Waste to energy: Trending key challenges and current technologies in waste plastic management.

Due to the 'forever' degrading nature of plastic waste, plastic waste management is often complicated. The applications of plastic are ubiquitous and inevitable in many scenarios. Current global waste plastics production is ca. 3.5 MMT per year, and with the current trend, plastic waste production will reach 25,000 MMT by 2040. However, the rapid growth in plastic manufacture and the material's inherent nature resulted in the accumulation of a vast amount of plastic garbage. The current recycling rate is <10 %, while the large volumes of discarded plastic waste cause environmental and ecological problems. Recycling rates for plastic vary widely by region and type of plastic. In some developed countries, the recycling rate for plastics is around 20-30 %, while in many developing nations, it is much lower. These statistics highlight the magnitude of the plastic waste problem and the urgent need for comprehensive strategies to manage plastic waste more effectively and reduce its impact on the environment. This review critically analyses past studies on the essential and efficient techniques for turning plastic trash into treasure. Additionally, an attempt has been made to provide a comprehensive understanding of the plastic upcycling process, the 3Rs policy, and the life-cycle assessment (LCA) of plastic conversion. The review advocates pyrolysis as one of the most promising methods of turning plastic trash into valuable chemicals. In addition, plastic waste management can be severely impacted due to uncontrollable events, such as Covid 19 pandemic. Recycling and chemical upcycling can certainly bring value to the end-of-life plastic. However, the LCA analysis indicated there is still a huge scope for innovation in chemical upcycling area compared to mechanical recycling. The formulation of policies and heightened public participation could play a pivotal role in reducing the environmental repercussions of plastic waste and facilitating a shift towards a more sustainable future.

Facile Hydrogenolysis of Sugars to 1,2-Glycols by Ru@PPh3/OPPh3 Confined Large-Pore Mesoporous Silica.

Tandem hydrogenation vis-à-vis hydrogenolysis of xylose to 1,2-glycols remains a major challenge. Although one-pot conversion of xylose to 1,2-glycols requires stringent conditions, a sustainable approach would be quite noteworthy. We have developed a microwave route for the one-pot conversion of pentose (C5) and hexose (C6) sugars into glycol and hexitol, without pressurized hydrogen reactors. A pronounced hydrogenolysis of sugars to glycols is observed by Ru single atom (SA) on triphenylphosphine/phosphine oxide-modified silica (Ru@SiP), in contrast to Ru SA on pristine (Ru@SiC) and 3-aminopropyl-modified silica (Ru@SiN). A promising "ligand effect" was observed through phosphine modification of silica that presents a 70% overall yield of all reduced sugars (xylitol + glycols) from a 99% conversion of xylose with Ru@SiP. A theoretical study by DFT depicts an electronic effect on Ru-SA by triphenylphosphine that promotes the catalytic hydrogenolysis of sugars under mild conditions. Hence, this research represents an important step for glycols from biomass-derived sources.

Multiobjective Bayesian Optimization Framework for the Synthesis of Methanol from Syngas Using Interpretable Gaussian Process Models.

Methanol production has gained considerable interest on the laboratory and industrial scale as it is a renewable fuel and an excellent hydrogen energy storehouse. The formation of synthesis gas (CO/H2) and the conversion of synthesis gas to methanol are the two basic catalytic processes used in methanol production. Machine learning (ML) approaches have recently emerged as powerful tools in reaction informatics. Inspired by these, we employ Gaussian process regression (GPR) to the model conversion of carbon monoxide (CO) and selectivity of the methanol product using data sets obtained from experimental investigations to capture uncertainty in prediction values. The results indicate that the proposed GPR model can accurately predict CO conversion and methanol selectivity as compared to other ML models. Further, the factors that influence the predictions are identified from the best GPR model employing "Shapley Additive exPlanations" (SHAP). After interpretation, the essential input features are found to be the inlet mole fraction of CO (Y(CO, in)) and the net inlet flow rate (Fin(nL/min)) for our best prediction GPR models, irrespective of our data sets. These interpretable models are employed for Bayesian optimization in a weighted multiobjective framework to obtain the optimal operating points, namely, maximization of both selectivity and conversion.

Controlled synthesis of Ru-single-atoms on ordered mesoporous phosphine polymers for microwave-assisted conversion of biomass-derived sugars to artificial sweeteners.

Atomically dispersed metal-single-atoms have become a frontier in solid catalysis due to their characteristic electronic properties. However, for biomass conversion, employing metal-single-atoms as catalysts is rather challenging since they suffer from poor selectivity and yield due to inadequate metal-support interactions. We show here that Ru/triphenylphosphine (PPh)-based ordered mesoporous polymers afford high yields of reduced sugars, xylitol (yield ∼95%) and sorbitol (yield ∼65%) in a microwave reactor with formic acid as the only hydrogen donor. We have established a unique relationship within Ru/triphenylphosphine that shows an important ligand effect, in contrast to, Ru/triphenylamine and Ru/catechol. The tailored electronic properties in Ru/phosphine were thoroughly examined by using state-of-the-art experimental techniques viz. EXAFS, XANES, XPS, DRIFTS and HAADF-STEM. The resulting phosphine-modified catalysts show a promotion in activity and selectivity towards less vulnerable aldehydes for hydrogenation, further confirmed by DFT calculations. This finding reveals a new protocol to tailor the activity of metal-single-atoms utilizing functional porous polymers as nanoreactors.

Unveiling the potential of water as a co-solvent in microwave-assisted delignification of sugarcane bagasse using ternary deep eutectic solvents.

Deep eutectic solvents (DESs) have become popular owing to their biodegradability and recyclability. In this study, the influence of water as a co-solvent is demonstrated to enhance the properties of choline based ternary DESs. A fast and energy-efficient microwave-assisted pre-treatment process was developed for delignification of sugarcane bagasse (SB). The effectiveness of SB fractionation was revealed by incorporating Lewis acids (MgCl2.6H20, NiCl2.6H20) with the DESs for pre-treatment and Choline chloride: Ethylene glycol: NiCl2.6H20 (CC:EG:NI) at a molar ratio 1:2:0.016 with 20w% water as a co-solvent provided the most promising result, with 84% delignification and 99% enzyme digestibility. Water was also employed as an anti-solvent to facilitate lignin solubility and exhibited up to 26w% lignin yield from DES liquor with maximum DES recovery of 95% (w/w). Water distinctly affects the density, viscosity, and intermolecular hydrogen bonding of the DES and its impact on the process dynamics is worth further exploration.

Catalytic production and application of bio-renewable butyl butyrate as jet fuel blend- A review.

Butyl butyrate (BB) derived from bio-renewable resources is the most promising jet fuel blend. This review highlights essential properties of jet fuel, including calorific value, kinematic viscosity, freezing point, flash point, auto-ignition temperature, and density to compare with different bio-renewable chemicals, which are compatible to be blended with the jet fuel. A detailed discussion follows on the importance of intermediate formation, reaction mechanism, and catalyst properties that are critical towards the production of bio-renewable resource-derived BB. BB is primarily produced via the esterification of butyric acid (BA) in butanol (BuOH) with or without using a catalyst. The corresponding reactions are carried out in both homogeneous and heterogeneous phases, provided it has acidic properties. Thus, a wide range of acidic catalysts such as [HSO3-pmim] HSO4 ionic liquids, heteropolyacid, methanesulfonic acid, Dowex 50 Wx8-400 resins, and sulfonated char causes up to 98%, 97.9%, 93.2%, 95.3%, and 90% of BB yield, respectively are critically reviewed. Moreover, reaction mechanism, product, and by-product formation that primarily dictate the BB yield and selectivity have been comprehensively reviewed. In addition, catalytic and mechanistic insights on BB production from other bio-renewable resources such as butyric anhydride, butyraldehyde, dibutyl ether, and methanol have been discussed in this review.

Co-Hydrothermal Liquefaction of algal and lignocellulosic biomass: Status and perspectives.

Hydrothermal liquefaction (HTL) effectively converts biomass to biofuels, thereby limiting the endless reliance on petroleum products derived from fossil fuels. However, the conversion is based on individual feedstock in the HTL process. In order to, further boost the conversion, HTL can be done by blending various feedstock, mainly algal and lignocellulosic biomass. Bibliometric analysis was carried out, and it was observed that there have been very few studies on Co-Hydrothermal Liquefaction (Co-HTL). There still exist several crucial gaps in process optimization when co-reactants are used due to their synergistic effects. The reaction kinetics and mechanism, catalyst screening and by-products application require further studies. Therefore, R&D is necessary to optimize the process to completely utilize the complementarity of the feedstocks under study resulting in better quality of products which require minor/ no upgradation steps.

Topotactic transformation of homogeneous phosphotungastomolybdic acid materials to heterogeneous solid acid catalyst for carbohydrate conversion to alkyl methylfurfural and alkyl levulinate.

The strong interaction of higher transition metal oxides with inorganic non-metals can be promising for generating highly acidic three-dimensional materials by design. A comprehensive controlled acidity of heteropolyacid-like catalyst and interpretation of the microstructure and mechanism of the formation of a versatile heterogeneous solid acid catalyst, HPW4Mo10O x has been heterogenized by biomass-derived cystine as organic linkers to control the acidity of as-synthesized materials, which have greater acidity and complexity in separation from the reaction mixture. The new and unique results obtained in catalysis done in biphasic reaction. Cystine binds to the surface of HPW4Mo10O x , and the topotactic transition occurred, change the morphology and lattice parameter. We described here a sustainable transformation of highly acidic (0.84 mmol g-1) heteropoly acid (HPW4Mo10O x ) to cystine anchored on the active surface of the heteropoly acid and controlled the acidity (0.63 mmol g-1) and heterogenized the materials. As synthesized materials have been showing that for the direct formation of alkyl levulinate and furanics intermediate from carbohydrates. HPW4Mo10O x and HPW4Mo10O x -Cys, act as acidic catalyst, and catalyse the mono- and disaccharides that are dissolved in primary and secondary alcohols to alkyl levulinate (AL) and alkyl methylfurfural at 170 °C under microwave irradiation with glucose as the substrate, AL yield reaches 62% with 84.95% selectivity. The catalyst can be easily recovered by filtration and minimum five times reused after calcination without any substantial change in the product selectivity. The analytical analysis of as-synthesis materials done by NH3-TPD, BET, XRD, FESEM, TEM, HRTEM, FTIR, ATR, TGA, DTA to stabilized the morphology and acidity controlled mechanism.

Pyrolysis and kinetic analyses of a perennial grass (Saccharum ravannae L.) from north-east India: Optimization through response surface methodology and product characterization.

The objective of the present investigation was to optimize the pyrolysis condition of an abundantly available and low cost perennial grass of north-east India Saccharum ravannae L. (S. ravannae) using response surface methodology based on central composite design. Kinetic study of the biomass was conducted at four different heating rates of 10, 20, 40 and 60 °C min-1 and results were interpreted by Friedman, Kissinger Akira Sunnose and Flynn-Wall-Ozawa methods. Average activation energy 151.45 kJ mol-1 was used for evaluation of reaction mechanism following Criado master plot. Maximum bio-oil yield of 38.1 wt% was obtained at pyrolysis temperature of 550 °C, heating rate of 20 °C min-1 and nitrogen flow rate of 226 mL min-1. Study on bio-oil quality revealed higher content of hydrocarbon, antioxidant property, total phenolic content and metal chelating capacity. These opened up probable applications of S. ravannae bio-oil in different fields including fuel, food industry and biomedical domain.

Weighted spline based integration for reconstruction of freeform wavefront.

In the present work, a spline-based integration technique for the reconstruction of a freeform wavefront from the slope data has been implemented. The slope data of a freeform surface contain noise due to their machining process and that introduces reconstruction error. We have proposed a weighted cubic spline based least square integration method (WCSLI) for the faithful reconstruction of a wavefront from noisy slope data. In the proposed method, the measured slope data are fitted into a piecewise polynomial. The fitted coefficients are determined by using a smoothing cubic spline fitting method. The smoothing parameter locally assigns relative weight to the fitted slope data. The fitted slope data are then integrated using the standard least squares technique to reconstruct the freeform wavefront. Simulation studies show the improved result using the proposed technique as compared to the existing cubic spline-based integration (CSLI) and the Southwell methods. The proposed reconstruction method has been experimentally implemented to a subaperture stitching-based measurement of a freeform wavefront using a scanning Shack-Hartmann sensor. The boundary artifacts are minimal in WCSLI which improves the subaperture stitching accuracy and demonstrates an improved Shack-Hartmann sensor for freeform metrology application.

Development and performance evaluation of an algal biofilm reactor for treatment of multiple wastewaters and characterization of biomass for diverse applications.

A modified algal biofilm reactor (ABR) was developed and assessed for high biomass productivity and treatment potential using variable strength wastewaters with accumulation of specialized bio-products. The nonwoven spun bond fabric (70GSM) was selected as suitable biofilm support on the basis of attachment efficiency, durability and ease of harvesting. The biomass productivity achieved by ABR biofilms were 4gm-2d-1, 3.64gm-2d-1 and 3.10gm-2d-1 when grown in livestock wastewater (LSW), domestic grey water (DGW) and anaerobically digested slurry (ADS), respectively. Detailed characterization of wastewater grown biomass showed specific distribution of biomolecules into high lipid (38%) containing biomass (DGW grown) and high protein (44%) biomass (LSW and ADS grown). The feasibility assessment of ABR in terms of net energy return (>1) favored its application in an integrated system for treatment and recycling of rural wastewaters with simultaneous production of biomethane, livestock feed supplement and bio fertilizers.

Depolymerization of microcrystalline cellulose to value added chemicals using sulfate ion promoted zirconia catalyst.

The transformation of lignocellulosic biomass to value added chemicals in a synergetic effect of sulfated zirconia (SZ) catalyst and ionic liquid was found to effectively depolymerize microcrystalline cellulose (MCC) to sugars and dehydrate sugars to 5-hydroxylmethylfurfural (5-HMF) and levulinic acid (LA). SZ was catalyst synthesized by wet impregnation method with predetermined concentration of sulphuric acid and then characterized using techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), BET-surface area analyzer, thermo-gravimetric analysis (TGA) and temperature programmed desorption of ammonia (Ammonia-TPD). SZ catalyst was effective in depolymerizing MCC yielding a maximum of total reducing sugar (TRS) of 57% (38% glucose and 14% fructose), 9.5% LA and 5.1 of 5-HMF at a temperature of 180°C and 3h of depolymerization time. In addition, SZ was tested for dehydration of glucose and fructose and a yield of 26% and 62% of 5-HMF were obtained, respectively.

Effect of heating/reheating of fats/oils, as used by Asian Indians, on trans fatty acid formation.

Heating/frying and reuse of edible fats/oils induces chemical changes such as formation of trans fatty acids (TFAs). The aim of this study was to investigate the effect of heating/frying on formation of TFAs in fats/oils. Using gas chromatography with flame ionisation detector, TFA was estimated in six commonly used fat/oils in India (refined soybean oil, groundnut oil, olive oil, rapeseed oil, clarified butter, partially hydrogenated vegetable oil), before and after subjecting them to heating/frying at 180°C and 220°C. All six fats/oils subjected to heating/frying demonstrated an increase in TFAs (p<0.001), saturated fatty acids (p<0.001) and decrease in cis-unsaturated fatty acids (p<0.001). The absolute increase in TFA content of edible oils (after subjecting to heating/reheating) ranged between 2.30±0.89g/100g and 4.5±1.43g/100g; amongst edible fats it ranged between 2.60±0.38g/100g and 5.96±1.94g/100g. There were no significant differences between the two treatment groups (heating and frying; p=0.892). Considering the undesirable health effects of TFA, appropriate guidelines for heating/re-frying of edible fats/oils by Asian Indians should be devised.

Intermediate pyrolysis of agro-industrial biomasses in bench-scale pyrolyser: Product yields and its characterization.

Pyrolysis of woody biomass, agro-residues and seed was carried out at 500 ± 10 °C in a fixed bed pyrolyser. Bio-oil yield was found varying from 20.5% to 47.5%, whereas the biochar and pyrolysis gas ranged from 27.5% to 40% and 24.5% to 40.5%, respectively. Pyrolysis gas was measured for flame temperature along with CO, CO2, H2, CH4 and other gases composition. HHV of biochar (29.4 MJ/kg) and pyrolitic gas (8.6 MJ/kg) of woody biomass was higher analogous to sub-bituminous coal and steam gasification based producer gas respectively, whereas HHV of bio-oil obtained from seed (25.6 MJ/kg) was significantly more than husks, shells and straws. TGA-DTG studies showed the husks as potential source for the pyrolysis. Bio-oils as a major by-product of intermediate pyrolysis have several applications like substitute of furnace oil, extraction of fine chemicals, whereas biochar as a soil amendment for enhancing soil fertility and gases for thermal application.

Perennial grass (Arundo donax L.) as a feedstock for thermo-chemical conversion to energy and materials.

In the present study, perennial grass species Arundo donax L. was pyrolysed in a fixed-bed reactor and characterization was performed for the liquid and the solid products. The effect of process parameters such as temperature (350-650 °C), heating rate (10 °C and 40 °C min(-1)) and sweeping gas flow rate (50-250 ml min(-1)) was also investigated. Maximum bio-oil yield of ∼ 26% was observed at 500 °C for the heating rate of 40 °C min(-1). Chemical composition of the bio-oil was analysed through NMR, FTIR and GC-MS. The biochar was characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy along with elemental analysis (CHN). The biochar produced as a co-product of A. donax pyrolysis can be a potential soil amendment with multiple benefits including increased soil fertility and C-sequestration. Current investigation suggests suitability of A. donax as a potential feedstock for exploitation of energy and biomaterials through pyrolytic route.

Subaperture stitching for measurement of freeform wavefront.

A method based on subaperture stitching for measurement of a freeform wavefront is proposed and applied to wavefronts calculated from the slope data acquired using a scanning Shack Hartmann sensor (SHS). The entire wavefront is divided into a number of subapertures with overlapping zones. Each subaperture is measured using the SHS, which is scanned over the entire wavefront. The slope values and thus the phase values of separately measured subapertures cannot be connected directly due to various misalignment errors during the scanning process. The errors lying in the vertical plane, i.e., piston, tilt, and power, are minimized by fitting them in the overlapping zone. The radial and rotational misalignment errors are minimized during registration in the global frame by using active numerical alignment before the stitching process. A mathematical model for a stitching algorithm is developed. Simulation studies are presented based on the mathematical model. The proposed mathematical model is experimentally verified on freeform surfaces of a cubic phase profile.

Hydrogen production from steam reforming of acetic acid over Cu-Zn supported calcium aluminate.

Hydrogen can be produced by catalytic steam reforming (CSR) of biomass-derived oil. Typically bio oil contains 12-14% acetic acid; therefore, this acid was chosen as model compound for reforming of biooil with the help of a Cu-Zn/Ca-Al catalyst for high yield of H(2) with low CH(4) and CO content. Calcium aluminate support was prepared by solid-solid reaction at 1350°C. X-ray diffraction indicates 12CaO·7Al(2)O(3) as major, CaA(l4)O(7) and Ca(5)A(l6)O(14) as minor phases. Cu and Zn were loaded onto the support by wet-impregnation at 10 and 1wt.%, respectively. The catalysts were characterized by Brunauer-Emmett-Teller (BET), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy TEM and the surface area for both support and Cu-Zn were 10.5 and 5.8m(2)/g, respectively. CSR was carried out in a tubular fixed bed reactor (I.D.=19mm) at temperatures between 600 and 800°C with 3-g loadings and (H(2)O/acetic acid) wt. ratio of 9:1. Significantly high (80%) yield of hydrogen was obtained over Cu-Zn/Ca-Al catalyst, as incorporation of Zn enhanced the H(2) yield by reducing deactivation of the catalyst. The coke formation on the support (Ca-12/Al-7) surface was negligible due to the presence of excess oxygen in the 12CaO·7Al(2)O(3) phase.