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Journal articleGreen SP, Wheelhouse KM, Payne AD, et al., 2020,
On the Use of Differential Scanning Calorimetry for Thermal Hazard Assessment of New Chemistry: Avoiding Explosive Mistakes
, Angewandte Chemie, Vol: 132, Pages: 15930-15934, ISSN: 0044-8249© 2020 Wiley-VCH GmbH Differential scanning calorimetry (DSC) is increasingly used as evidence to support a favourable safety profile of novel chemistry, or to highlight the need for caution. DSC enables preliminary assessment of the thermal hazards of a potentially energetic compound. However, unlike other standard characterisation methods, which have well defined formats for reporting data, the current reporting of DSC results for thermal hazard assessment has shown concerning trends. Around half of all results in 2019 did not include experimental details required to replicate the procedure. Furthermore, analysis for thermal hazard assessment is often only conducted in unsealed crucibles, which could lead to misleading results and dangerously incorrect conclusions. We highlight the specific issues with DSC analysis of hazardous compounds currently in the organic chemistry literature and provide simple “best practice” guidelines which will give chemists confidence in reported DSC results and the conclusions drawn from them.
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Journal articleGreen SP, Wheelhouse KM, Payne AD, et al., 2020,
On the Use of Differential Scanning Calorimetry for Thermal Hazard Assessment of New Chemistry: Avoiding Explosive Mistakes
, Angewandte Chemie International Edition, Vol: 59, Pages: 15798-15802, ISSN: 1433-7851<jats:title>Abstract</jats:title> <jats:p>Differential scanning calorimetry (DSC) is increasingly used as evidence to support a favourable safety profile of novel chemistry, or to highlight the need for caution. DSC enables preliminary assessment of the thermal hazards of a potentially energetic compound. However, unlike other standard characterisation methods, which have well defined formats for reporting data, the current reporting of DSC results for thermal hazard assessment has shown concerning trends. Around half of all results in 2019 did not include experimental details required to replicate the procedure. Furthermore, analysis for thermal hazard assessment is often only conducted in unsealed crucibles, which could lead to misleading results and dangerously incorrect conclusions. We highlight the specific issues with DSC analysis of hazardous compounds currently in the organic chemistry literature and provide simple “best practice” guidelines which will give chemists confidence in reported DSC results and the conclusions drawn from them.</jats:p>
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Journal articleTan S-Y, Hallett J, Geoff K, 2020,
Electrodeposition of lead from methanesulfonic acid and methanesulfonate ionic liquid derivatives
, Electrochimica Acta, Vol: 353, Pages: 1-11, ISSN: 0013-4686The influence is reported of electrolyte composition on the electrochemistry of PbII and electrodeposition morphology of Pb in aqueous methanesulfonic acid (MSA) and two methanesulfonate-based ionic liquids: 1-butyl-3-methylimidazolium methanesulfonate and N,N-dimethylbutylammonium methanesulfonate. Cyclic voltammetry and chronoamperometry indicated that the reduction of PbII ions to Pb was a diffusion-controlled process proceeding via a two-electron transfer process at -0.67 V vs. Ag (1 M MSA) and involved 3-D progressive nucleation. Scanning electron microscopy showed a strong influence of deposition potential and electrolyte composition on the morphology of Pb deposits. Experimental data was used to model predictions of the specific electrical energy consumption for cathodic PbII electrodeposition coupled with either anodic oxygen evolution or PbO2 electrodeposition.
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Journal articleChen M, Malaret F, Firth AEJ, et al., 2020,
Design of a combined ionosolv-organosolv biomass fractionation process for biofuel production and high value-added lignin valorisation
, GREEN CHEMISTRY, Vol: 22, Pages: 5161-5178, ISSN: 1463-9262- Author Web Link
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- Citations: 59
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Journal articleGschwend FJ, Hennequin LM, Brandt-Talbot A, et al., 2020,
Towards an environmentally and economically sustainable biorefinery: heavy metal contaminated waste wood as a low-cost feedstock in a low-cost ionic liquid process
, Green Chemistry, Vol: 22, Pages: 5032-5041, ISSN: 1463-9262In the present study, we used a low-cost protic ionic liquid, 1-methylimidazolium chloride, to simultaneously fractionate heavy metal contaminated wood and extract the metals from the wood at elevated temperature and short reaction time. This treatment selectively dissolves the lignin and hemicellulose in the biomass, leaving a solid cellulose-rich pulp, while coordinating and extracting 80–100% of the metal species present in the wood in a one-pot process. The lignin stream was recovered from the liquor and the cellulose was hydrolysed and then fermented into ethanol. The ionic liquid was recycled 6 times and the metals were recovered from the liquor via electrodeposition. This is the first time that highly contaminated waste wood has been integrated into a process which does not produce a contaminated waste stream, but instead valorises the wood as a feedstock for renewable chemicals, materials and fuels, while efficiently recovering the metals, converting a toxic environmental hazard into a rich source of biorenewables. We have therefore used an otherwise problematic waste as a low-cost lignocellulsoic feedstock for a circular bioeconomy concept.
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Journal articleFirth AEJ, Mac Dowell N, Fennell PS, et al., 2020,
Assessing the economic viability of wetland remediation of wastewater, and the potential for parallel biomass valorisation
, Environmental Science: Water Research & Technology, Vol: 6, Pages: 2103-2121, ISSN: 2053-1400Constructed wetlands have been shown to consistently remove a wide range of pollutants from contaminated water. However, no wide-ranging studies exist on the economic viability of this technology. This paper performs a high-level economic comparison between wetland remediation and conventional water remediation technologies, for a wide range of contaminant inputs, outputs, and flow rates. The cases considered are nutrient removal from wastewater, and remediation of low-pH and circumneutral acid mine drainage (AMD). The first-order P-k-C* model is used for nutrient removal, while a zeroth-order model is used for AMD remediation, with removal rate data taken from the literature. The number of wetland cells employed was found to significantly affect the overall cost of nutrient removal, allowing savings of up to 86% and 42% for biochemical oxygen demand and phosphorus removal, particularly for low concentrations and flow rates. For integrated secondary and tertiary treatment, wetland remediation was economically competitive down to stringent effluent standards. A sensitivity analysis was performed on sizing and costing parameters of nutrient removal wetlands, with required wetland size found to be most strongly correlated with the assumed removal rate, and land costs found to have relatively little effect on overall costs. Wetland remediation of AMD was only found to be economically favourable for less severe conditions and lower flow rates when treating low-pH drainage, and was heavily influenced by the acidity removal rate. However, the majority of site data from literature was found to fall within this range of conditions. For circumneutral AMD, wetland remediation was found to be cheaper for all simulated cases. The feasibility of offsetting wetland remediation costs through biomass valorisation was investigated for a range of products, with area requirements for minimum economic production identified as the principal barrier.
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Journal articleClarke CJ, Bui-Le L, Corbett PJ, et al., 2020,
Implications for heavy metal extractions from hyper saline brines with [NTf2](-) ionic liquids: performance, solubility, and cost
, Industrial and Engineering Chemistry Research, Vol: 59, Pages: 12536-12544, ISSN: 0888-5885The bis(trifluoromethanesulfonyl)imide anion, [NTf2]−, can be paired with organic cations to give hydrophobic ionic liquids (ILs) that form secondary phases with water. These ILs are often identified as green solvents and considered as replacements for traditional organic solvents in chemical processes, i.e., aqueous biphasic extractions. Here, we consider a range of hydrophobic [NTf2]− ILs as extraction phases with hypersaline brines for heavy metal remediation. Extraction experiments were complicated by the partial solubility of the hydrophobic ILs, and ion chromatography was used to quantify the anion and cation losses to the aqueous phase. Although IL leaching was lower in hypersaline brine than in water (i.e., salting-out), IL losses were significant at relatively low volume ratios (Vaq/VIL) for short-chain and functional ILs. IL purity was also affected by cation exchange; more organic cations were lost to the aqueous phase than [NTf2]− anions. Solvent replenishment costs were extremely high due to loss to the aqueous phase and high IL prices. New separation technologies will be required if these ILs are to be used industrially; recovery is unlikely to offset the cost with current separation methodologies.
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Journal articleChambon CL, Karia T, Sandwell P, et al., 2020,
Techno-economic assessment of biomass gasification-based mini-grids for productive energy applications: The case of rural India
, Renewable Energy, Vol: 154, Pages: 432-444, ISSN: 0960-1481As the costs of solar PV continuously decrease and pollution legislation imposes less burning of agricultural residues, decentralized renewable energy is increasingly affordable for providing electricity to one billion people lacking access to a power grid. This paper presents a techno-economic feasibility case study of biomass gasification in off-grid and grid-connected mini-grids for community-scale energy application in rural Uttar Pradesh, India. Energy demand data was collected through surveys in a village with irrigation and agro-processing loads and off-grid households and used to construct a seasonal load profile based on statistical methods. This was used to simulate single-source and hybrid mini-grids based on solar PV, biomass gasification and diesel generation using HOMER Pro. Hybrid PV-biomass or PV-diesel systems were found to offer the highest reliability for off-grid power at the lowest cost. Single-source PV was cheaper than biomass gasification, though the cost of electricity is highly sensitive to biomass supply and gasifier maintenance. Both renewable options were around half the cost of diesel generation. The findings held across grid-connected systems with weak, moderate and strong reliability of grid supply. This suggests that biomass gasification-based mini-grids are not cost-competitive with PV unless the two generation sources are combined in a hybrid system, though they require operational testing prior to implementation.
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Journal articleClarke CJ, Bui-Le L, Hallett JP, et al., 2020,
Thermally-Stable Imidazolium Dicationic Ionic Liquids with Pyridine Functional Groups
, ACS SUSTAINABLE CHEMISTRY & ENGINEERING, Vol: 8, Pages: 8762-8772, ISSN: 2168-0485- Author Web Link
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- Citations: 33
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Journal articleNakasu PYS, Clarke CJ, Rabelo SC, et al., 2020,
Interplay of Acid–Base Ratio and Recycling on the Pretreatment Performance of the Protic Ionic Liquid Monoethanolammonium Acetate
, ACS Sustainable Chemistry & Engineering, Vol: 8, Pages: 7952-7961
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