Research Outputs
Evidence of synergy effects between zinc and copper oxides with acidic sites on natural zeolite during photocatalytic oxidation of ethylene using operando DRIFTS studies
In this article, the role of surface sites of modified zeolites with semiconductor nanoparticles as alternative photocatalyts for protecting post-harvest foodstuff from the detrimental effects of ethylene is addressed. Two single and one double catalyst based on zinc and copper oxides supported over modified zeolite samples were prepared. Physical, chemical, and surface properties of prepared materials were studied by several characterization methods. UV-Vis absorption spectra show that the applied modification procedures increase the optical absorption of light in the UV and visible regions, suggesting that an increase in the photocatalytic activity could take place mainly in the obtained co-impregnated catalyst. An ethylene conversion around 50% was achieved when the parent natural zeolite support was modified with both transition metal oxides, obtaining higher removal efficiency in comparison to single oxide catalysts. Adsorption and photocatalytic oxidation experiments were also performed using single and double catalysts supported over fumed silica, attaining lower ethylene conversion and thus highlighting the role of zeolite surfaces as adsorption sites for ethylene during photocatalytic reactions. Operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies reveal that a synergistic mechanism occurs, involving ethylene adsorption at acidic sites of zeolite and its photocatalytic oxidation due to the generation of radicals by the light activation of nanoparticles of zinc and copper oxides.
Adsorption of a cationic dye from aqueous solution using low-cost Moroccan diatomite: adsorption equilibrium, kinetic and thermodynamic studies
This article presents the adsorption of Methylene Blue (MB) onto diatomite, in order to develop a low-cost treatment technology as a process alternative for dye removal. Diatomite used in this work was taken from the Nador area in the northeast of Morocco. Diatomite is characterised by different physical–chemical methods (X-ray diffraction, nitrogen adsorption-desorption isotherm, scanning electron microscopy and Fourier transform infrared). Results showed that the adsorption of MB onto diatomite mineral is affected by various operating parameters like contact time, initial dye concentration, adsorbent dosage, pH and temperature. Adsorption equilibrium is reached after 1.5 h of contact time. Maximum MB removal is obtained at pH = 12. MB removal rate decreases as pH decreases. Adsorption equilibrium data are fitted to Langmuir, Freundlich, Redlich–Peterson and Toth models. Adsorption data are well described by Langmuir isotherm model indicating that a homogeneous adsorption occurs. A maximum adsorption capacity (or monolayer coverage) of 11 mg g–1 is obtained at 45°C. A value of the enthalpy of adsorption of 12.78 kJ mol–1 is found confirming the endothermic nature of adsorption process, while a Gibb’s free energy change (∆G°) falling in the range −30.8 to −35.34 kJ mol–1 confirms the spontaneity of the process. Adsorption kinetics are fitted to a pseudo-second-order kinetic model. Experimental results indicate that the Moroccan diatomite could be used as a potential adsorbent for the removal of cationic dye molecules, at lower cost.
Ethylene elimination using activated carbons obtained from Baru (Dipteryx alata vog.) waste and impregnated with copper oxide
Ethylene is a plant hormone regulator that stimulates chlorophyll loss and promotes softening and aging, resulting in a deterioration and reduction in the post-harvest life of fruit. Commercial activated carbons have been used as ethylene scavengers during the storage and transportation of a great variety of agricultural commodities. In this work, the effect of the incorporation of copper oxide over activated carbons obtained from baru waste was assessed. Samples were characterized by X-ray diffraction (XRD), N2 adsorption-desorption at −196 °C, field-emission scanning electron microscopy (FESEM) coupled with energy-dispersive X-ray spectroscopy (EDS), and infrared (IR) spectroscopy. The results showed that the amount of ethylene removed using activated carbon obtained from baru waste and impregnated with copper oxide (1667 μg g−1) was significantly increased in comparison to the raw activated carbon (1111 μg g−1). In addition, carbon impregnated with copper oxide exhibited better adsorption performance at a low ethylene concentration. Activated carbons produced from baru waste are promising candidates to be used as adsorbents in the elimination of ethylene during the storage and transportation of agricultural commodities at a lower cost.
Use of combination of coagulation and adsorption process for the landfill leachate treatment from Casablanca city
This article presents a combination of coagulation–flocculation and powder activated carbon (PAC) adsorption as a treatment process for landfill leachate. Leachates were collected from a municipal solid waste landfill in Mediouna site, Casablanca city. Ferric chloride (FeCl3) is used here as a coagulant to study the optimum conditions for the removal of chemical oxygen demand (COD), colour, total suspended solids (TSS) and turbidity in jar tests. This coagulant showed the highest removal efficiency in terms of COD (62.5%), turbidity (92.5%), colour (80%) and least sludge volume generation (30% v/v) for an optimum coagulant dose of 12 g Fe3+ L–1. Combining coagulation with adsorption process onto PAC enhances the removal of COD, turbidity and colour reduction by a 77%, a 99% and a 99.7%, respectively. These results show that coagulation-adsorption could be used as a promising hybrid process for the treatment of landfill leachates.
Toluene, Methanol and Benzaldehyde removal from gas streams by adsorption onto natural clay and Faujasite-Y type Zeolite
A great number of pollution problems come as a result of the emission of Volatile Organic Compounds (VOCs) into the environment and their control becomes a serious challenge for the global chemical industry. Adsorption is a widely used technique for the removal of VOCs due to its high efficiency, low cost, and convenient operation. In this study, the feasibility to use a locally available clay, as adsorbent material to control VOCs emissions is evaluated. Natural clay is characterised by different physical-chemical methods and adsorptive interaction features between VOCs and natural clay are identified. Toluene (T), methanol (M) and benzaldehyde (B) are used here as representatives of three different kinds of VOCs. Adsorption isotherms onto natural clay and faujasite-Y type zeolite (Fau Y) are obtained at room temperature. According to Langmuir model data, maximum adsorption capacities (qm) of Fez natural clay and zeolite toward methanol (M), toluene (T) and benzaldehyde (B) at 300 K are 8, 0.89 and 3.1 mmol g–1, and 15, 1.91 and 13.9 mmol g–1 respectively. In addition, the effect of temperature on the adsorption of toluene onto natural clay is evaluated in the range from 300 to 323K. An increase on temperature reduces the adsorption capacity of natural clay toward toluene, indicating that an exothermic physical adsorption process takes place. The enthalpy of adsorption of toluene onto Fez natural clay was found to be –54 kJ mol–1. A preliminary cost analysis shows that natural clay could be used as an alternative low cost adsorbent in the control of VOCs from contaminated gas streams with a cost of US$ 0.02 kg–1 compared to Fau Y zeolite with US$ 10 kg–1.
Use of a copper- and zinc-modified natural zeolite to improve ethylene removal and postharvest quality of tomato fruit
Ethylene stimulates ripening and senescence by promoting chlorophyll loss, red pigment synthesis, and softening of tomatoes and diminishes their shelf-life. The aim of this work was to study the performance of a novel copper- and zinc-based ethylene scavenger supported by ion-exchange on a naturally occurring zeolite by analyzing its ethylene adsorption capacity and the influence of ethylene scavenging on quality attributes during the postharvest life of tomatoes. The influence of copper- and zinc-modified zeolites on ethylene and carbon dioxide concentrations and postharvest quality of tomatoes was compared with unmodified zeolite. Interactions among ethylene molecules and zeolite surface were studied by diffuse reflectance infrared Fourier transform spectroscopy in operando mode. The percentage of ethylene removal after eight days of storage was 57% and 37% for the modified zeolite and pristine zeolite, respectively. The major ethylene increase appeared at 9.5 days for the modified zeolite treatment. Additionally, modified zeolite delayed carbon dioxide formation by six days. Zeolite modified with copper and zinc cations favors ethylene removal and delays tomato fruit ripening. However, the single use of unmodified zeolite should be reconsidered due to its ripening promoting effects in tomatoes at high moisture storage conditions, as water molecules block active sites for ethylene adsorption.
Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination
In this study, a hydrophobic synthetic zeolite, namely ZSM-5 is chosen as an adsorbent/ catalyst for toluene removal. Experimental results showed that toluene adsorption onto ZSM-5 was favourable, following a Langmuir adsorption isotherm model. ZSM-5 zeolite was regenerated using gaseous ozone at low temperature. Adsorbed toluene was oxidised, releasing mainly CO2 and H2O. Traces of oxidation by-products such as acetic acid and acetaldehyde were formed and remained adsorbed after the oxidativate regeneration with ozone. After four successive cycles of adsorption/ozonation, the adsorption efficiency was not affected (92%–99%). These results showed that volatile organic compound (VOC) removal by adsorption onto ZSM-5 zeolite followed by ozone regeneration could be used as a promising hybrid process for the control of VOC emissions in terms of efficiency.
Removal of basic and acid dyes from aqueous solutions using cone powder from Moroccan cypress Cupressus sempervirens as a natural adsorbent
This study aims to evaluate the technical feasibility of applying a low-cost alternative natural bioadsorbent obtained from the cone of the Moroccan cypress Cupressus sempervirens to remove dyes from contaminated waters. Methylene Blue (MB) and Congo Red (CR) dyes are used to represent basic and acid compounds present in wastewater of textile industries. The cone of this medium-sized coniferous evergreen tree was obtained from the Fez area and was characterised by different physical– chemical methods, including nitrogen adsorption–desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy, Boehm titration method and the pH of the point of zero charge (pHpzc). Additionally, the influence of operating conditions such as contact time, initial dye concentration, binary mixture of dye solutions, bioadsorbent dosages and solution pH were evaluated. Experimental results reveal that the adsorption processes take place very rapidly, reaching equilibrium at 30 and 45 min for MB and CR, respectively. Maximum adsorption capacities result to be pH dependents. Hence, MB adsorption is favoured under basic pH conditions, while CR is favoured at acidic pH. A pseudo-second-order kinetic model provides the best fit of the experimental data of MB and CR adsorption onto the biomaterial. Adsorption isotherm data are well represented by Langmuir, Freundlich and Dubinin–Radushkevich models. Langmuir model gives the best fit with a maximum monolayer sorption capacity of 144 and 25.02 mg g–1 for MB and CR, respectively. Experimental results indicate that the cone of Cupressus sempervirens could be used as a potential, low-cost bioadsorbent for the elimination of dyes from contaminated waters.
Ethylene adsorption onto natural and transition metal modified Chilean zeolite: An operando DRIFTS approach
Ethylene is a plant growth regulator that induces accelerated softening and ripening of fruits during transport and storage. Among the most applied methods for ethylene control, adsorption appears as a cheap and efficient technique. In this work, the effect of the incorporation of transition metals into natural Chilean zeolite on ethylene adsorption is investigated. Natural zeolite mainly composed of clinoptilotite and mordenite is modified using copper and zinc nitrate solutions and calcined under oxygen flow at 623 K, generating different transition metal modified zeolites. Parent and modified zeolites were characterised by X-ray diffraction, X-ray fluorescence spectroscopy and nitrogen adsorption. Zeolite surface modifications were assessed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Experimental results reveal the incorporation of Cu2+ and Zn(2+ )as new compensating cations into the zeolite framework. Ethylene adsorption isotherms show an enhancement on the adsorption capacity of Cu-exchanged zeolite. This result is not only associated to the higher micropore surface area of this sample, but also to the higher affinity of ethylene molecules to copper cations incorporated on this zeolite. DRIFTS operando experiments of ethylene adsorption in the absence and in the presence of moisture reveal a competitive mechanism of water and ethylene molecules toward hydroxyl sites. Si-OH-Al and Si-OH sites are rapidly occupied with water, reducing the adsorption of ethylene.