Optimization of bio-oil extraction from Chlorella biomass via a green approach to obtain algal-based Di-ethyl phthalate.

This study focuses on determining the optimum external operating parameters of algal cell lysis for extraction of bio-oil from Chlorella biomass. Response surface methodology has been applied to a regression analysis model for optimizing solvent ratios, i.e., ethyl acetate to ethanol (E.A.:E) ratio for maximum extraction of bio-oil and aqueous deep eutectic solvent to biomass (aDES:biomass) ratio for algal pretreatment for the enhanced yield of bio-oil. Optimized process conditions were 15 min of homogenization combined with ultrasonication (hybrid method). The aDES:biomass ratio of 8.25 caused the highest cell disruption efficiency to liberate bio-oil from encapsulated cells. The solvent ethyl acetate to ethanol ratio (E.A.:E) was optimum at 0.8 for maximum extraction of bio-oil, and studies indicated a maximum bio-oil yield of 94.0% using this hybrid pretreatment process combined with ultrasonication and homogenization. The GC-MS characterization technique was used to analyze the bio-oil, which showed it consisted of 67.93% Di-ethyl phthalate (DEP) and 32.07% esters compounds (C12-C40 hydrocarbons range). The produced DEP from Chlorella biomass using this sustainable green approach is very promising. The estimated cost was around Rs 49 per gm (equivalent to Rs 664.56 for 13.58 gm), which indicates the potential for a cost-effective method to produce pure DEP from Chlorella biomass.

Performance, combustion, and emission characteristics of bio-oil produced by in situ catalytic pyrolysis of polypropylene using spent FCC.

Plastic waste is a rich source of hydrocarbons that can be converted into bio-oil through pyrolysis. In this study, bio-oil was produced by pyrolysis of waste-polypropylene using spent FCC catalyst. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that catalytically produced oil has the majority of compounds in the hydrocarbon range of C6-C18. The catalytic pyrolysis oil was blended with conventional fuel (diesel) to extensively investigate its suitability as a fuel substitute in a single-cylinder, four-stroke, 3.5 kW, diesel internal combustion (IC) engine. Furthermore, four fuels, i.e., CF100PO00 (pure diesel), CF90PO10 (10% v/v pyrolysis oil blended with diesel), CF85PO15 (15% v/v pyrolysis oil blended with diesel), and CF80PO20 (20% v/v pyrolysis oil blended with diesel), were tested in IC diesel engine for performance, combustion, and exhaust emission analysis at 1500 rpm. The tests were carried out at five loads, i.e., 1, 5, 10, 15, and 20 Nm. It was found that CF90PO10 produced 6.61% higher brake thermal efficiency (BTE), whereas CO2 exhaust emission decreased by 20% for CF80PO20 with respect to the pure diesel. Diesel blends with plastic pyrolysis oil can be a promising biofuel to improve engine performance and combustion characteristics without any significant engine modification.

Bio-adsorbent hydroxyapatite for drinking water defluoridation: column performance modelling studies.

Waste marble powder (WMP) is a rich source of calcium and magnesium salts having an affinity for fluoride ions and therefore serves as a good defluoridation agent. Hydroxyapatite was synthesized from WMP generated by the marble processing industry to make an adsorbent for drinking water defluoridation. The synthesized marble hydroxyapatite (MA-Hap LR) powder was further formed into 2-3 mm pellets by extrusion spheronization technique using a polyvinyl alcohol binder. Continuous column defluoridation studies were conducted to obtain optimized column parameters such as input fluoride concentration, column inflow rates, optimum pellet size, and adsorbent bed parameters to obtain maximum fluoride adsorption capacity. The best breakthrough column performance was a maximum adsorption capacity of 1.21 mg/g, treating 10 mg/L fluoride concentration. The optimized column flow rate was at 1 LPH using an adsorbent bed height of 25 cm, which processed 28.5-bed volumes at an adsorbent exhaustion rate of 7.4 g/L. The column breakthrough performance data were fit into various kinetic models (Thomas model and Yoon-Nelson model) to describe adsorption kinetics and obtain correlation coefficients. Thomas's model fitted well with a high correlation coefficient value. Modelling studies indicate MA-Hap as a promising adsorbent for drinking water treatment, and optimum column design parameters were identified for scale-up for real applications.

Green calcium-based photocatalyst derived from waste marble powder for environmental sustainability: A review on synthesis and application in photocatalysis.

Calcium, with its excellent adsorptive property and higher permissible limits in the environment, emerges as an effective wastewater treatment earth metal. Most of the catalysts, photocatalysts, and adsorbents reported in the literature have heavy metal complex, which creates a leaching problem. Majorly, precursors used for the synthesis of heterogeneous catalysts for wastewater treatment are costly. Therefore, the use of such precursors would be not suitable and feasible approach from an economic point of view. This review work is focused on giving an overview of the utilisation of calcium-based catalysts (adsorbents and photocatalyst) for the removal/degradation of various types of dye water pollutants and summarises the reported effects of calcium as a base on the removal efficiency of dopants. In this article, an extensive literature survey is presented on the various photocatalysts developed and the different syntheses involved in their preparation. As the utilisation of marble powder is a green sustainable approach, the scope of various calcium-based photocatalysts and their application is presented. This article also aims for the elementary and inclusive determination of the effect of introducing calcium as a base for different catalysts and adsorbents.

Modeling & simulation studies on batch anaerobic digestion of hydrodynamically cavitated tannery waste effluent for higher biogas yield.

This study describes the efficacy of the pretreatment method of tannery waste effluent (TWE) by hydrodynamic cavitation (HC) prior to anaerobic digestion (AD) using a slit venturi cavitating device operated at 5 bar pressure for 2 h. The HC effect caused faster disintegration and solubilization of larger organic molecules into smaller ones, so that it could be easily digested by the microbial cells resulting in higher degradation rates, lower acclimatization time, higher COD reduction of the TWE and higher biogas generation. The biogas yield and % COD reduction was almost twice higher in HC treated TWE compared to raw TWE. Biogas yield of 68.57 mL/g volatile solids with 43.17% COD reduction was obtained during AD of HC treated TWE in 2 L bioreactor with 10% seed dosage. 'AD' Simulator developed in MATLAB represented the AD performance for both raw and HC treated TWE feed and predicted for concentrations of organic polymers, monomers, VFA and biogas produced, in which model parameter optimization was done by validations using methane production data from bioreactors. The AD simulator estimated higher hydrolysis rate constants for HC treated TWE than for raw TWE as observed in the experiments. Biogas production increased up to 7.8 and 11.8 folds for raw and HC treated TWE samples respectively by adding food waste to TWE feed with organic loading rate of 48 h. Cost estimations proved that cost of excess biogas produced by anaerobic digestion of HC treated TWE mixed with food waste, recovers the extra cost of HC pretreatment when compared to raw TWE alone, establishing HC as an effective pre-treatment tool prior to AD.

Curcumin Encapsulation in Multilayer Oil-in-Water Emulsion: Synthesis Using Ultrasonication and Studies on Stability and Antioxidant and Release Activities.

Curcumin is a natural polyphenol compound obtained from the turmeric plant, having numerous promising health benefits. To deliver curcumin into the human body, it is necessary to develop an efficient carrier system for its encapsulation such that the physicochemical properties of curcumin can be preserved during storage. In this study, the encapsulation stability, antioxidant activity, and release properties of curcumin encapsulated in the primary emulsion (PE: 0.0022% (w/w) curcumin, 9.99% (w/w) oil, 0.9% (w/w) whey protein isolate, pH 7) and secondary emulsion (SE: 0.00108% (w/w) curcumin, 4.90% (w/w) oil, 0.443% (w/w) WPI, 0.2% (w/w) sodium alginate, pH 5) prepared using ultrasonication were analyzed. It was observed that the formation of a double-layer coating of secondary biopolymer over the primary coated droplet enhanced the encapsulation efficiency and antioxidant activity of the curcumin during storage for 3 weeks. Moreover, the multilayer emulsions were freeze-dried to see the effect of dehydration of emulsion on the stability of multilayer-coated droplets. Fourier transform infrared analysis indicated the presence of all of the constituents, including curcumin, after the freeze drying of the emulsions. Scanning electron microscopy images showed that the microstructure of emulsion droplets was found to be uniformly distributed in the case of SE. The antioxidant activity of curcumin encapsulated in SE was found to be higher during storage, whereas it was significantly reduced in other encapsulated systems like PE, olive oil, and ethanol. In vitro release of curcumin from the multilayer emulsion was carried out under the simulated intestinal conditions of pancreatin enzyme and bile salt. Maximum releases of 71 and 63% were obtained in SE and PE, respectively, within 2 h of digestion. Overall, this study provides useful information on the formation of multilayer emulsion as a carrier system for the better protection and release of curcumin useful for food and pharmaceutical applications.

Treatment of textile dyeing industry effluent using hydrodynamic cavitation in combination with advanced oxidation reagents.

Treatment of textile dyeing industry (TDI) effluent was investigated using hydrodynamic cavitation (HC) and in combination with advanced oxidation reagents such as air, oxygen, ozone and Fenton's reagent. Slit venturi was used as the cavitating device in HC reactor. The effects of process parameters such as inlet pressure, cavitation number, effluent concentration, ozone and oxygen flow rate, loading of H2O2 and Fenton's reagent on the extent of reduction of TOC, COD and color were studied. Efficiency of the hybrid treatment processes were evaluated on the basis of their synergetic coefficient. It was observed that almost 17% TOC, 12% COD, and 25% color removal was obtained using HC alone at inlet pressure of 5bar and pH of 6.8. The rate of reduction of TOC and COD decreased with dilution of the samples. HC in combination with Fenton's reagent (FeSO4·7H2O:H2O2 as 1:5) was most effective with reduction of 48%TOC and 38% COD in 15min and 120min respectively with almost complete decolorization (98%) of the TDI effluent. Whereas HC in combination with oxygen (2L/min) and ozone (3g/h) produced reduction of 48% TOC, 33% COD, 62% decolorization and 48% TOC, 23% COD, 88%, decolorization of TDI effluent respectively.

An advanced pretreatment strategy involving hydrodynamic and acoustic cavitation along with alum coagulation for the mineralization and biodegradability enhancement of tannery waste effluent.

In the present study, coagulation followed by cavitation was studied as a pretreatment tool for tannery waste effluent (TWE) with the aim of reducing its COD, TOC, TSS etc. and enhancing its biodegradability to make it suitable for anaerobic digestion. Initially, coagulation was applied to TWE using alum as a coagulant. The residual pH of treated effluent was found to be around pH of 4.5 where maximum COD and TSS reduction was achieved. In order to enhance the efficiency of pretreatment process, coagulated tannery waste effluent (CTWE) was further subjected to hydrodynamic cavitation (HC) and ultrasonication (US). In case of HC, effect of process parameters such as inlet pressure and dilution on the treatment of CTWE was initially investigated. Lower operating pressure (5 bar) was more favorable for the treatment of CTWE using HC in order to enhance the biodegradability index (BI) from 0.14 to 0.57 in 120 min. The CTWE samples when subjected to 50% dilution, HC pretreatment exhibited higher percentage and quantum reduction in TOC and COD. On the other hand, pretreatment of TWE using coagulation followed by US demonstrated that BI of effluent was enhanced from 0.10 to 0.41 in 150 min. Energy efficiency evaluation for all processes at their optimized conditions was done based on the actual amount of COD reduced per unit energy delivered to the system. Coagulation followed by HC for the pretreatment of TWE was found to be six times more energy efficient as compared to coagulation followed by US.

In-vitro synthesis of marble apatite as a novel adsorbent for removal of fluoride ions from ground water: An ultrasonic approach.

Marble waste powder consisting of calcium and magnesium compounds was used to synthesize a novel biocompatible product, marble apatite (MA) primarily hydroxyapatite (Hap) for applications in defluoridation of drinking water. Synthesis of marble apatite was carried out by using calcium compounds (mixture of hydroxide and nitrate) extracted from marble waste powder which was treated with potassium dihydrogen phosphate at 80°C under alkaline conditions using conventional precipitation method (CM) and ultrasonication method (USM). Qualitative analysis of synthesized marble apatite from both the methods was carried out using FTIR, phase analysis by XRD and microstructure analysis by SEM and TEM. When ultrasonication (USM) method was used, the yield of marble apatite was improved from 67.5% to 78.4%, with reduction in crystallite size (58.46nm), lesser agglomeration and comparatively well-defined spherical morphology compared to the CM method. Studies also include estimation of the defluoridation capacity of MA as an adsorbent for drinking water treatment and effects of process parameters such as pH, contact time, initial fluoride concentration, dosage and presence of other co-ions on fluoride removal capacity. The results showed that the experimental adsorption capacity of the marble apatite synthesized using USM method was significantly higher (1.826mg/g) than marble apatite synthesized using conventional method (0.96mg/g) at pH 7 with a contact time of 90min. The mechanism of adsorption was studied, and it was observed that Langmuir isotherm model fitted best to the experimental data, while the kinetic studies revealed that the process followed pseudo-second order model. This novel compound, marble apatite synthesized from marble waste powder is found to be promising for defluoridation of drinking water and will help in alleviating the problems of fluorosis as well as reduce the problems of disposal of marble waste.

Degradation of reactive blue 13 using hydrodynamic cavitation: Effect of geometrical parameters and different oxidizing additives.

Decolorization of reactive blue 13 (RB13), a sulphonated azo dye, was investigated using hydrodynamic cavitation (HC). The aim of research article is to check the influence of geometrical parameters (total flow area, the ratio of throat perimeter to its cross-sectional area, throat shape and size, etc.) and configuration of the cavitating devices on decolorization of RB13 in aqueous solution. For this purpose, eight cavitating devices i.e. Circular and slit venturi, and six orifice plates having different flow area and perimeter were used in the present work. Initially, the effects of various operating parameters such as solution pH, initial dye concentration, operating inlet pressure and cavitation number on the decolorization of RB13 have been investigated, and the optimum operating conditions were found. Kinetic analysis revealed that the decolorization and mineralization of RB13 using HC followed first order reaction kinetics. Almost 47% decolorization of RB13 was achieved using only HC with slit venturi as a cavitating device at an optimum inlet pressure of 0.4MPa and pH of the solution as 2.0. It has been found that in case of orifice plates, higher decolorization rate of 4×10-3min-1 was achieved using orifice plate 2 (OP2) which is having higher flow area and perimeter (α=2.28). The effect of process intensifying agents (hydrogen peroxide and ferrous sulphate) and different gaseous additives (oxygen and ozone) on the extent of decolorization of RB13 were also examined. Almost 66% decolorization of RB13 was achieved using HC combined with 2Lmin-1 of oxygen and in combination with ferrous sulphate (1:3). Nearly 91% decolorization was achieved using HC combined with H2O2 at an optimum molar ratio (dye:H2O2) of 1:20 while almost complete decolorization was observed in 15min using a combination of HC and ozone at 3gh-1 ozone feed rate. Maximum 72% TOC was removed using HC coupled with 3gh-1 ozone feed rate.

Synthesis of hydroxyapatite nanorods for application in water defluoridation and optimization of process variables: Advantage of ultrasonication with precipitation method over conventional method.

This research work presents the synthesis of hydroxyapatite (Hap) nanorods for defluoridation of drinking water by using both conventional (CM) and ultrasonication with precipitation (USPM) methods. Calcium nitrate was reacted with potassium phosphate in presence of ammonia for controlled pH to synthesize Hap nanorods, which was characterized using FTIR, XRD, SEM, TG-DTA, and TEM/EDS for determining its phase composition, structural and thermal decomposition behavior. When USPM method was used for synthesis, the yield of the Hap nanorods was improved from 83.24±1.0% to 90.2±1.0%, and complete phase transformation occurred with formation of elongated Hap nanorods. Effects of process parameters such as solution pH, contact time and adsorbent dose were studied through response surface methodology (RSM). A simple quadratic model was developed using Central Composite Design (CCD) and optimum parameters for fluoride adsorption process were determined to be pH 7, contact time 3h and adsorbent dose 7g/L for maximum removal capacity. Fluoride removal efficiency was predicted to be 93.64% which was very close to the experimental value obtained at 92.86% using ultrasonically prepared Hap. Fluoride adsorption isotherms fitted the Freundlich isotherm with an adsorption capacity of 1.49mg/g, while the kinetic studies revealed that the process followed pseudo-second order model. The treated water quality parameters such as residual fluoride, calcium leached, total hardness and alkalinity was investigated, and it was observed that all these parameters were within the permissible limits as per WHO and BIS standards.

Ultrasonic assisted formation and stability of mustard oil in water nanoemulsion: Effect of process parameters and their optimization.

The present work reports the ultrasound assisted preparation of mustard oil in water nanoemulsion stabilized by Span 80 and Tween 80 at different operating conditions. Effects of various operating parameters such as HLB (Hydrophilic Lipophilic Balance) value, surfactant volume fraction (φS), oil volume fraction (φO) and power amplitude were investigated and optimized on the basis of droplet size and stability of nanoemulsions. It was observed that minimum droplet size of about 87.38nm was obtained within 30min of ultrasonication at an optimum HLB value of 10, φS of 0.08 (8%, v/v), φO of 0.1 (10%, v/v) and ultrasonic power amplitude of 40%. The stability of the nanoemulsion was measured through visual observation and it was found that the unstable emulsions got separated within 24h whereas, stable emulsions never showed any separation until 90days. In addition to that, the kinetic stability of the prepared nanoemulsions was also assessed under centrifuge and thermal stress conditions. The emulsion stability was found to be unaffected by these forces as the droplet size remained unchanged. The ultrasound prepared emulsion was found to be long term stable even after 3months of storage at ambient conditions without any visual evidence of creaming and phase separation and also remained kinetically stable. FTIR analysis of the emulsions at different sonication conditions was carried out to examine the possible impact of ultrasonically induced chemical effects on oil structure during emulsification and it was found that the oil molecular structure was unaffected by ultrasonication process. The present work illustrates the formation and stability of mustard oil in water nanoemulsion using ultrasound cavitation which may be useful in food and cosmetic based applications.

Degradation of a cationic dye (Rhodamine 6G) using hydrodynamic cavitation coupled with other oxidative agents: Reaction mechanism and pathway.

In the present study, decolorization and mineralization of a cationic dye, Rhodamine 6G (Rh6G), has been carried out using hydrodynamic cavitation (HC). Two cavitating devices such as slit and circular venturi were used to generate cavitation in HC reactor. The process parameters such as initial dye concentration, solution pH, operating inlet pressure, and cavitation number were investigated in detail to evaluate their effects on the decolorization efficiency of Rh6G. Decolorization of Rh6G was marginally higher in the case of slit venturi as compared to circular venturi. The kinetic study showed that decolorization and mineralization of the dye fitted first-order kinetics. The loadings of H2O2 and ozone have been optimized to intensify the decolorization and mineralization efficiency of Rh6G using HC. Nearly 54% decolorization of Rh6G was obtained using a combination of HC and H2O2 at a dye to H2O2 molar ratio of 1:30. The combination of HC with ozone resulted in 100% decolorization in almost 5-10min of processing time depending upon the initial dye concentration. To quantify the extent of mineralization, total organic carbon (TOC) analysis was also performed using various processes and almost 84% TOC removal was obtained using HC coupled with 3g/h of ozone. The degradation by-products formed during the complete degradation process were qualitatively identified by liquid chromatography-mass spectrometry (LC-MS) and a detailed degradation pathway has been proposed.

Degradation of reactive orange 4 dye using hydrodynamic cavitation based hybrid techniques.

In the present work, degradation of reactive orange 4 dye (RO4) has been investigated using hydrodynamic cavitation (HC) and in combination with other AOP's. In the hybrid techniques, combination of hydrodynamic cavitation and other oxidizing agents such as H2O2 and ozone have been used to get the enhanced degradation efficiency through HC device. The hydrodynamic cavitation was first optimized in terms of different operating parameters such as operating inlet pressure, cavitation number and pH of the operating medium to get the maximum degradation of RO4. Following the optimization of HC parameters, the degradation of RO4 was carried out using the combination of HC with H2O2 and ozone. It has been found that the efficiency of the HC can be improved significantly by combining it with H2O2 and ozone. The mineralization rate of RO4 increases considerably with 14.67% mineralization taking place using HC alone increases to 31.90% by combining it with H2O2 and further increases to 76.25% through the combination of HC and ozone. The synergetic coefficient of greater than one for the hybrid processes of HC+H2O2 and HC+Ozone has suggested that the combination of HC with other oxidizing agents is better than the individual processes for the degradation of dye effluent containing RO4. The combination of HC with ozone proves to be the most energy efficient method for the degradation of RO4 as compared to HC alone and the hybrid process of HC and H2O2.

Synergetic effect of combination of AOP's (hydrodynamic cavitation and H2O2) on the degradation of neonicotinoid class of insecticide.

In the present work, degradation of imidacloprid (neonicotinoid class of insecticide) in aqueous solution has been systematically investigated using hydrodynamic cavitation and combination of hydrodynamic cavitation (HC) and H2O2. Initially, effect of different operating parameters such as inlet pressure to the cavitating device (5-20 bar) and operating pH (2-7.5) has been investigated. Optimization of process parameters was followed by the study of effect of combination of HC and H2O2 process on the rate of degradation of imidacloprid. Significant enhancement in the rate of degradation of imidacloprid has been observed using HC+H2O2 process which lead to a complete degradation of imidacloprid in 45 min of operation using optimal molar ratio of imidacloprid:H2O2 as 1:40. Substantial synergetic effect has been observed using HC+H2O2 process which confer the synergetic coefficient of 22.79. An attempt has been made to investigate and compare the energy efficiency and extent of mineralization of individual and combined processes applied in the present work. Identification of the byproducts formed during degradation of imidacloprid has also been done using LC-MS analysis. The present work has established a fact that hydrodynamic cavitation in combination with H2O2 can be effectively used for degradation of imidacloprid.

Effect of geometry of hydrodynamically cavitating device on degradation of orange-G.

In this research work, we have carried out geometric optimization of different cavitating devices using degradation of orange-G dye [OG] as a model pollutant. Three different cavitating devices viz. orifice plate, circular venturi and slit venturi were optimized and the degradation of orange-G dye was studied. The optimization of all three cavitating devices was done in terms of fluid inlet pressure to the cavitating devices and cavitation number. The effect of pH and initial concentration of the dye on the degradation rate was also studied. The geometry of cavitating device (flow cross sectional area, perimeter, shape, etc.) was found to be an important parameter in getting the maximum cavitational effect using hydrodynamic cavitation. The cavitational yield of all three cavitating devices were compared on the basis of mg of total organic carbon (TOC) reduction per unit energy supplied. The slit venturi gives almost 50% higher degradation rate and cavitational yield among all three cavitating devices studied for the same amount of energy supplied.

Cavitationally induced biodegradability enhancement of a distillery wastewater.

Hydrodynamic cavitation (HC) was evaluated as a pretreatment option for the complex/recalcitrant biomethanated distillery wastewater (B-DWW). The effect of various process parameters such as inlet pressure, dilution and reaction time on reduction of COD/TOC and enhancement of biodegradability index (BI:BOD(5):COD ratio) of the B-DWW was studied with an aim to maximize the biodegradability index and reducing the toxicity of the distillery wastewater. It was observed that higher operating pressure (13 bar) yielded the maximum BI whereas the lower pressure (5 bar) is suitable for the reduction in the toxicity of B-DWW. The toxicity of the distillery wastewater was analyzed by measuring the COD, TOC and color of the wastewater sample. The HC pretreatment under optimized conditions leads to a BI of 0.32, COD and TOC reduction of 32.24% and 31.43%, respectively along with a color reduction by 48%. These results indicate the potential of HC as a pretreatment option for enhancing the biodegradability index of the recalcitrant wastewater such as B-DWW along with reduced toxicity of wastewater as observed from COD, TOC and color reduction profile under optimized conditions.