attributed to changes in the pore characteristics and available surface for adsorption. Silver exchanged Y (AgY(IE)) with lower hydrophobicity showed higher uptake capacity of up to 35%, longer adsorbent service time and easier desorption compared to AgZSM-5(IE). The presence of water vapour in the feed suppressed the butyl acetate adsorption of AgY(IE) by 42% due to the competitive adsorption of water on the surface and the effect was more pronounced at lower GHSV. Conversely, the adsorption capacity of AgZSM-5(IE) was minimally affected, attributed to the higher hydrophobicity of the material. A mathematical model is proposed to simulate the adsorption behaviour of butyl acetate over AgY(IE) and AgZSM-5(IE). The model parameters were successfully evaluated and used to accurately predict the breakthrough curves under various process conditions with root square mean errors of between 0.05 and 0.07.
Zeolite socony mobil-5 (ZSM-5) is a common catalyst used for biomass pyrolysis. Nevertheless, the quantitative information on the catalytic behavior of ZSM-5 on biomass pyrolysis is absent so far. This study focuses on the catalytic pyrolysis phenomena and mechanisms of biomass wastes using ZSM-5 via thermogravimetric analyzer and pyrolysis-gas chromatography/mass spectrometry, with particular emphasis on catalytic level identification and aromatic hydrocarbons (AHs) formation. Two biomass wastes of sawdust and sorghum distillery residue (SDR) are investigated, while four biomass-to-catalyst ratios are considered. The analysis suggests that biomass waste pyrolysis processes can be divided into three zones, proceeding from a heat-transfer dominant zone (zone 1) to catalysis dominant zones (zones 2 and 3). The indicators of the intensity of difference (IOD), catalytic effective area, catalytic index (CI), and aromatic enhancement index are conducted to measure the catalytic effect of ZSM-5 on biomass waste pyrolysis and AHs formation. The maximum IOD occurs in zone 2, showing the highest intensity of the catalytic effect. The CI values of the two biomass wastes increase with increasing the biomass-to-catalyst ratio. However, there exists a threshold for sawdust pyrolysis, indicating a limit for the catalytic effect on sawdust. The higher the catalyst addition, the higher the AHs proportion in the vapor stream. When the biomass-to-catalyst ratio is 1/10, AHs formation is intensified significantly, especially for sawdust. Overall, the indexes conducted in the present study can provide useful measures to identify the catalytic pyrolysis dynamics and levels.
Cylinder-shaped NaY zeolite was used as an adsorbent for eradicating both heavy metal ions (Cu2+, Zn2+, Ni2+, and Co2+) and proteins from the waste streams. As a pseudo-metal ion affinity adsorbent, NaY zeolite was used in the capture of heavy metal ions in the first stage. The amount (molar basis) of metal ions adsorbed onto NaY zeolite decreased in the order of Cu2+ > Zn2+ > Co2+ > Ni2+. Bovine serum albumin (BSA) was utilized as a model of proteins used in the waste adsorption process by NaY zeolite. The adsorption capacities of NaY zeolite and Cu/NaY zeolite for BSA were 14.90 mg BSA/g zeolite and 84.61 mg BSA/g zeolite, respectively. Moreover, Cu/NaY zeolite was highly stable in the solutions made of 2 M NaCl, 500 mM imidazole or 125 mM EDTA solutions. These conditions indicated that the minimal probability of secondary contamination caused by metal ions and soluble proteins in the waste stream. This study demonstrates the potential of Cu/NaY zeolite complex as an efficient pseudo-metal chelate adsorbent that could remove metal ions and water-soluble proteins from wastewater concurrently.
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.
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.
The main objective of this work was to determine the effectiveness of various biofouling reducers (BFRs) to operational condition in hybrid membrane bioreactor (MBR) of palm oil mill effluent (POME). A series of tests involving three bench scale (100 L) hybrid MBR were operated at sludge retention times (SRTs) of 30 days with biofouling reducer (BFR). Three different biofouling reducers (BFRs) were powdered actived carbon (PAC), zeolite (Ze), and Moringa oleifera (Mo) with doses of 4, 8 and 12 g L(-1) respectively were used. Short-term filtration trials and critical flux tests were conducted. Results showed that, all BFRs successfully removed soluble microbial products (SMP), for PAC, Ze, and Mo at 58%, 42%, and 48%, respectively. At their optimum dosages, PAC provided above 70% reductions and 85% in fouling rates during the short-term filtration and critical flux tests.
Fibrinogen is one of the key proteins that participate in the protein corona composition of many types of nanoparticles (NPs), and its conformational changes are crucial for activation of immune systems. Recently, we demonstrated that the fibrinogen highly contributed in the protein corona composition at the surface of zeolite nanoparticles. Therefore, understanding the interaction of fibrinogen with zeolite nanoparticles in more details could shed light of their safe applications in medicine. Thus, we probed the molecular interactions between fibrinogen and zeolite nanoparticles using both experimental and simulation approaches. The results indicated that fibrinogen has a strong and thermodynamically favorable interaction with zeolite nanoparticles in a non-cooperative manner. Additionally, fibrinogen experienced a substantial conformational change in the presence of zeolite nanoparticles through a concentration-dependent manner. Simulation results showed that both E- and D-domain of fibrinogen are bound to the EMT zeolite NPs via strong electrostatic interactions, and undergo structural changes leading to exposing normally buried sequences. D-domain has more contribution in this interaction and the C-terminus of γ chain (γ377-394), located in D-domain, showed the highest level of exposure compared to other sequences/residues.