Sustainable Hydrogel Nanocomposites Based on Grafted Chitosan and Clay for Effective Adsorption of Cationic Dye

Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (qm) was found to increase from 2173 mg g−1 until 2221 mg g−1 by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.

First and Second Analysis on the Reheat Organic Rankine Cycle

In recent years the increasing use of fossil fuels has led to various environmental problems including urban pollution, ozone layer depletion and acid rains. Moreover, with the increased number of industrial centers and higher consumption of these fuels, the end point of the fossil energy reserves has become more evident. Considering the environmental pollution caused by fossil fuels and their limited availability, renewable sources can be considered as the main substitute for non-renewable resources. One of these resources is the Organic Rankine Cycles (ORCs). These cycles while having high safety, have low maintenance requirements. Combining the ORCs with other systems, such as ejector and reheater will increase overall cycle efficiency. In this study, ejector and reheater are used to improve the thermal efficiency (ηth), exergy efficiency (η_ex) and net output power (w_net); therefore, the ORCs with reheater (RORCs) are proposed. A computational program has been developed to calculate the thermodynamic parameters required in Engineering Equations Solver (EES). In this program, the analysis of the first and second law in RORC is conducted, and a comparison is made between them and the ORCs with Ejector (EORC). R245fa is selected as the working fluid and water is chosen as low temperature heat source with a temperature of 95 °C and a mass transfer rate of 1 kg/s. The pressures of the second evaporator and reheater are optimized in terms of maximum exergy efficiency. The environment is at 298.15 k and at 101.325 kpa. The results indicate that the thermodynamic parameters in the RORC have improved compared to EORC.

Biosorption of Azo Dye Reactive Black B onto Nonviable Biomass of Cladosporium cladosporioides LM1: Thermodynamic, Kinetic and Equilibrium Modeling

This study investigated the biosorption of the azo dye reactive Black B (RBB) from aqueous solution using the nonviable biomass of Cladosporium cladosporioides LM1. The biosorption systems were carried out in batch mode considering different conditions of initial pH, contact time, temperature, initial dye concentration and biosorbent dosage. Higher removal rate of RBB was obtained at pH 2. Biosorption data were successfully described by pseudo-second-order kinetic model and Langmuir isotherm model with the maximum monolayer biosorption capacity estimated at 71.43 mg/g. The values of thermodynamic parameters such as ∆G°, ∆H° and ∆S° indicated that the biosorption of RBB onto fungal biomass was spontaneous and exothermic in nature. It can be concluded that nonviable biomass of Cladosporium cladosporioides LM1 may be an attractive low-cost biosorbent for the removal of azo dye RBB from aqueous solution.

Malt Bagasse Waste as Biosorbent for Malachite Green: An Ecofriendly Approach for Dye Removal from Aqueous Solution

In this study, malt bagasse, a low-cost waste biomass, was tested as a biosorbent to remove the cationic dye Malachite green (MG) from aqueous solution. Batch biosorption experiments were investigated as functions of different experimental parameters such as initial pH, salt (NaCl) concentration, contact time, temperature and initial dye concentration. Higher removal rates of MG were obtained at pH 8 and 10. The equilibrium and kinetic studies suggest that the biosorption follows Langmuir isotherm and the pseudo-second-order model. The maximum monolayer adsorption capacity was estimated at 117.65 mg/g (at 45 °C). According to Dubinin–Radushkevich (D-R) isotherm model, biosorption of MG onto malt bagasse occurs physically. The thermodynamic parameters such as Gibbs free energy, enthalpy and entropy indicated that the MG biosorption onto malt bagasse is spontaneous and endothermic. The results of the ionic strength effect indicated that the biosorption process under study had a strong tolerance under high salt concentrations. It can be concluded that malt bagasse waste has potential for application as biosorbent for removal of MG from aqueous solution.

Kinetics and Thermodynamics Adsorption of Phenolic Compounds on Organic-Inorganic Hybrid Mesoporous Material

Mesoporous materials are very commonly used as adsorbent materials for removing phenolic compounds. However, the adsorption mechanism of these compounds is still poorly controlled. However, understanding the interactions mesoporous materials/adsorbed molecules is very important in order to optimize the processes of liquid phase adsorption. The difficulty of synthesis is to keep an orderly and cubic pore structure and achieve a homogeneous surface modification. The grafting of Si(CH3)3 was chosen, to transform hydrophilic surfaces hydrophobic surfaces. The aim of this work is to study the kinetics and thermodynamics of two volatile organic compounds VOC phenol (PhOH) and P hydroxy benzoic acid (4AHB) on a mesoporous material of type MCM-48 grafted with an organosilane of the Trimethylchlorosilane (TMCS) type, the material thus grafted or functionalized (hereinafter referred to as MCM-48-G). In a first step, the kinetic and thermodynamic study of the adsorption isotherms of each of the VOCs in mono-solution was carried out. In a second step, a similar study was carried out on a mixture of these two compounds. Kinetic models (pseudo-first order, pseudo-second order) were used to determine kinetic adsorption parameters. The thermodynamic parameters of the adsorption isotherms were determined by the adsorption models (Langmuir, Freundlich). The comparative study of adsorption of PhOH and 4AHB proved that MCM-48-G had a high adsorption capacity for PhOH and 4AHB; this may be related to the hydrophobicity created by the organic function of TMCS in MCM-48-G. The adsorption results for the two compounds using the Freundlich and Langmuir models show that the adsorption of 4AHB was higher than PhOH. The values ​​obtained by the adsorption thermodynamics show that the adsorption interactions for our sample with the phenol and 4AHB are of a physical nature. The adsorption of our VOCs on the MCM-48 (G) is a spontaneous and exothermic process.

Voyage Analysis of a Marine Gas Turbine Engine Installed to Power and Propel an Ocean-Going Cruise Ship

A gas turbine-powered cruise Liner is scheduled to transport pilgrim passengers from Lagos-Nigeria to the Islamic port city of Jeddah in Saudi Arabia. Since the gas turbine is an air breathing machine, changes in the density and/or mass flow at the compressor inlet due to an encounter with variations in weather conditions induce negative effects on the performance of the power plant during the voyage. In practice, all deviations from the reference atmospheric conditions of 15 oC and 1.103 bar tend to affect the power output and other thermodynamic parameters of the gas turbine cycle. Therefore, this paper seeks to evaluate how a simple cycle marine gas turbine power plant would react under a variety of scenarios that may be encountered during a voyage as the ship sails across the Atlantic Ocean and the Mediterranean Sea before arriving at its designated port of discharge. It is also an assessment that focuses on the effect of varying aerodynamic and hydrodynamic conditions which deteriorate the efficient operation of the propulsion system due to an increase in resistance that results from some projected levels of the ship hull fouling. The investigated passenger ship is designed to run at a service speed of 22 knots and cover a distance of 5787 nautical miles. The performance evaluation consists of three separate voyages that cover a variety of weather conditions in winter, spring and summer seasons. Real-time daily temperatures and the sea states for the selected transit route were obtained and used to simulate the voyage under the aforementioned operating conditions. Changes in engine firing temperature, power output as well as the total fuel consumed per voyage including other performance variables were separately predicted under both calm and adverse weather conditions. The collated data were obtained online from the UK Meteorological Office as well as the UK Hydrographic Office websites, while adopting the Beaufort scale for determining the magnitude of sea waves resulting from rough weather situations. The simulation of the gas turbine performance and voyage analysis was effected through the use of an integrated Cranfield-University-developed computer code known as ‘Turbomatch’ and ‘Poseidon’. It is a project that is aimed at developing a method for predicting the off design behavior of the marine gas turbine when installed and operated as the main prime mover for both propulsion and powering of all other auxiliary services onboard a passenger cruise liner. Furthermore, it is a techno-economic and environmental assessment that seeks to enable the forecast of the marine gas turbine part and full load performance as it relates to the fuel requirement for a complete voyage.

Equilibrium, Kinetic and Thermodynamic Studies of the Biosorption of Textile Dye (Yellow Bemacid) onto Brahea edulis

Environmental contamination is a major problem being faced by the society today. Industrial, agricultural, and domestic wastes, due to the rapid development in the technology, are discharged in the several receivers. Generally, this discharge is directed to the nearest water sources such as rivers, lakes, and seas. While the rates of development and waste production are not likely to diminish, efforts to control and dispose of wastes are appropriately rising. Wastewaters from textile industries represent a serious problem all over the world. They contain different types of synthetic dyes which are known to be a major source of environmental pollution in terms of both the volume of dye discharged and the effluent composition. From an environmental point of view, the removal of synthetic dyes is of great concern. Among several chemical and physical methods, adsorption is a promising technique due to the ease of use and low cost compared to other applications in the process of discoloration, especially if the adsorbent is inexpensive and readily available. The focus of the present study was to assess the potentiality of Brahea edulis (BE) for the removal of synthetic dye Yellow bemacid (YB) from aqueous solutions. The results obtained here may transfer to other dyes with a similar chemical structure. Biosorption studies were carried out under various parameters such as mass adsorbent particle, pH, contact time, initial dye concentration, and temperature. The biosorption kinetic data of the material (BE) was tested by the pseudo first-order and the pseudo-second-order kinetic models. Thermodynamic parameters including the Gibbs free energy ΔG, enthalpy ΔH, and entropy ΔS have revealed that the adsorption of YB on the BE is feasible, spontaneous, and endothermic. The equilibrium data were analyzed by using Langmuir, Freundlich, Elovich, and Temkin isotherm models. The experimental results show that the percentage of biosorption increases with an increase in the biosorbent mass (0.25 g: 12 mg/g; 1.5 g: 47.44 mg/g). The maximum biosorption occurred at around pH value of 2 for the YB. The equilibrium uptake was increased with an increase in the initial dye concentration in solution (Co = 120 mg/l; q = 35.97 mg/g). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The best fit was obtained by the Langmuir model with high correlation coefficient (R2 > 0.998) and a maximum monolayer adsorption capacity of 35.97 mg/g for YB.

Kinetic, Thermodynamic and Process Modeling of Synthesis of UV Curable Glyceryl and Neopentyl Glycol Acrylates

Curing of paints by exposure to UV radiations is emerging as one of the best film forming technique as an alternative to traditional solvent borne oxidative and thermal curing coatings. The composition and chemistry of UV curable coatings and role of multifunctional and monofunctional monomers, oligomers, and photoinitiators have been discussed. The limitations imposed by thermodynamic equilibrium and tendency for acrylic double bond polymerizations during synthesis of multifunctional acrylates have been presented. Aim of present investigation was thus to explore the reaction variables associated with synthesis of multifunctional acrylates. Zirconium oxychloride was evaluated as catalyst against regular acid functional catalyst. The catalyzed synthesis of glyceryl acrylate and neopentyl glycol acrylate was conducted by variation of following reaction parameters: two different reactant molar ratios- 1:4 and 1:6; catalyst usage in % by moles on polyol- 2.5, 5.0 and 7.5 and two different reaction temperatures- 45 and 75 0C. The reaction was monitored by determination of acid value and hydroxy value at regular intervals, besides TLC, HPLC, and FTIR analysis of intermediates and products. On the basis of determination of reaction progress over 1-60 hrs, the esterification reaction was observed to follow 2nd order kinetics with rate constant varying from 1*10-4 to 7*10-4. The thermal and catalytic components of second order rate constant and energy of activation were also determined. Uses of these kinetic and thermodynamic parameters in design of reactor for manufacture of multifunctional acrylate ester have been presented. The synthesized multifunctional acrylates were used to formulate and apply UV curable clear coat followed by determination of curing characteristics and mechanical properties of cured film. The overall curing rates less than 05 min. were easily attained indicating economical viability of radiation curable system due to faster production schedules

Adsorption of Crystal Violet onto BTEA- and CTMA-bentonite from Aqueous Solutions

CTMA-bentonite and BTEA-Bentonite prepared by Na-bentonite cation exchanged with cetyltrimethylammonium(CTMA) and benzyltriethylammonium (BTEA). Products were characterized by XRD and IR techniques.The d001 spacing value of CTMA-bentonite and BTEA-bentonite are 7.54Å and 3.50Å larger than that of Na-bentonite at 100% cation exchange capacity, respectively. The IR spectrum showed that the intensities of OH stretching and bending vibrations of the two organoclays decreased greatly comparing to untreated Na-bentonite. Batch experiments were carried out at 303 K, 318 K and 333 K to obtain the sorption isotherms of Crystal violet onto the two organoclays. The results show that the sorption isothermal data could be well described by Freundlich model. The dynamical data for the two organoclays fit well with pseudo-second-order kinetic model. The adsorption capacity of CTMA-bentonite was found higher than that of BTEA-Bentonite. Thermodynamic parameters such as changes in the free energy (ΔG°), the enthalpy (ΔH°) and the entropy (ΔS°) were also evaluated. The overall adsorption process of Crystal violet onto the two organoclays were spontaneous, endothermic physisorption. The CTMA-bentonite and BTEA-Bentonite could be employed as low-cost alternatives to activated carbon in wastewater treatment for the removal of color which comes from textile dyes.

Removal of Copper (II) from Aqueous Solutions Using Teak (Tectona grandis L.f) Leaves

The experiments were performed in a batch set up under different concentrations of Cu (II) (0.2 g.l-1 to 0.9 g.l-1), pH (4- 6), temperatures (20oC – 40oC) with varying teak leaves powder (as biosorbent) dosage of 0.3 g.l-1 to 0.5 g.l-1. The kinetics of interactions were tested with pseudo first order Lagergran equation and the value for k1 was found to be 6.909 x 10-3 min-1. The biosorption data gave a good fit with Langmuir and Fruendlich isotherms and the Langmuir monolayer capacity (qm) was found to be 166.78 mg. g-1. Similarly the Freundlich adsorption capacity (Kf) was estimated as 2.49 l g-1. The mean values of the thermodynamic parameters ΔH, ΔS, and ΔG were -62.42 KJ. mol-1, -0.219 KJ.mol-1 K-1 and -1.747 KJ.mol-1 at 293 K from a solution containing 0.4 g l-1 of Cu(II) showing the biosorption to be thermodynamically favourable. These results show good potentiality of using teak leaves as a biosorbent for the removal of Cu(II) from aqueous solutions.

Thermodynamic Study for Aggregation Behavior of Hydrotropic Solution

Aggregation behavior of sodium salicylate and sodium cumene sulfonate was studied in aqueous solution at different temperature. Specific conductivity and relative viscosity were measured at different temperature to find minimum hydrotropic concentration. The thermodynamic parameters (free energy, enthalpy and entropy) were evaluated in the temperature range of 30°C-70°C. The free energy decreased with increase in temperature. The aggregation was found to be exothermic in nature and favored by positive value of entropy.

Thermodynamic Optimization of Turboshaft Engine using Multi-Objective Genetic Algorithm

In this paper multi-objective genetic algorithms are employed for Pareto approach optimization of ideal Turboshaft engines. In the multi-objective optimization a number of conflicting objective functions are to be optimized simultaneously. The important objective functions that have been considered for optimization are specific thrust (F/m& 0), specific fuel consumption ( P S ), output shaft power 0 (& /&) shaft W m and overall efficiency( ) O η . These objectives are usually conflicting with each other. The design variables consist of thermodynamic parameters (compressor pressure ratio, turbine temperature ratio and Mach number). At the first stage single objective optimization has been investigated and the method of NSGA-II has been used for multiobjective optimization. Optimization procedures are performed for two and four objective functions and the results are compared for ideal Turboshaft engine. In order to investigate the optimal thermodynamic behavior of two objectives, different set, each including two objectives of output parameters, are considered individually. For each set Pareto front are depicted. The sets of selected decision variables based on this Pareto front, will cause the best possible combination of corresponding objective functions. There is no superiority for the points on the Pareto front figure, but they are superior to any other point. In the case of four objective optimization the results are given in tables.

Recycling Poultry Feathers for Pb Removal from Wastewater: Kinetic and Equilibrium Studies

Chicken feathers were used as biosorbent for Pb removal from aqueous solution. In this paper, the kinetics and equilibrium studies at several pH, temperature, and metal concentration values are reported. For tested conditions, the Pb sorption capacity of this poultry waste ranged from 0.8 to 8.3 mg/g. Optimal conditions for Pb removal by chicken feathers have been identified. Pseudo-first order and pseudo-second order equations were used to analyze the experimental data. In addition, the sorption isotherms were fitted to classical Langmuir and Freundlich models. Finally, thermodynamic parameters for the sorption process have been determined. In summary, the results showed that chicken feathers are an alternative and promising sorbent for the treatment of effluents polluted by Pb ions.

Multi-Objective Optimization of Gas Turbine Power Cycle

Because of importance of energy, optimization of power generation systems is necessary. Gas turbine cycles are suitable manner for fast power generation, but their efficiency is partly low. In order to achieving higher efficiencies, some propositions are preferred such as recovery of heat from exhaust gases in a regenerator, utilization of intercooler in a multistage compressor, steam injection to combustion chamber and etc. However thermodynamic optimization of gas turbine cycle, even with above components, is necessary. In this article multi-objective genetic algorithms are employed for Pareto approach optimization of Regenerative-Intercooling-Gas Turbine (RIGT) cycle. In the multiobjective optimization a number of conflicting objective functions are to be optimized simultaneously. The important objective functions that have been considered for optimization are entropy generation of RIGT cycle (Ns) derives using Exergy Analysis and Gouy-Stodola theorem, thermal efficiency and the net output power of RIGT Cycle. These objectives are usually conflicting with each other. The design variables consist of thermodynamic parameters such as compressor pressure ratio (Rp), excess air in combustion (EA), turbine inlet temperature (TIT) and inlet air temperature (T0). At the first stage single objective optimization has been investigated and the method of Non-dominated Sorting Genetic Algorithm (NSGA-II) has been used for multi-objective optimization. Optimization procedures are performed for two and three objective functions and the results are compared for RIGT Cycle. In order to investigate the optimal thermodynamic behavior of two objectives, different set, each including two objectives of output parameters, are considered individually. For each set Pareto front are depicted. The sets of selected decision variables based on this Pareto front, will cause the best possible combination of corresponding objective functions. There is no superiority for the points on the Pareto front figure, but they are superior to any other point. In the case of three objective optimization the results are given in tables.

The Removal of Cu (II) Ions from Aqueous Solutions on Synthetic Zeolite NaA

In this study the adsorption of Cu (II) ions from aqueous solutions on synthetic zeolite NaA was evaluated. The effect of solution temperature and the determination of the kinetic parameters of adsorption of Cu(II) from aqueous solution on zeolite NaA is important in understanding the adsorption mechanism. Variables of the system include adsorption time, temperature (293- 328K), initial solution concentration and pH for the system. The sorption kinetics of the copper ions were found to be strongly dependent on pH (the optimum pH 3-5), solute ion concentration and temperature (293 – 328 K). It was found, the pseudo-second-order model was the best choice among all the kinetic models to describe the adsorption behavior of Cu(II) onto ziolite NaA, suggesting that the adsorption mechanism might be a chemisorptions process The activation energy of adsorption (Ea) was determined as Cu(II) 13.5 kJ mol-1. The low value of Ea shows that Cu(II) adsorption process by zeolite NaA may be an activated chemical adsorption. The thermodynamic parameters (ΔG0, ΔH0, and ΔS0) were also determined from the temperature dependence. The results show that the process of adsorption Cu(II) is spontaneous and endothermic process and rise in temperature favors the adsorption.

A Study on Removal of Toluidine Blue Dye from Aqueous Solution by Adsorption onto Neem Leaf Powder

Adsorption of Toluidine blue dye from aqueous solutions onto Neem Leaf Powder (NLP) has been investigated. The surface characterization of this natural material was examined by Particle size analysis, Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy and X-Ray Diffraction (XRD). The effects of process parameters such as initial concentration, pH, temperature and contact duration on the adsorption capacities have been evaluated, in which pH has been found to be most effective parameter among all. The data were analyzed using the Langmuir and Freundlich for explaining the equilibrium characteristics of adsorption. And kinetic models like pseudo first- order, second-order model and Elovich equation were utilized to describe the kinetic data. The experimental data were well fitted with Langmuir adsorption isotherm model and pseudo second order kinetic model. The thermodynamic parameters, such as Free energy of adsorption (AG"), enthalpy change (AH') and entropy change (AS°) were also determined and evaluated.

Removal of Cibacron Brilliant Yellow 3G-P Dye from Aqueous Solutions Using Coffee Husks as Non-Conventional Low-Cost Sorbent

The purpose of this research is to establish the experimental conditions for removal of Cibacron Brilliant Yellow 3G-P dye (CBY) from aqueous solutions by sorption onto coffee husks as a low-cost sorbent. The effects of various experimental parameters (e.g. initial CBY dye concentration, sorbent mass, pH, temperature) were examined and the optimal experimental conditions were determined. The results indicated that the removal of the dye was pH dependent and at initial pH of 2, the dye was removed effectively. The CBY dye sorption data were fitted to Langmuir, Freundlich, Temkin and Dubinin-Radushkevich equilibrium models. The maximum sorption capacity of CBY dye ions onto coffee husks increased from 24.04 to 35.04 mg g-1 when the temperature was increased from 293 to 313 K. The calculated sorption thermodynamic parameters including ΔG°, ΔH°, and ΔS° indicated that the CBY dye sorption onto coffee husks is a spontaneous, endothermic and mainly physical in nature.

Equilibrium, Kinetic and Thermodynamic Studies on Biosorption of Cd (II) and Pb (II) from Aqueous Solution Using a Spore Forming Bacillus Isolated from Wastewater of a Leather Factory

The equilibrium, thermodynamics and kinetics of the biosorption of Cd (II) and Pb(II) by a Spore Forming Bacillus (MGL 75) were investigated at different experimental conditions. The Langmuir and Freundlich, and Dubinin-Radushkevich (D-R) equilibrium adsorption models were applied to describe the biosorption of the metal ions by MGL 75 biomass. The Langmuir model fitted the equilibrium data better than the other models. Maximum adsorption capacities q max for lead (II) and cadmium (II) were found equal to 158.73mg/g and 91.74 mg/g by Langmuir model. The values of the mean free energy determined with the D-R equation showed that adsorption process is a physiosorption process. The thermodynamic parameters Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were also calculated, and the values indicated that the biosorption process was exothermic and spontaneous. Experiment data were also used to study biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. Kinetic parameters, rate constants, equilibrium sorption capacities and related correlation coefficients were calculated and discussed. The results showed that the biosorption processes of both metal ions followed well pseudo-second-order kinetics.