Machine learning aided experimental approach for evaluating the growth kinetics of Candida antarctica for lipase production.

A hybrid machine learning (ML) aided experimental approach was proposed in this study to evaluate the growth kinetics of Candida antarctica for lipase production. Different ML models were trained and optimized to predict the growth curves at various substrate concentrations. Results on comparison demonstrate the superior performance of the Gradient boosting regression (GBR) model in growth curves prediction. GBR-based growth kinetics was found to be matching well with the results of the conventional experimental approach while significantly reducing the experimental effort, time, and resources by âˆ¼ 50%. Further, the activity and enzyme kinetics of lipase produced in this study was investigated on hydrolysis of p-nitrophenyl butyrate resulting in a maximum lipase activity of 24.07 U at 44 h. The robustness and significance of developed kinetic models were ensured through detailed statistical analysis. The application of the proposed hybrid approach can be extended to any other microbial process.

Determination of risk of spontaneous waste ignition and leachate quality for open municipal solid waste dumpsite.

The waste receiving capacity of most municipal solid waste (MSW) landfill sites in India is exhausted, resulting in the formation of larger waste heaps. In the majority of Indian cities, these old waste heaps are prone to frequent smoldering and ignition resulting into fires. In this study, the potential risk of spontaneous ignition of landfilled waste at landfill surface was analyzed based on the physico-chemical characteristics of waste, carbon monoxide (CO) levels, landfill surface temperature (LST). The leachate pollution index was also determined to analyze the leachate quality for three different seasons (monsoon, pre-monsoon and post-monsoon). The regression analysis was carried out to understand the thermal properties (smoldering temperature, smoldering time, ignition temperature etc.) of MSW. The results showed that old waste has a higher tendency to undergo ignition compared to fresh waste. It has also been observed that the lower MC of old waste samples in the range of 3.4% and 18.2% is the most likely cause of early smoldering (106.6-109.5 °C) and ignition (198.6-208.4 °C) of old waste. In pre-monsoon season, CO concentrations for sub-surface (10-30 cm depth) smoldering events (SSE) were observed to be between âˆ¼ 150 to 200 ppm. This CO level substantially dropped to 10 ± 1 ppm in the post-monsoon season. The estimation of the leachate pollution index (LPI) showed an index score of 27.35, 30.47 and 10.71 for pre-monsoon, monsoon and post-monsoon seasons, respectively. The determination of CO levels, increased LST and physico-chemical properties of landfilled waste will greatly assist in the abatement of environmental pollution arising from landfill fires.

Leveraging Cu/CuFe2O4-Catalyzed Biomass-Derived Furfural Hydrodeoxygenation: A Nanoscale Metal-Organic-Framework Template Is the Prime Key.

Enormous efforts have been initiated in the production of biobased fuels and value-added chemicals via biorefinery owing to the scarcity of fossil resources and huge environmental synchronization. Herein, non-noble metal-based metal/mixed metal oxide supported on carbon employing a metal-organic framework as a sacrificial template is demonstrated for the first time in the selective hydrodeoxygenation (HDO) of biomass-derived furfural (FFR) to 2-methyl furan (MF). The aforementioned catalyst (referred to as Cu/CuFe2O4@C-A) exhibited extraordinary catalytic proficiency (100% selectivity toward MF) compared with the conventional Cu/CuFe2O4@C-B catalyst which was prepared by the wet impregnation method. High-resolution transmission electron microscopy and synchrotron X-ray diffraction studies evidenced the existence of both metal (Cu) and mixed metal oxide (CuFe2O4) phases, in which the metal could help in hydrogenation to alcohol and metal oxide could assist in the hydroxyl group removal step during HDO reaction. The stabilization of encapsulated metal/metal oxide nanoparticles in the carbon matrix, modulation of the electronic structure, and regulation of geometric effects in the Cu/CuFe2O4@C-A are thought to play an important role in its excellent catalytic performance, confirmed by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy investigations. Furthermore, the structure and activity interconnection was confirmed by in situ attenuated total reflection-IR studies, which manifested the strong interfacial interaction between FFR and the Cu/CuFe2O4@C-A catalyst. This finding was further supported by NH3 temperature-programmed desorption analysis, which suggested that the presence of more Lewis/weak acidic sites in this catalyst was beneficial for the hydrogenolysis step in HDO reaction. Additionally, H2 temperature-programmed reduction studies revealed that the adsorption of H2 was stronger on the Cu/CuFe2O4@C-A than that over the conventional Cu/CuFe2O4@C-B catalyst; thus, the former catalyst promoted activation of H2. A detailed kinetic analysis which demonstrated the lower activation energy barrier along with dual active sites attributed for the activation of the two separate reactions in the HDO process on the Cu/CuFe2O4@C-A catalyst. This work has great implication in developing a highly stable catalyst for the selective upgradation of biomass without deactivation of metal sites in extended catalytic cycles and opens the door of opportunity for developing a sustainably viable catalyst in biomass refinery industries.

Porous Organic Polymer-Driven Evolution of High-Performance Cobalt Phosphide Hybrid Nanosheets as Vanillin Hydrodeoxygenation Catalyst.

Hydrodeoxygenation (HDO) is a promising route for the upgrading of bio-oils to eco-friendly biofuel produced from lignocellulose. Herein, we report the sequential synthesis of a hybrid nanocatalyst CoxP@POP, where substoichiometric CoxP nanoparticles are distributed in a porous organic polymer (POP) via solid-state phosphidation of the Co3O4@POP nanohybrid system. We also explored the catalytic activity of the above two nanohybrids toward the HDO of vanillin, a typical compound of lignin-derived bio-oil to 2-methoxy-4-methylphenol, which is a promising future biofuel. The CoxP@POP exhibited superior catalytic activity and selectivity toward desired product with improved stability compared to the Co3O4@POP. Based on advanced sample characterization results, the extraordinary selectivity of CoxP@POP is attributed to the strong interaction of the cation of the CoxP nanoparticle with the POP matrix and the consequent modifications of the electronic states. Through attenuated total reflectance-infrared spectroscopy, we have also observed different interaction strengths between vanillin and the two catalysts. The decreased catalytic activity of Co3O4@POP compared to CoxP@POP catalyst could be attributed to the stronger adsorption of vanillin over the Co3O4@POP catalyst. Also from kinetic investigation, it is clearly demonstrated that the Co3O4@POP has higher activation energy barrier than the CoxP@POP, which also reflects to the reduction of the overall efficiency of the Co3O4@POP catalyst. To the best of our knowledge, this is the first approach in POP-encapsulated cobalt phosphide catalyst synthesis and comprehensive study in establishing the structure-activity relationship in significant step-forwarding in promoting biomass refining.

Removal of mercury from an alumina refinery aqueous stream.

Digestion condensate is formed as a by-product of the alumina refinery digestion process. The solution exhibits a high pH and is chemically reducing, containing many volatile species such as water, volatile organics, ammonia, and mercury. Because digestion condensate is chemically unique, an innovative approach was required to investigate mercury removal. The mercury capacity and adsorption kinetics were investigated using a number of materials including gold, silver and sulphur impregnated silica and a silver impregnated carbon. The results were compared to commercial sorbents, including extruded and powdered virgin activated carbons and a sulphur impregnated mineral. Nano-gold supported on silica (88% removal under batch conditions and 95% removal under flow conditions) and powdered activated carbon (91% under batch conditions and 98% removal under flow conditions) were the most effective materials investigated. The silver and sulphur impregnated materials were unstable in digestion condensate under the test conditions used.

Wet peroxide oxidation and catalytic wet oxidation of stripped sour water produced during oil shale refining.

Catalytic wet oxidation (CWO) and wet peroxide oxidation (WPO) of stripped sour water (SSW) from an oil shale refinery was investigated. Greater than 70% total organic carbon (TOC) removal from SSW was achieved using Cu(NO(3))(2) catalysed WO under the following conditions using a glass lined reaction vessel: 200 degrees C, pO(2)=0.5MPa, 3h, [Cu(NO(3))(2)]=67mmol/L. Significant TOC removal ( approximately 31%) also occurred in the system without added oxygen. It is proposed that this is predominantly due to copper catalysed oxidative decarboxylation of organics in SSW based on observed changes in copper oxidation state. Greater than 80% TOC removal was achieved using WPO under the following conditions: 150 degrees C, t=1.5h, [H(2)O(2)]=64g/L. Significantly more TOC could be removed from SSW by adding H(2)O(2) in small doses as opposed to adding the same total amount in one single dose. It was concluded that WPO was a far more effective process for removing odorous compounds from SSW.

Pyrolysis of activated sludge: energy analysis and its technical feasibility.

A comprehensive study on the potential of pyrolysis of activated sludge to generate substances that can be used to produce energy was evaluated for its technical and environmental viability. The products of the process viz., pyrolysis gas, pyrolysis oil and char can readily be used by the major energy consumers viz., electricity and transportation. Based on the results obtained it is estimated that a 1 ton capacity process for pyrolysis of activated sludge can serve the electrical needs of a maximum of 239, 95 and 47 Indian houses per day, considering lower middle class, middle class and upper middle class, respectively. In addition the process would also produce the daily methane (CNG) requirement of 128 public transport buses. The process was determined to be technically feasible at low and medium temperatures for both, pyrolysis gas and electrical energy. The gas generated could be utilized as fuel directly while the oil generated would require pretreatment before its potential application. The process is potentially sustainable when commercialized and can self-sustain in continuous mode of operation in biorefinery context.

Synthesis and characterisation of the uranium pyrochlore betafite [(Ca,U)2(Ti,Nb,Ta)2O7].

Betafite of composition [(Ca,U)2(Ti,Nb,Ta)2O7] was prepared via a solid state synthesis route. The synthesis was shown to be sensitive to initial reactant ratios, the atmosphere used (oxidising, neutral, reducing) and time. The optimum conditions for the synthesis of betafite were found to be heating the reactants required at 1150°C for 48 h under an inert gas atmosphere. XRD characterisation revealed that the synthesised betafite contained minor impurities. EPMA analysis of a sectioned surface showed very small regions of Ca-free betafite on grain boundaries as well as minor rutile impurities. Some heterogeneity between the Nb:Ta ratio was observed by quantitative EPMA but was generally within the nomenclature requirements stated for betafite. SEM analysis revealed the synthesised betafite was comprised mostly of hexaoctohedral crystals of ∼ 3 µm in diameter. XPS analysis of the sample showed that the uranium in the synthesised betafite was predominately present in the U(5+) oxidation state. A minor amount of U(6+) was also detected which was possibly due to surface oxidation.

Performance assessment and hydrodynamic analysis of a submerged membrane bioreactor for treating dairy industrial effluent.

Submerged membrane bioreactor (SMBR) is a relatively advanced technology for waste water treatment that involves integrated aerobic and anaerobic biological processes with membrane filtration. In the present investigation, hydrophobic polyvinylidene fluoride (PVDF) and hydrophilic polyacrylonitrile (PAN) hollow fiber (HF) membranes were tested in an indigenously fabricated SMBR for dairy effluent treatment under aerobic conditions using mixed microbial consortia. Effect of operating parameters such as suction pressure, degree of aeration and trans-membrane pressure (TMP) on membrane performance in terms of flux, rejection of turbidity, BOD and COD besides fouling characteristics was investigated. The observed optimum permeabilities of PVDF and PAN HF membranes were approximately 108 and 115 LMH bar(-1) with high extent of impurity removal. The rejection of COD was found to be 93% for PVDF and 91% for PAN HF membranes whereas corresponding rejection of BOD was observed to be 92% and 86%. A two-dimensional comprehensive model was developed to predict the hydrodynamic profile inside the module. Regression analysis revealed that the simulation results agreed well with experimental data.

Gold nanospikes based microsensor as a highly accurate mercury emission monitoring system.

Anthropogenic elemental mercury (Hg(0)) emission is a serious worldwide environmental problem due to the extreme toxicity of the heavy metal to humans, plants and wildlife. Development of an accurate and cheap microsensor based online monitoring system which can be integrated as part of Hg(0) removal and control processes in industry is still a major challenge. Here, we demonstrate that forming Au nanospike structures directly onto the electrodes of a quartz crystal microbalance (QCM) using a novel electrochemical route results in a self-regenerating, highly robust, stable, sensitive and selective Hg(0) vapor sensor. The data from a 127 day continuous test performed in the presence of volatile organic compounds and high humidity levels, showed that the sensor with an electrodeposted sensitive layer had 260% higher response magnitude, 3.4 times lower detection limit (~22 µg/m(3) or ~2.46 ppb(v)) and higher accuracy (98% Vs 35%) over a Au control based QCM (unmodified) when exposed to a Hg(0) vapor concentration of 10.55 mg/m(3) at 101°C. Statistical analysis of the long term data showed that the nano-engineered Hg(0) sorption sites on the developed Au nanospikes sensitive layer play a critical role in the enhanced sensitivity and selectivity of the developed sensor towards Hg(0) vapor.

Critical analysis of pyrolysis process with cellulosic based municipal waste as renewable source in energy and technical perspective.

To understand the potential of cellulosic based municipal waste as a renewable feed-stock, application of pyrolysis by biorefinery approach was comprehensively studied for its practicable application towards technical and environmental viability in Indian context. In India, where the energy requirements are high, the pyrolysis of the cellulosic waste shows numerous advantages for its applicability as a potential waste-to-energy technology. The multiple energy outputs of the process viz., bio-gas, bio-oil and bio-char can serve the two major energy sectors, viz., electricity and transportation. The process suits best for high bio-gas and electrical energy production when energy input is satisfied from bio-char in form of steam (scheme-1). The bio-gas generated through the process shows its direct utility as a transportation fuel while the bio-oil produced can serve as fuel or raw material to chemical synthesis. On a commercial scale the process is a potent technology towards sustainable development. The process is self-sustained when operated on a continuous mode.

Biohydrogen production from kitchen based vegetable waste: effect of pyrolysis temperature and time on catalysed and non-catalysed operation.

Pyrolysis of kitchen based vegetable waste (KVW) was studied in a designed packed bed reactor. The effect of process parameters like temperature, time and catalyst on bio-gas yield and its composition was studied. The total bio-gas yield was found to be maximum with non-catalysed operation (260ml/g) at 1073K (180min). Higher hydrogen (H(2)) yield with non-catalysed operation (32.68%) was observed at 1073K (180min) while with catalysed operation the requisite temperature (873K) and time (120min) reduced with both silica gel (33.34%) and sand (41.82%) thus, saving energy input. Methane (CH(4)) yield was found to be highest (4.44times than non-catalysed and 1.42 with silica gel) in presence of sand (71.485ml/g) at medium temperature (873K) and time (60min). The catalyst operation reduced the carbondioxide (CO(2)) share from 47.29% to 41.30% (silica gel catalysed) and 21.91% (sand catalysed) at 873K.

High surface area Au-SBA-15 and Au-MCM-41 materials synthesis: tryptophan amino acid mediated confinement of gold nanostructures within the mesoporous silica pore walls.

Advantages of confining the gold nanostructures formation within the mesoporous silica pore walls during its silica condensation and consequent improvement in the textural properties such as specific surface area, pore volume, pore diameter have been demonstrated, while retaining gold nanostructures within the silica walls. This has been achieved by tryptophan mediated confinement of gold nanoparticles formation within the condensing silica framework, to obtain Au-SBA-15 (SSA 1247 m(2)/g, V(t)~1.37 cm(3)/g) and Au-MCM-41 (SSA 1287 m(2)/g, V(t)~1.1 cm(3)/g), mesoporous silica materials having the combination of very high surface area from the porous support as well as gold nanoparticles infiltrated silica walls. Choice of tryptophan for this purpose is that it has an indole group, which was known to reduce gold ions to form gold nanoparticles and its amine and carboxylic acid groups, catalyze the hydrolysis of silica precursors in a wide range of pH. These properties have been utilized in restricting the gold nanostructures formation inside the condensing silica phase without affecting the self assembly between the silica precursors and the triblock copolymer (for SBA-15) or cetyltrimethylammonium bromide template (for MCM-41). The polytryptophan and the gold nanostructures, which were encapsulated within the silica framework and upon removal of the template by calcination resulting in the formation mesoporous materials wherein the silica walls become microporous due to the removal of occluded polytryptophan and the resulting microchannels contain very small gold nanostructures. Hence, the resulting materials have very high surface area, high pore volume and narrow pore size distribution as compared to their parent SBA-15, MCM-41 and SBA-15, MCM-41 post functionalized with gold nanoparticles inside the pores.