Selective production of phenolic monomer via catalytic depolymerization of lignin over cobalt-nickel-zirconium dioxide catalyst.

The utilization of lignin, an abundant and renewable bio-aromatic source, is of significant importance. In this study, lignin oxidation was examined at different temperatures with zirconium oxide (ZrO2)-supported nickel (Ni), cobalt (Co) and bimetallic Ni-Co metal catalysts under different solvents and oxygen pressure. Non-catalytic oxidation reaction produced maximum bio-oil (35.3 wt%), while catalytic oxidation significantly increased the bio-oil yield. The bimetallic catalyst Ni-Co/ZrO2 produced the highest bio-oil yield (67.4 wt%) compared to the monometallic catalyst Ni/ZrO2 (59.3 wt%) and Co/ZrO2 (54.0 wt%). The selectively higher percentage of vanillin, 2-methoxy phenol, acetovanillone, acetosyringone and vanillic acid compounds are found in the catalytic bio-oil. Moreover, it has been observed that the bimetallic Co-Ni/ZrO2 produced a higher amount of vanillin (43.7% and 13.30 wt%) compound. These results demonstrate that the bimetallic Ni-Co/ZrO2 catalyst promotes the selective cleavage of the ether ß-O-4 bond in lignin, leading to a higher yield of phenolic monomer compounds.

Trigeneration based on the pyrolysis of rural waste in India: Environmental impact, economic feasibility and business model innovation.

Pyrolysis-based waste-to-bioenergy development has the potential to resolve some of the major challenges facing rural communities in India such as poor electrification, household air pollution, and farmland degradation and contamination. Existing understanding and analysis of the economic feasibility and environmental impact of bioenergy deployment in rural areas is limited by parameter uncertainties, and relevant business model innovation following economic evaluation is even scarcer. This paper uses findings from a new field survey of 1200 rural households to estimate the economic feasibility and environmental impact of a pyrolysis-based bioenergy trigeneration development that was designed to tackle these challenges. Based on the survey results, probability distributions were constructed and used to supply input parameters for cost-benefit analysis and life cycle assessment. Monte Carlo simulation was applied to characterise the uncertainties of economic feasibility and environmental impact accounting. It was shown that the global warming potential of the development was 350 kg of CO2-eq per capita per annum. Also, the survey identified a significant mismatch between feedstock prices considered in the literature and prices asked for by the surveyed villagers. The results of the cost-benefit analysis and life cycle assessment were then applied to propose two novel business models inspired by the Business Model Canvas, which had the potential to achieve up to 90 % economic profitability and result in a benefit-cost ratio of 1.35-1.75. This is the first study achieving combined environmental and economic analysis and business model innovation for rural bioenergy production in developing countries.

Characterization of slow pyrolysis products from three different cashew wastes.

A huge amount of waste is generated by the cashew processing industries. This study aims to valorise these cashew wastes generated at different levels while processing cashew nuts in factories. The feedstocks include cashew skin, cashew shell and cashew shell de-oiled cake. Slow pyrolysis of these three different cashew wastes was performed at varying temperatures (300-500℃) at a heating rate of 10℃/min in a lab scale glass-tubular reactor under inert atmosphere of nitrogen with flow rate of 50 ml/min. The total bio-oil yield for cashew skin and the de-oiled shell cake was 37.1 and 48.6 wt% at 400℃ and 450℃, respectively. However, the maximum bio-oil yield obtained for cashew shell waste was 54.9 wt% at 500℃. The bio-oil was analysed using GC-MS, FTIR, and NMR. Along with the various functionalities observed in bio-oil through GC-MS, phenolics were observed to have maximum area% for all the feedstocks at all temperatures. At all the slow pyrolysis temperatures, cashew skin led to more biochar yield (40 wt%) as compared to cashew de-oiled cake (26 wt%) and cashew shell waste (22 wt%). Biochar was characterized by various analytical tools such as XRD, FTIR, Proximate analyser, CHNS, Py-GC/MS and SEM. Characterization of biochar revealed its carbonaceous and amorphous nature along with porosity.

Investigations into pyrolytic behaviour of spent citronella waste: Slow and flash pyrolysis study.

Slow and flash pyrolysis of spent citronella biomass has been studied at varying temperatures. It is aimed to understand the pyrolytic behavior of spent citronella aromatic biomass with temperatures. Maximum bio-oil yield of 37.7 wt% was obtained with conversion of 71 wt% at 450 °C through slow pyrolysis. GC/MS, 1H NMR, and FTIR analysis of pyrolytic liquid (bio-oil) was done which indicated various functionalities with maximum area% for phenolics. However, flash pyrolysis at high heating rate of 20 °C/ms resulted into maximum area% for carbonyls at all temperatures. In addition, an increasing trend for phenolics with temperature was also observed. The properties of obtained biochar are analysed by CHNS, FTIR, TOC, XRD, and SEM, which confirmed the significant decomposition of biomass constituents. The characterisation results revealed the potential usage of pyrolytic liquid i.e., bio-oil and pyrolytic residue i.e., biochar for different applications.

Biochar for Supercapacitor Application: A Comparative Study.

Biochar is a carbon-rich solid that can be prepared through heat treatment of biomass under an inert atmosphere. In the present work, biochar prepared from different feedstocks, namely, Litchi chinensis (Litchi) seeds, Syzygium cumini (Jamun) seeds, and pine cone, were evaluated for charge storage in the form of supercapacitors. The physicochemical and electrochemical properties of the biochar were highly dependent on the preparation temperature and the choice of feedstock. Among the three feedstocks, Litchi seed-derived biochar showed the highest specific capacitance of 190 F g-1 at 1 A g-1 in a symmetric cell configuration. N and O heteroatom functionalities in the Litchi seed-derived biochar, higher specific surface area, and pore volume for electrolyte adsorption were responsible for its superior capacitive performance as compared to Jamun seeds and pine cone biochar.

Oxidative catalytic valorization of industrial lignin into phenolics: Effect of reaction parameters and metal oxides.

Oxidative depolymerization of an industrial lignin was performed to study the effect of various metal oxides in oxygen and air atmosphere. CeO2 exhibited excellent catalytic property, and promoted the production of bio-oil yield up to a maximum of 49 wt% in 10 bar O2, whereas 31 wt% bio-oil was noticed in atmospheric air. GC-MS analysis of bio-oil showed that high selectivity towards acetosyringone was observed in the presence of air (70.5 area%) as compared to oxygen (48.1 area%). Herein, we have also applied transitional metals (Co, Mn and Cu) doped CeO2 catalysts. Compared to Cu and Mn, Co metal showed efficient activity that promoted the breaking of labile ß-O-4 linkages via the conversion of Cα-OH in to carbonyl group in atmospheric air resulting in the formation of acetosyringone up to 78 area%. Moreover, it exhibited excellent catalytic activity up to four successive cycles. Catalyst has been characterized by XRD, BET, TEM, FT-IR and Raman spectroscopy.

Hydrothermal oxidative valorisation of lignin into functional chemicals: A review.

Lignin is a waste by-product of bio-refineries and paper-pulp industries. It has an attractive potential to produce numerous valuable chemicals due to its highly aromatic character. At present, large amount of lignin is burnt as a source of energy due to lack of suitable efficient lignin valorisation processes. The challenge exists in handling its complex heterogeneous structure and bond breaking at selective locations. The production of high value chemicals/petrochemical feedstocks will improve the economic viability of a bio-refinery. Oxidative depolymerization is a promising way to produce functional compounds from lignin. The aim of the current review is to present the novel methodologies currently used in the area of lignin oxidative depolymerization including effect of temperature, residence time, solvent, oxidizing agents, homogeneous and heterogeneous catalysis etc. It aims to present an insight into the structure of lignin and its breakdown mechanism.

Oxidative valorisation of lignin into valuable phenolics: Effect of acidic and basic catalysts and reaction parameters.

The aromatic nature of lignin makes it a good source for the production of numerous platform chemicals. The valorization of lignin into valuable compounds depends upon the type of bonds and functionality present in lignin. Here, we have studied the depolymerization of rice straw alkali lignin in N2 and O2 with acidic (ZSM-5), basic (MgO) catalyst and with their mixtures (1:1, 3:7 and 7:3). The effect of hydrogen peroxide on lignin depolymerization was also examined. Maximum yield of bio-oil (50 wt%) was obtained with pure ZSM-5 and 1 ml hydrogen peroxide in nitrogen atmosphere, while maximum conversion (60%) was observed in oxygen environment during the non-catalytic depolymerization of lignin. Bio-oil characterization through GC-MS showed maximum selectivity towards 2-methoxy-4-vinylphenol with 38.5 area% in the bio-oil of ZSM-5-N2. The bio-oils have also been characterized using 1H NMR, FT-IR and GC-MS.

Catalytic hydrothermal liquefaction of alkali lignin over activated bio-char supported bimetallic catalyst.

Carbon-based support catalysts are beneficial on account of low material cost, prominent surface area, and stability at high temperature. In this study, biochar derived activated carbon (AC) supported metal catalysts were tested for hydrothermal liquefaction (HTL) of alkali lignin. Catalytic HTL of alkali lignin was carried out at various temperatures (260 to 300 °C) with varying catalysts quantity (5 to 20 wt%), and solvents (water, ethanol, methanol) for 15 min reaction time. As the reaction temperature increased from 260 to 300 °C, conversion increased from 76.2 to 85.5 wt%. Bimetallic catalyst Ni-Co/AC with ethanol solvent system at 280 °C gave highest bio-oil yield (72.0 wt%). Lignin catalytic depolymerization produces monomer phenolic compounds due to efficient breaking of the lignin macromolecule. Thus, the presence of catalyst and solvent increased the cleavage of ß-O-4 bonds resulting in increased selectivity towards vanillin (32.3-36.2%).

Pyrolysis of de-oiled yeast biomass of Rhodotorula mucilaginosa IIPL32: Kinetics and thermodynamic parameters using thermogravimetric analysis.

The increasing demand for natural resources has highlighted the need to search for unutilized carbon resource that satisfy the demand and pose a minor threat to the environment. Yeast is a microbe with large industrial applications, and the biomass leftover after fermentation needs utilization for achieving increased efficiency. De-oiled yeast biomass (DYB), the residue after yeast lipid extraction, has not yet been evaluated for its potential application in the pyrolysis process. The present study was performed to understand its detailed pyrolysis kinetics. The observed activation energy (87-216 KJ/mol), random nucleation mechanism, pre-exponential factor (7.87 × 1031-3.24 × 1031/min), and thermodynamic profile showed the DYB pyrolysis process to be feasible. .

A review on the production of renewable aviation fuels from the gasification of biomass and residual wastes.

This article reviews the production of renewable aviation fuels from biomass and residual wastes using gasification followed by syngas conditioning and Fischer-Tropsch catalytic synthesis. The challenges involved with gasifying wastes are discussed along with a summary of conventional and emerging gasification technologies. The techniques for conditioning syngas including removal of particulate matter, tars, sulphur, carbon dioxide, compounds of nitrogen, chlorine and alkali metals are reported. Recent developments in Fischer-Tropsch synthesis, such as new catalyst formulations are described alongside reactor technologies for producing renewable aviation fuels. The energy efficiency and capital cost of converting biomass and residual wastes to aviation fuels are major barriers to widespread adoption. Therefore, further development of advanced technologies will be critical for the aviation industry to achieve their stated greenhouse gas reduction targets by 2050.

Advances in the thermo-chemical production of hydrogen from biomass and residual wastes: Summary of recent techno-economic analyses.

This article outlines the prospects and challenges of hydrogen production from biomass and residual wastes, such as municipal solid waste. Recent advances in gasification and pyrolysis followed by reforming are discussed. The review finds that the thermal efficiency of hydrogen from gasification is ~50%. The levelized cost of hydrogen (LCOH) from biomass varies from ~2.3-5.2 USD/kg at feedstock processing scales of 10 MWth to ~2.8-3.4 USD/kg at scales above 250 MWth. Preliminary estimates are that the LCOH from residual wastes could be in the range of ~1.4-4.8 USD/kg, depending upon the waste gate fee and project scale. The main barriers to development of waste to hydrogen projects include: waste pre-treatment, technology maturity, syngas conditioning, the market for clean hydrogen, policies to incentivize pioneer projects and technology competitiveness. The main opportunity is to produce low cost clean hydrogen, which is competitive with alternative production routes.

Pyrolysis of azolla, sargassum tenerrimum and water hyacinth for production of bio-oil.

Pyrolysis of azolla, sargassum tenerrimum and water hyacinth were carried out in a fixed-bed reactor at different temperatures in the range of 300-450°C in the presence of nitrogen (inert atmosphere). The objective of this study is to understand the effect of compositional changes of various aquatic biomass samples on product distribution and nature of products during slow pyrolysis. The maximum liquid product yield of azolla, sargassum tenerrimum and water hyacinth (38.5, 43.4 and 24.6wt.% respectively) obtained at 400, 450 and 400°C. Detailed analysis of the bio-oil and bio-char was investigated using 1H NMR, FT-IR, and XRD. The characterization of bio-oil showed a high percentage of aliphatic functional groups and presence of phenolic, ketones and nitrogen-containing group. The characterization results showed that the bio-oil obtained from azolla, sargassum tenerrimum and water hyacinth can be potentially valuable as a fuel and chemicals.

Non-isothermal kinetic study of de-oiled seeds cake of African star apple (Chrosophyllum albidum) using thermogravimetry.

Thermal decomposition and kinetics behaviour of the de-oiled seed cake of African star apple (Chrosophyllum albidum) has been investigated using thermogravimetry under the nitrogen atmosphere from ambient temperature to 900 °C. The thermogravimetric data for the cake decomposition at six different heating rates (5, 10, 15, 20, 30 and 40 °C/min) were used to evaluate the kinetic decomposition of the cake using Friedman (FD), Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) models. Thermal decomposition of the cake showed thermograms indicating dehydration and devolitilization stages (200-400 °C). The maximum temperature for the decomposition of the cake (Tmax) increases from 289.42-335.96 °C with increase in heating rates. The average apparent activation energy (Ea) values of 153.15, 145.14 and 147.15 kJ/mol were calculated using Friedman, Kissinger-Akahira-Sunose, and Flynn-Wall-Ozawa models respectively. The extent of mass conversion (α) shows dependence on apparent activation Ea values which is an evidence of multi-step decomposition kinetic. The thermal profile and kinetic data obtained could be helpful in evaluating the thermal stability of the cake as well as modeling, designing and developing a thermo-chemical system for the conversion of the cake to fuel.

Slow pyrolysis of prot, alkali and dealkaline lignins for production of chemicals.

Effect of different lignins were studied during slow pyrolysis. Maximum bio-oil yield of 31.2, 34.1, and 29.5wt.% was obtained at 350, 450 and 350°C for prot lignin, alkali lignin and dealkaline lignin respectively. Maximum yield of phenolic compounds 78%, 80% and 92% from prot lignin, alkali and dealkaline lignin at 350, 450 and 350°C. The differences in the pyrolysis products indicated the source of lignins such as soft and hard wood lignins. The biochar characterisation revealed that the various ether linkages were broken during pyrolysis and lignin was converted into monomeric substituted phenols. Bio-oil showed that the relative contents of each phenolic compound changes significantly with pyrolysis temperature and also the relative contents of each compound changes with different samples.

Opportunities for utilization of non-conventional energy sources for biomass pretreatment.

The increasing concerns over the depletion of fossil resources and its associated geo-political issues have driven the entire world to move toward sustainable forms of energy. Pretreatment is the first step in any biochemical conversion process for the production of valuable fuels/chemicals from lignocellulosic biomass to eliminate the lignin and produce fermentable sugars by hydrolysis. Conventional techniques have several limitations which can be addressed by using them in tandem with non-conventional methods for biomass pretreatment. Electron beam and γ (gamma)-irradiation, microwave and ultrasound energies have certain advantages over conventional source of energy and there is an opportunity that these energies can be exploited for biomass pretreatment.