High-purity alkaline lignin extraction from Saccharum ravannae and optimization of lignin recovery through response surface methodology.

Saccharum ravannae, known as "Ekra" in the Northeast region of India, is an elephant grass species that abundantly grows in the natural habitat of Assam. This study aims to utilize this wild grass species and extract alkaline lignin of high purity through KOH-mediated alkaline hydrothermal pretreatment using the Oil bath process. Lignin recovery was optimized using RSM (response surface methodology) combined with a central composite model. Three process parameters, namely KOH concentration (1-3 %), reaction time (50-200 min), and solid loading (5-15 %), varied to optimize the combined effect of these parameters. RSM predicted a maximum lignin recovery of 15.38 g/100 g of raw biomass at optimum conditions (2.4 % KOH, 6.41 % solid loading, 176.57 min). Three experimental runs were performed at optimum conditions, and 15.81 ± 0.32 g/100 g lignin recovery was obtained, thus verifying the predicted result. Maximum 93.7 % purity of extracted lignin was achieved in a different operating condition (3 % KOH, 10 % solid loading, 125 min). The commercial and extracted alkaline lignin with maximum purity was characterized by Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The extracted lignin shows higher phenolic content and more functional groups than commercial lignin and can be used for future applications.

Promising integrated technique for the treatment of highly saline nanofiltration rejected stream of steel industry.

This work presents a novel concept for the integration of closed-circuit reverse osmosis (CCRO) technology and solvent-based precipitation as a means of producing an exceptional quality of water by separating the salts especially chlorides and sulphates from highly saline nanofiltration (NF) rejected stream of the steel industry. The NF rejected stream was extremely concentrated with salts like chloride (1560 mg/L), sulphate (4212 mg/L), manganese (28 mg/L), sodium (418 mg/L) and total dissolved solids (TDS), as high as 8100 mg/L, which are well above the permissible limit for surface discharge. The outcome of this work showed that reverse osmosis (RO) with continuous brine recycling achieved excellent desalination performance. Miscible organic solvents such as diisopropylamine (DIIPA), isopropylamine (IPA), and ethylamine (EA) were found to be effective in precipitating chloride and sulphate ions from highly concentrated RO brine. The overall removal efficiency of sulphate and chloride was found to be 99.88% and 91%, respectively. Preliminary treatment cost was estimated and found to be around 7.35 $/m3. The treated water can either be recycled in the system or safely released into the environment. The readers of this research article will be benefitted by gaining a thorough understanding of the treatment of concentrated brine from nanofiltration using an integrated RO-precipitation technique.

Integrated ozonation assisted electrocoagulation process for the removal of cyanide from steel industry wastewater.

This work focuses on the removal of cyanide, chemical oxygen demand (COD), biological oxygen demand (BOD), and chloride from biological oxidation treated (BOT) effluent of the steel industry by integrated ozonation assisted electrocoagulation method. The removal efficiency of the pollutants was found to be inefficient when the electrocoagulation or ozonation process was performed separately. However, a combination of ozonation and electrocoagulation gives a highly satisfactory result. Such an integrated approach for the treatment of BOT effluent has not been previously investigated. The effects of operating variables viz. ozone generation rate, current density, and analysis time on pollutant removal were primarily analyzed for the hybrid process. The experimental operating condition was optimized and was seen that ozone generation rate of 1.33 mg s-1, ozonation time of 40 min, a current density of 100 A m-2, and electrolysis time of 30 min were sufficient for reducing the pollutant concentration below its permissible limits. The removal efficiencies of the combined process at optimum conditions were 99.8%, 94.7%, 95%, and 46.5% for cyanide, COD, BOD, and chloride ions, respectively. A kinetic study was performed for the degradation of the pollutants during ozonation. The pseudo-first-order kinetic model was found to be best suited for the analysis with the highest R2 value of 0.99 for cyanide, COD, BOD, and chloride, respectively. The mass transfer study conducted further showed that the volumetric mass transfer coefficient, Kla, was increased with that of the ozone generation rate. Cost estimation of the hybrid process was done and compared with that of the other reported integrated process.

Fabrication of ultrasound-mediated tunable graphene oxide nanoscrolls.

In this work, a cost-effective and facile method was adopted for the fabrication of graphene oxide nanoscrolls (GONS) by low frequency (20 kHz) ultrasonication with tunable dimensions. The graphene oxide (GO) was synthesized by modified Hummer's method using synthetic graphite as a base material. Later, GO suspension (0.05 g L-1) were made using methanol as solvent and subjected to different ultrasonication conditions. It was found that GO sheets curls themselves into nanoscrolls by overcoming the energy barrier for scrolling with the help of bubble cavitation energy provided by ultrasonication. Also, the effect of ultrasonication power (100-150 W) for irradiation time (0.5-3 h) over the GONS dimensions were investigated. The spiral wounded GONS structures were shown using electron microscopy. Raman Spectroscopy, Thin-film X-Ray Diffraction, Energy Dispersive X-Ray, FT Infrared Spectroscopic analysis were also done to endorse GONS formation. Factors affecting GONS formation such as sonication power and solvent selection were studied as scrolling of GO sheets are strongly dependent on sonication parameters and solvent characteristics. It was found that GONS length varies inversely with irradiation time for identical power density. Also, a solvent with relatively large Hansen solubility parameter, lower dipole movement and less negative value of zeta potential support GONS formation of longer length. Raman analysis overlays the rapid oxygen-defect site cleavage mechanism. The obtained GONS unlocks further developments in various engineering applications like adsorption, drug delivery and filtration membrane.

Utilization of LD slag from steel industry for the preparation of MF membrane.

This work is focused on utilizing the solid waste generated from steel industry for the fabrication of porous ceramic membrane from Linz Donawitz (LD) slag. Membranes were fabricated using uniaxial method sintered at three different temperatures like 650 °C, 850 °C and 950 °C. Membranes fabricated with raw LD slag gave a highly basic filtrate. In contrast with this issue, LD slag was modified using acetic acid and CO2 purging to convert calcium oxide which is present in the slag to calcium carbonate. The membranes fabricated from modified LD slag showed a filtrate pH of 8.4 and 8.5. Porosity, pore size distribution, flexural strength, chemical stability was determined and pure water flux experiments were conducted to evaluate the efficiency of the prepared membranes. Considering the raw materials cost, the cost of the fabricated membranes was estimated in the range of 32.55-55.7 USD/m2. This work gives a potential path to develop microfiltration ceramic membrane with, high porosity and great quality in terms of strength and chemical stability. The fabricated membranes were utilized in a hybrid technique (flocculation followed by microfiltration) for the treatment of cold roll mill (CRM) wastewater generated from steel industry. Use of LD slag for the fabrication of ceramic membrane is not only an appealing option towards the commercialization of membrane, yet also great option to reduce the solid waste which is dumped to the environment.

Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production.

This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity.

Ultrasonic assisted removal of sunset yellow from aqueous solution by zinc hydroxide nanoparticle loaded activated carbon: Optimized experimental design.

The efficiency of zinc hydroxide nanoparticle loaded on activated carbon (Zn(OH)2-NP-AC) in the removal of sunset yellow from aqueous solutions using ultrasonic-assisted adsorption method was investigated. This nanomaterial was characterized using different techniques such as SEM, XRD and UV-vis spectrophotometer. A central composite design (CCD) was used for the optimization of significant factors using response surface methodology (RSM). Under the best conditions (5.2 min of sonication time, pH3, 0.023 g of adsorbent and 30 mg L(-1) of SY), Langmuir model was fitting the experimental equilibrium data well. The small amount of proposed adsorbent (0.023 g) is applicable for the successful removal of SY (>97%) in short time (5 min) with high adsorption capacity (83-114 mg g(-1)).

Application of central composite design for simultaneous removal of methylene blue and Pb(2+) ions by walnut wood activated carbon.

Activated carbon was prepared from walnut wood which was locally available, non-toxic, abundant and cheap. This new adsorbent was characterized using BET, FTIR and SEM. Point of zero charge (pHpzc) and oxygen containing functional groups were also determined. The prepared adsorbent was applied for simultaneous removal of Pb(2+) ions and methylene blue (MB) dye from aqueous solution. The prominent effect and interaction of variables such as amount of adsorbent, contact time, concentration of MB and Pb(2+) ions were optimized by central composite design. The equilibrium data obtained at optimum condition were fitted to conventional isotherm models and found that Langmuir model was the best fitted isotherm. Kinetic data were fitted using various models. It was revealed that the adsorption rate follows pseudo-second order kinetic model and intraparticle diffusion model.

Simultaneous ultrasound-assisted removal of sunset yellow and erythrosine by ZnS:Ni nanoparticles loaded on activated carbon: optimization by central composite design.

The present study focused on the simultaneous ultrasound-assisted removal of sunset yellow and erythrosine dyes from aqueous solutions using ZnS:Ni nanoparticles loaded on activated carbon (ZnS:Ni-NP-AC) as an adsorbent. ZnS:Ni nanoparticles were synthesized and characterized using different techniques such as FESEM, XRD and TEM. The effects of various parameters such as sonication time, pH, initial dye concentrations and adsorbent dose on the percentage of dye removal were investigated. Parameters were optimized by central composite design (CCD) combined with response surface methodology (RSM) and desirability function (DF). A good agreement between experimental and predicted values was observed. The ultrasound-assisted adsorbent (0.04 g) was capable of high percentage removal (98.7% and 99.6%) of sunset yellow and erythrosine in short time (3.8 min).

Cadmium telluride nanoparticles loaded on activated carbon as adsorbent for removal of sunset yellow.

Adsorption is a promising technique for decolorization of effluents of textile dyeing industries but its application is limited due to requirement of high amounts of adsorbent required. The objective of this study was to assess the potential of cadmium telluride nanoparticles loaded onto activated carbon (CdTN-AC) for the removal of sunset yellow (SY) dye from aqueous solution. Adsorption studies were conducted in a batch mode varying solution pH, contact time, initial dye concentration, CdTN-AC dose, and temperature. In order to investigate the efficiency of SY adsorption on CdTN-AC, pseudo-first-order, pseudo-second-order, Elovich, and intra-particle diffusion kinetic models were studied. It was observed that the pseudo-second-order kinetic model fits better than other kinetic models with good correlation coefficient. Equilibrium data were fitted to the Langmuir model. Thermodynamic parameters such as enthalpy, entropy, activation energy, and sticking probability were also calculated. It was found that the sorption of SY onto CdTN-AC was spontaneous and endothermic in nature. The proposed adsorbent is applicable for SY removal from waste of real effluents including pea-shooter, orange drink and jelly banana with efficiency more than 97%.

Oxidative desulfurization: kinetic modelling.

Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

Adsorption characteristics of brilliant green dye on kaolin.

Experimental investigations were carried out to adsorb toxic brilliant green dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring: (i) particle size distribution using particle size analyzer, (ii) BET surface area using BET surface analyzer, and (iii) structural analysis using X-ray diffractometer. The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH and temperature were studied for the adsorption of brilliant green in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on pH of solution. Free energy of adsorption (DeltaG0), enthalpy (DeltaH0) and entropy (DeltaS0) changes are calculated to know the nature of adsorption. The calculated values of DeltaG0 at 299K and 323K indicate that the adsorption process is spontaneous. The estimated values of DeltaH0 and DeltaS0 both show the negative sign, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in less randomly fashion than in solution. The adsorption kinetic has been described by first-order, pseudo-second-order and intra-particle-diffusion models. It was observed that the rate of dye adsorption follows pseudo-second-order model for the dye concentration range studied in the present case. Standard adsorption isotherms were used to fit the experimental equilibrium data. It was found that the adsorption of brilliant green on kaolin follows the Langmuir adsorption isotherm.

Treatment of fluoride containing drinking water by electrocoagulation using monopolar and bipolar electrode connections.

Electrocoagulation was investigated for the effective removal of fluoride from drinking water. Different initial concentrations (2-10 mg L(-1)) of fluoride were considered for the experiment. Two different electrode connections (monopolar and bipolar) were examined for choosing the better alternative in order to intensify the performance of the process. It was observed that the removal of fluoride was better for bipolar connection than for monopolar connection. The final recommendable limit of fluoride (1 mg L(-1)) was obtained in 30 min at 625 Am(-2) using bipolar connection. The corrosion of electrodes as well as the sludge formed during the process was estimated for the bipolar connection. Thickness of film generated on the electrode surfaces in bipolar connection was also estimated at different current densities as well as for different initial fluoride concentrations. By-products obtained from the electrocoagulation bath were analyzed using SEM, EDAX, FTIR and XRD and explained. Comparative cost estimation for both electrode connections was adopted and presented as well. Total operating costs for monopolar and bipolar connections were 0.38 and 0.62 US$ m(-3), respectively, for the initial fluoride concentration of 10 mg L(-1). These findings might be useful in order to treat the fluoride contaminated water for drinking.

Precipitation of cetyl (hexadecyl) pyridineum chloride using mono and divalent oxyanions.

Experimental investigations have been carried out to observe the performance of precipitation behavior of potassium permanganate (KMnO4) and potassium dichromate (K2Cr2O7) in cetyl (hexadecyl) pyridineum chloride (CPC) solution. As in the case of Al3+-dodecylbenzenesulfonate systems [P. Somasundaran, K.P. Anathapadmanabhan, M.S. Celik, Langmuir 4 (1988) 1061-1063], the precipitation is found to be caused by interaction of CPC micelles with oxyanions. The counter oxyanions have a strong tendency to bind themselves to the surface of cationic CPC micelles. This lowered the free oxyanion concentration in solution. Therefore, to start precipitation, higher oxyanion concentration is required for higher CPC concentration. The effects of temperature, concentrations of both counter ions and CPC on the precipitation have been studied in detail. It has been observed that at CPC to KMnO4 concentration ratio of 1.0 (concentration of CPC and KMnO4 is 400ppm), the percentage precipitation of CPC is around 99.3 at 30 degrees C. The percent precipitation of CPC decreases to about 94% when temperature increases to 70 degrees C at the same condition. The extent of CPC precipitation increases at the same experimental condition when K2Cr2O7 is used instead of KMnO4.

SEM analysis and gas permeability test to characterize polysulfone membrane prepared with polyethylene glycol as additive.

Phase inversion method is applied to prepare flat sheet asymmetric polymeric membranes from homogeneous solution of 12 wt% polysulfone (PSf) with two different solvents--N-methyl-2-pyrrolidone (NMP) and dimethyl acetamide (DMAc). 5.0 wt% polyethylene glycol (PEG) of three different molecular weight (400, 6000, and 20,000 Da) is used as the polymeric additives in the casting solution. Membranes are characterized by two different techniques viz. scanning electron microscopy (SEM) and gas permeation tests. Finally, the results of both the techniques are compared with those calculated from pure water permeation tests using Hagen-Poiseuille equation. It is found that though the values obtained from all the techniques vary from each other, their trend with increase in molecular weight of PEG seems to be the same. It is seen that when molecular weight of PEG increases from 400 to 20,000 Da, the mean pore size of the prepared membranes decreases, while the porosity and pore density show an increasing trend; the pressure normalized gas flux rises significantly and the thickness of the top layer of the prepared membrane sheet increases.

Removal of Fe(II) from tap water by electrocoagulation technique.

Electrocoagulation (EC) is a promising electrochemical technique for water treatment. In this work electrocoagulation (with aluminum as electrodes) was studied for iron Fe(II) removal from aqueous medium. Different concentration of Fe(II) solution in tap water was considered for the experiment. During EC process, various amorphous aluminum hydroxides complexes with high sorption capacity were formed. The removal of Fe(II) was consisted of two principal steps; (a) oxidation of Fe(II) to Fe(III) and (b) subsequent removal of Fe(III) by the freshly formed aluminum hydroxides complexes by adsorption/surface complexation followed by precipitation. Experiments were carried out with different current densities ranging from 0.01 to 0.04 A/m2. It was observed that the removal of Fe(II) increases with current densities. Inter electrode distance was varied from 0.005 to 0.02 m and was found that least inter electrode distance is suitable in order to achieve higher Fe(II) removal. Other parameters such as conductivity, pH and salt concentration were kept constant as per tap water quality. Satisfactory iron removal of around 99.2% was obtained at the end of 35 min of operation from the initial concentration of 25 mg/L Fe(II). Iron concentration in the solution was determined using Atomic absorption spectrophotometer. By products obtained from the electrocoagulation bath were analyzed by SEM image and corresponding elemental analysis (EDAX). Cost estimation for the electrocoagulation was adopted and explained well. Up to 15 mg/L of initial Fe(II) concentration, the optimum total cost was 6.05 US$/m3. The EC process for removing Fe(II) from tap water is expected to be adaptable for household use.

Removal of congo red using activated carbon and its regeneration.

Activated carbon is used for the removal of colored toxic congo red dye. The effects of different operating conditions like, initial dye concentration, contact time, pH and temperature are studied for adsorption of congo red by a known amount of activated carbon (1.0g/L) under stirred batch condition. The zero point of charge of the activated carbon is found about 6.6. About 90% dye is removed for initial concentration of 50 and 100mg/L, it is about 80% at pH 7.0. Maximum adsorption (about 100%) of dye is observed at pH 2.0 for the concentration range studied here. Freundlich isotherm is found to fit the equilibrium data more adequately. Pseudo second order kinetic model explain successfully the kinetic data. The surfactant enhanced carbon regeneration (SECR) technique using both cationic and anionic surfactants is adopted for the regeneration of spent carbon by desorbing the dye. A kinetic model for dye desorption from the commercial activated carbon (CAC) is also proposed. Anionic surfactants show better performance than the cationic ones. Efficiency of dye desorption using surfactants is also compared with the desorption using pH change.

Performance of TX-100 and TX-114 for the separation of chrysoidine dye using cloud point extraction.

Cloud point extraction (CPE) is carried out to extract chrysoidine dye from aqueous solution using two different non-ionic surfactants, TX-100 and TX-114. The effects of different operating parameters, e.g., concentrations of surfactant, dye and salt, temperature, pH on extraction of both dye and surfactant have been studied in detail. The extraction of dye increases with temperature, surfactant concentration and salt concentration. Various design parameters of a CPE process have been estimated by developing correlations for dye solubilization and fractional coacervate phase volume with the operating conditions. The equilibrium solubilization data at four different temperatures follow Langmuir type isotherm. A method is presented to calculate the feed surfactant concentration required for the removal of dyes up to a level of 3.82x10(-6) M. The developed correlations may be useful to design a cloud point extractor of a desired efficiency.

Micellar enhanced ultrafiltration of eosin dye using hexadecyl pyridinium chloride.

Surfactant-based separation of toxic eosin dye is studied to estimate the potential of micellar enhanced ultrafiltration (MEUF) using cetyl(hexadecyl) pyridinium chloride (CPC) as the cationic surfactant. The optimum feed CPC concentration is found from the experimental results of pure CPC solution in a batch cell. It is in the range of 10-20 kg/m(3) to have a reasonable permeate flux and lower surfactant concentration in the permeate. Selecting 10 kg/m(3) as the feed surfactant concentration, MEUF experiments are conducted to study the retention characteristics of eosin dye in the continuous cross flow system. The effects of operating conditions, i.e., feed dye concentration, operating pressure and cross flow rate on the permeate flux and observed retention of dye are investigated.

Cloud point extraction of toxic eosin dye using Triton X-100 as nonionic surfactant.

An attempt has been made to remove color from wastewater containing toxic eosin dye (anionic dye) by cloud point extraction (CPE) in batch mode using a nonionic surfactant, Triton X-100 (TX-100). Most of the dye molecules get solubilized in the coacervate phase leaving a color free dilute phase. The effects of the concentration of feed mixture, temperature and salt concentration on the concentration of both dye and surfactant in the coacervate phase and dilute phase have been studied after the complete separation of two phases. Experimental investigations have also been carried out for the recovery of surfactant from dilute phase applying solvent extraction (SE) in batch condition. It has been observed that 87.5-100 percent eosin removal is possible for the feed dye concentration of up to 200 ppm using 0.1(M) of TX-100 and 0.2(M) of salt (NaCl) at 80 degrees C. About 88 percent of TX-100 can be recovered from dilute phase using solvent extraction method. It is concluded that the cloud point extraction techniques for the dye removal may be an alternative to the present dye removal processes.