Emerging trends and advances in valorization of lignocellulosic biomass to biofuels.

Sustainable technologies pave the way to address future energy demand by converting lignocellulosic biomass into fuels, carbon-neutral materials, and chemicals which might replace fossil fuels. Thermochemical and biochemical technologies are conventional methods that convert biomass into value-added products. To enhance biofuel production, the existing technologies should be upgraded using advanced processes. In this regard, the present review explores the advanced technologies of thermochemical processes such as plasma technology, hydrothermal treatment, microwave-based processing, microbial-catalyzed electrochemical systems, etc. Advanced biochemical technologies such as synthetic metabolic engineering and genomic engineering have led to the development of an effective strategy to produce biofuels. The microwave-plasma-based technique increases the biofuel conversion efficiency by 97% and the genetic engineering strains increase the sugar production by 40%, inferring that the advanced technologies enhances the efficiency. So understanding these processes leads to low-carbon technologies which can solve the global issues on energy security, the greenhouse gases emission, and global warming.

Sustainable ecological engineering systems for the treatment of domestic wastewater using emerging, floating and submerged macrophytes.

Water scarcity is perceived as a global systemic risk since there is an inexorable rise in water demand. An ecological engineering system mimics a natural ecosystem by balancing the trophic conditions for effective treatment of wastewater in a sequential manner. The present study was designed using emergent, floating and submerged macrophytic plants in a systematic approach. The study was evaluated with several components such as plants (water hyacinth, water lettuce and water thymes), aeration (supply of oxygen), and physical adsorption (activated carbon). Domestic wastewater collected from the local effluent treatment plant was treated individually and by combining all the components. Diverse experimental setups viz., lake sediment (control reactor), aeration, activated carbon blocks, water hyacinth, water lettuce, and water thymes were individually studied. Further the above components were combined, such as lake sediment + aeration + activated carbon blocks with plants like water hyacinth, water lettuce, and water thymes. The study inferred along with phytoremediation, and the external factors enhanced the treatment performances. Water hyacinth documented enhanced chemical oxygen demand removal efficiency of 85.71%, followed by water lettuce (80%), and water thymes (77.14%) along with the plants, both aeration, and activated carbon had stimulated the wastewater treatment. The highest removal efficiency of nitrate (70.23%), phosphate (63.64%), and sulphate (61.16%) were observed in water hyacinth due to its thick roots, and fibrous tissues reported effective treatment. The study hypothesized that these processes could be an effective strategy to restore the lakes and regulate the environmental flow. The study infers that an ecological engineering system symbiotically enables to self-organize the ecosystem within the boundary.

Carbon credit reduction: A techno-economic analysis of "drop-in" fuel production.

The current study elucidates the fundamentals of technical, financial, and environmental viability of the processes used for sustainable "drop-in" fuel generation. At present, the price of producing "drop-in" fuels is around two times as costly (5-6 USD/gallon) as the cost of fossil fuels (3 USD/gallon), especially when using second-generation feedstocks. Hence, this necessitates a comprehensive techno-economic understanding of the current technologies with respect to "drop-in"-fuel. This entitles technical-economic viability, and environmental sustainability to make the processes involved commercially viable. In this context, the present review addresses unique contrasts among the various processes involved in "drop-in" fuel production. Furthermore, principles and process flow of techno-economic analysis as well as environmental implications in terms of reduced carbon footprint and carbon credit are elucidated to discuss fundamentals of techno-economic analysis in terms of capital and operational expenditure, revenue, simulation, cash flow analysis, mass and energy balances with respect to evidence-based practices. Case specific techno-economic studies with current developments in this field of research with emphasis on software tools viz., Aspen Plus, Aspen HYSIS, Aspen Plus Economic Analyser (APEC) Aspen Icarus Process Evaluator (AIPE) are also highlighted. The study also emphasis on the carbon foot print of biofuels and its carbon credits (Carbon Offset Credits (COCs) and Carbon Reduction Credits (CRCs)) by leveraging a deep technical and robust business-oriented insights about the techno-economic analysis (TEA) exclusively for the biofuel production.

Integrated biorefinery processes for conversion of lignocellulosic biomass to value added materials: Paving a path towards circular economy.

Lignocellulosic biomass is an effective and sustainable alternative for petroleum-derived fuels and chemicals to produce biofuels and bio-based products. Despite the high availability, the degradation of biomass is a substantial challenge. Hence, it is necessary to integrate several unit processes such as biochemical, thermochemical, physical, and catalytic conversion to produce wide range of bio-based products. Integrating these processes enhances the yield, reduces the reaction time, and can be cost-effective. Process integration could significantly lead to various outcomes which guides towards the circular economy. This review addresses integration of several biorefinery processes for the production of multifaceted products. In addition, modern and sustainable biorefinery technologies are discussed to pave the path towards circular economy through the closed-loop approach.

Catalytic microwave preheated co-pyrolysis of lignocellulosic biomasses: A study on biofuel production and its characterization.

In this present study, microwave pre-treatment has been used for sustainable biofuel production from three different biowastes through catalytic aided co-pyrolysis techniques. The experimental investigations have been carried out to develop biofuel at temperature (350-550℃), heating rate (15-50℃/min) and particle size (0.12-0.38 mm). The resultant biofuels were characterized using TGA, DTA, FE-SEM, FTIR spectroscopy and NMR spectrum. The pyrolysis process of biomasses without and with catalyst resulted in the yield rate of 29-37% and 39-51% respectively. Moreover, the CaO catalytic co-pyrolysis process of pomegranate peel, groundnut shell and palmcone wastes with a ratio of 50:50 at 0.25 mm particle size has resulted in the highest yield rate of 51.6%. The NMR result of bio-oil samples produced hydroxyl group and aliphatics which clearly state the suitability of bio-oils for automotive application. The bio-oil had promising fuel characteristics consisting more energy density (29.1 MJ/kg), less oxygen content and free of nitrogen.

State of art of valorising of diverse potential feedstocks for the production of alcohols and ethers: Current changes and perspectives.

Alcohols could be the biggest factor for the improvement of world biofuel economy in the present century due to their excellent properties compared to petroleum products. The primary concerns of sustainable alcohol production for meeting the growing energy demand owing to the selection of viable feedstock and this might enhance the opportunities for developing numerous advanced techniques. In this review, the valorization of alcohol production from several production routes has been exposed by covering the traditional routes to the present state of the art technologies. Even though the fossil fuel conversion could be dominant method for methanol production, many recent innovations like photo electrochemical synthesis and electrolysis methods might play vital role in production of renewable methanol in future. There have been several production routes for production of ethanol and among which the fermentation of lignocellulose biomass would be the ultimate choice for large scale shoot up. The greenhouse gas recovery in the form of alcohols through electrochemistry technique and hydrogenation method are the important methods for commercialization of alcohols in future. It is also observed that algae based renewable bio-alcohols is highly influenced by carbohydrate content and sustainable approaches in algae conversion to bio-alcohols would bring greater demand in future market. There is a lack of innovation in higher alcohols production in single process and this could be bounded by combining dehydrogenation and decarboxylation techniques. Finally, this review enlists the opportunities and challenges of existing alcohols production and recommended the possible routes for making significant enhancement in production.

Bio-electrocatalytic remediation of hydrocarbons contaminated soil with integrated natural attenuation and chemical oxidant.

The present study aimed to assess the possibility of integrating natural attenuation (NA) and chemical oxidation (O) with the bio-electrocatalytic remediation (BET) process to remediate petroleum hydrocarbons contaminated soil. Six different reactors were operated, wherein in the first reactor was a NA system, and the second condition to the NA was supplemented with a chemical oxidant (NAO). These systems were compared with BET systems which were differentiated based on the position and distance between the electrodes. The study was performed by considering NA as a common condition in all the six different reactors viz., NA, NAO, NA + BET with 0.5 cm space amid electrodes (BETH-0.5), NAO + BET with 0.5 cm space amid electrodes (BETOH-0.5), NAO + BET with 1.0 cm space amid electrodes (BETOH-1.0), and NAO + BET with vertical electrodes at 1.0 cm distance (BETOV-1.0). The highest total petroleum hydrocarbons (TPH) degradation efficiency was observed with BETOH-0.5 (67 ± 0.8%) followed by BETOH-1.0 (62 ± 0.6%), BETH-0.5 (60%), BETOV-1.0 (56 ± 0.5%), NAO (46.6%), and NA (27.7%). In NA, the indigenous microorganisms remediate the organic contaminants. In the NAO system, KMnO4 actively breakdown the carbon-carbon double bond functional group. Further, in BETOH-0.5, an anodophilic bacteria enriched around the electrode reported enhanced treatment efficiency along with a maximum of 260 mV (1.65 mA). BET systems integrated with chemical oxidation processes were much more effective in the TPH removal process than an individual process. The BET method adopted here thus provides a good opportunity for bio-electrocatalytic remediation of TPH and resource recovery in the form of bioelectricity.

Biodegradable and non-biodegradable fraction of municipal solid waste for multifaceted applications through a closed loop integrated refinery platform: Paving a path towards circular economy.

An increase in population, rapid urbanization and industrialization has accelerated the rate of municipal solid waste generation. The current disposal of solid waste is a burgeoning issue and it's in immediate need to shift the existing disposal processes to a sustainable manner. Circular economy (CE) is a conceptual model which is been used for better use of resources and minimization of waste in a closed loop approach which could be appropriate for waste management. In this context, the present review illustrates the effective use of biodegradable and non-biodegradable fraction of solid waste in a closed loop integrated refinery platforms for the recovery of bioenergy resources and for the production of value added products. The biodegradable fraction of solid waste could be treated by advanced biological processes with the simultaneous production of bioenergy such as biohydrogen, biomethane, bioelectricity, etc., and other value added products like butanol, ethanol, methanol etc. The scheme illustrates the closed loop approach, the bioenergy generated from the biodegradable fraction of solid waste could be used for the operation of internal combustion engines and the energy could be further used for processing the waste. The non-biodegradable fraction of solid waste could be used for construction and pavement processes. Overall the study emphasizes the paradigm shift of solid waste management concepts from linear economy to a circular economy following the "Zero Waste" concept. The study also explains the circular economy policies practiced for solid waste management that stimulates the economy of the country and identify the pathways to maximize the local resources. In addition the review addresses the advanced information and communication technologies to unfold the issues and challenges faced in the solid waste management. The smart governance of managing waste using the "Internet of Things" (IoT) is one of the great precursors of technological development that could lead innovations in waste management.

Stacking of microbial fuel cells with continuous mode operation for higher bioelectrogenic activity.

The effect of stacking multiple microbial fuel cells for stable power output was evaluated in continuous mode operation. Three single chambered air cathode CMFCs with Nafion (CMFCN), Terry cotton (CMFCT) as membranes and one without membrane (CMFCML) were operated in continuous mode. Maximum power density (PD) and COD removal efficiency was obtained for CMFCN (0.1 W/m2, 50%) followed by CMFCML (0.062 W/m2, 47%) and CMFCT (0.025 W/m2, 39%) and were stable throughout the operation. To increase the power output further, stacking of CMFCs was carried in series/parallel circuitry, which yielded high power density in parallel (2.0 W/m2; 7.2 W/m3) and high voltage in series (1.1 V). Study also evidenced that stacking resulted in high and stable bioelectricity by minimizing the electron losses in comparison to individual CMFCs operation. Stable and high power output signifies the impact of continuous mode operation that constantlty replenishes the substrate.

Multi-electrode bioelectrochemical system for the treatment of high total dissolved solids bearing chemical based wastewater.

Multi-electrode bioelectrochemical treatment system (ME-BET; membrane less) consisting of six electrode assemblies (E1-E6) was designed and fabricated for the treatment of complex chemical based wastewater with high salt concentration. The performance was compared with single electrode assembly BET reactor (SE-BET). Enhanced TDS and COD removal was observed in ME-BET (32%; 56%) compared to SE-BET (15%; 23%) as a result of in situ bio-potential from multi-electrodes through the oxidation of organic substrate in the wastewater. Inorganic pollutants viz., nitrates (28%; 8%), sulphates (25%; 9%) and phosphates (20%; 7%) removal was higher in ME-BET in comparison with SE-BET and this was also supported with bioelectrogenic activity (584; 160mW/m3). The study infers that designing of compact reactors with multiple electrodes in a single system enhances the anodic reactions and enable effective treatment of complex wastewaters with simultaneous power production.

Microbial mediated desalination for ground water softening with simultaneous power generation.

A novel three-chambered microbial desalination cell (MDC) was designed for evaluating desalination of synthetic ground water with simultaneous energy generation and resource recovery. The specific design enabled efficient interelectrode communication by reducing the distance of separation and also maintained an appropriate surface area to volume ratio. MDC were evaluated in different circuitry modes (open and closed) to assess the desalination efficiency, bioelectricity generation, resource recovery, substrate utilization and bioelectrokinetics. The closed circuit operation has showed efficient desalination efficiency (51.5%) and substrate utilization (70%). Owing to the effective electron transfer kinetics, closed circuit mode of operation showed effective desalination of the synthetic ground water with simultaneous power production (0.35W/m2). Circuitry specific biocatalyst activity was observed with higher peak currents (10.1mA; -5.98mA) in closed circuit mode. MDC can function as sustainable and alternative solution for ground and surface water treatment with power productivity and resource recovery.

Functional behavior of bio-electrochemical treatment system with increasing azo dye concentrations: Synergistic interactions of biocatalyst and electrode assembly.

Treatment of dye bearing wastewater through biological machinery is particularly challenging due to its recalcitrant and inhibitory nature. In this study, functional behavior and treatment efficiency of bio-electrochemical treatment (BET) system was evaluated with increasing azo dye concentrations (100, 200, 300 and 500mg dye/l). Maximum dye removal was observed at 300mg dye/l (75%) followed by 200mg dye/l (65%), 100mg dye/l (62%) and 500mg dye/l (58%). Concurrent increment in dye load resulted in enhanced azo reductase and dehydrogenase activities respectively (300mg dye/l: 39.6U; 4.96µg/ml). Derivatives of cyclic voltammograms also supported the involvement of various membrane bound redox shuttlers, viz., cytochrome-c, cytochrome-bc1 and flavoproteins during the electron transfer. Bacterial respiration during BET operation utilized various electron acceptors such as electrodes and dye intermediates with simultaneous bioelectricity generation. This study illustrates the synergistic interaction of biocatalyst with electrode assembly for efficient treatment of azo dye wastewater.

A Circular Bioeconomy with Biobased Products from CO2 Sequestration.

The unprecedented climate change influenced by elevated concentrations of CO2 has compelled the research world to focus on CO2 sequestration. Although existing natural and anthropogenic CO2 sinks have proven valuable, their ability to further assimilate CO2 is now questioned. Thus, we highlight here the importance of biological sequestration methods as alternate and viable routes for mitigating climate change while simultaneously synthesizing value-added products that could sustainably fuel the circular bioeconomy. Four conceptual models for CO2 biosequestration and the synthesis of biobased products, as well as an integrated CO2 biorefinery model, are proposed. Optimizing and implementing this biorefinery model might overcome the limitations of existing sequestration methods and could help realign the carbon balance.

Bioelectrogenic role of anoxic microbial anode in the treatment of chemical wastewater: microbial dynamics with bioelectro-characterization.

A membrane-less anoxic bioelectrochemical treatment (AxBET) system was evaluated to study the influence of bioelectrogenic activity during the treatment of chemical wastewater (CW). Increment in power generation was observed with increase in substrate loading (61-204 mW/m(2)) indicating the ability of anodic bacteria in BET system to utilize the complex chemicals as the sole carbon source. Derivative analysis of voltammograms depicted by positive and negative peak potentials which relate to the extracellular electron transport sites (EETs) that presumably play a significant role in electron transfer. These self-driven redox mediators varied with respect to the substrate load. The microbial population was dominated by anaerobic microorganisms which are commonly involved in effluent treatment plants during the initial phase of operation. A gradual shift in the microbial community was observed towards enrichment of electrogenically active bacteria belonging to phyla viz., Firmicutes and Proteobacteria after prolonged operation. Shannon Index and principal component analysis correlated with the microbial profile studies. The feasibility of self-driven bioremediation of chemical wastewater in an AxBET system demonstrated bioelectricity production along with multipollutant removal simultaneously.

Reductive behaviour of acid azo dye based wastewater: Biocatalyst activity in conjunction with enzymatic and bio-electro catalytic evaluation.

Present study illustrates the significance of biocatalyst's reductive behaviour in the degradation of dye molecules using glucose as co-substrate. An anaerobic system was operated at a dye concentration of 50mg/l with an organic loading rate (OLR) of 1.36 kg COD/m(3)-day. Decolourization and COD removal efficiencies were observed to be 42% and 48% respectively. Azo reductase (18.9 U) and dehydrogenase enzyme (1.4 µg/ml) activities showed increment with operation time. Anaerobic microenvironment showed dye reduction converting them into aromatic amines. The presence of mediators viz., cytochromes, quinines and Fe-S proteins depicted in the cyclic voltammetry profiles played a crucial role in transfer of electrons for the reduction of dye molecules. Bio-electro kinetic profiles obtained through Tafel analysis showed persistent reduction behaviour, which is in good correlation with dye degradation in the anaerobic microenvironment.

Integrating sequencing batch reactor with bio-electrochemical treatment for augmenting remediation efficiency of complex petrochemical wastewater.

The present study evaluates the sequential integration of two advanced biological treatment methods viz., sequencing batch reactor (SBR) and bioelectrochemical treatment systems (BET) for the treatment of real-field petrochemical wastewater (PCW). Initially two SBR reactors were operated in aerobic (SBR(Ae)) and anoxic (SBR(Ax)) microenvironments with an organic loading rate (OLR) of 9.68 kg COD/m(3)-day. Relatively, SBR(Ax) showed higher substrate degradation (3.34 kg COD/m(3)-day) compared to SBR(Ae) (2.9 kg COD/m(3)-day). To further improve treatment efficiency, the effluents from SBR process were fed to BET reactors. BET(Ax) depicted higher SDR (1.92 kg COD/m(3)-day) with simultaneous power generation (17.12 mW/m(2)) followed by BET(Ae) (1.80 kg COD/m(3)-day; 14.25 mW/m(2)). Integrating both the processes documented significant improvement in COD removal efficiency due to the flexibility of combining multiple microenvironments sequentially. Results were supported with GC-MS and FTIR, which confirmed the increment in biodegradability of wastewater.

Anoxic bio-electrochemical system for treatment of complex chemical wastewater with simultaneous bioelectricity generation.

Bioelectrochemical treatment system (BET) with anoxic anodic microenvironment was studied with chemical wastewater (CW) in comparison with anoxic treatment (AxT, sequencing batch reactor (SBR)) with same parent anaerobic consortia. BET system documented relatively higher treatment efficiency at higher organic load (5.0 kg COD/m(3)) accounting for COD removal efficiency of (90%) along with nitrate (48%), phosphate (51%), sulphates (68%), colour (63%) and turbidity (90%) removal, compared to AxT operation (COD, 47%; nitrate, 36%; phosphate, 32%; sulphate, 35%; colour, 45% and turbidity, 54%). The self-induced bio-potential developed due to the electrode assembly in BET resulted in effective treatment with simultaneous bioelectricity generation (631 mA/m(2)). AxT operation showed persistent reduction behaviour, while simultaneous redox behaviour was observed with BET indicating balanced electron transfer. BET operation illustrated higher wastewater toxicity reduction compared to the AxT system which documents the variation in bio-electrocatalytic behaviour of same consortia under different microenvironment.

Microbial catalyzed electrochemical systems: a bio-factory with multi-facet applications.

Microbial catalyzed electrochemical systems (MCES) have been intensively pursued in both basic and applied research as a futuristic and sustainable platform specifically in harnessing energy and generating value added bio-products. MCES have documented multiple/diverse applications which include microbial fuel cell (for harnessing bioelectricity), bioelectrochemical treatment system (waste remediation), bioelectrochemical system (bio-electrosynthesis of various value added products) and microbial electrolytic cell (H2 production at lower applied potential). Microorganisms function as biocatalyst in these fuel cell systems and the resulting electron flux from metabolism plays pivotal role in bio-electrogenesis. Exo-electron transfer machineries and strategies that regulate metabolic flux towards exo-electron transport were delineated. This review addresses the contemporary progress and advances made in MCES, focusing on its application towards value addition and waste remediation.

Acid azo dye remediation in anoxic-aerobic-anoxic microenvironment under periodic discontinuous batch operation: bio-electro kinetics and microbial inventory.

Functional behavior of anoxic-aerobic-anoxic microenvironment on azo dye (C.I. Acid black 10B) degradation was evaluated in a periodic discontinuous batch mode operation for 26 cycles. Dye removal efficiency and azo-reductase activity (30.50 ± 1 U) increased with each feeding event until 13th cycle and further stabilized. Dehydrogenase activity also increased gradually and stabilized (2.0 ± 0.2 µg/ml) indicating the stable proton shuttling between metabolic intermediates providing higher number of reducing equivalents towards dye degradation. Voltammetric profiles showed drop in redox catalytic currents during stabilized phase also supports the consumption of reducing equivalents towards dye removal. Change in Tafel slopes, polarization resistance and other bioprocess parameters correlated well with the observed dye removal and biocatalyst behavior. Microbial community analysis documented the involvement of specific organism pertaining to aerobic and facultative functions with heterotrophic and autotrophic metabolism. Integrating anoxic microenvironment with aerobic operation might have facilitated effective dye mineralization due to the possibility of combining redox functions.

Biocatalyst behavior under self-induced electrogenic microenvironment in comparison with anaerobic treatment: evaluation with pharmaceutical wastewater for multi-pollutant removal.

Biocatalyst behavior was comparatively evaluated under diverse microenvironments viz., self-induced electrogenic (bioelectrochemical treatment, BET) and anaerobic treatment (AnT) microenvironments, with real-field pharmaceutical wastewater. Relatively higher treatment efficiency was observed with BET (COD removal, 78.70%) over AnT (32%) along with the power output. Voltammetric profiles of AnT showed persistent reduction behavior, while BET depicted simultaneous redox behavior. BET operation documented significantly higher bio-electrocatalytic activity (kapp, 245.22 s(-1)) than AnT (kapp, 7.35 s(-1)). The electron accepting conditions due to the presence of electrode in the BET might contributed to higher electrogenesis leading to enhanced substrate degradation along with the removal of multiple pollutants accounting for the effective reduction of toxicity levels of wastewater. Even at higher organic loads, BET operation showed good treatment efficiency without process inhibition. Introduction of electrode-membrane assembly in anaerobic microenvironment showed significant change in the electrocatalytic behavior of biocatalyst resulting in enhanced treatment of complex wastewater.