Environmental impacts of valorisation of crude glycerol from biodiesel production - A life cycle perspective.

Biodiesel production produces significant quantities of impure crude glycerol as a by-product. Recent increases in the global biodiesel production have led to a surplus of crude glycerol, rendering it a waste. As a result, different methods for its valorisation are currently being investigated. This paper assesses the life cycle environmental impacts of an emerging technology for purification of crude glycerol - a multi-step physico-chemical treatment - in comparison to incineration with energy recovery commonly used for its disposal. For the former, three different acids (H3PO4, H2SO4 and HCl) are considered for the acidification step in the purification process. The results suggest that the H2SO4-based treatment is the best option with 17 net-negative impacts out of the 18 categories considered; this is due to system credits for the production of purified glycerol, heat and potassium salts. In comparison to incineration with energy recovery, the H2SO4-based process has lower savings for the climate change impact (-311 versus -504 kg CO2 eq./t crude glycerol) but it performs better in ten other categories. Sensitivity analyses suggest that that the impacts of the physico-chemical treatment are highly dependent on crude glycerol composition, allocation of burdens to crude glycerol and credits for glycerol production. For example, treating crude glycerol with lower glycerol content would increase all impacts except climate change and fossil depletion due to the higher consumption of chemicals and lower production of purified glycerol. Considering crude glycerol as a useful product rather than waste and allocating to it burdens from biodiesel production would increase most impacts significantly, including climate change (22-40 %), while fossil depletion, freshwater and marine eutrophication would become net-positive. The findings of this research will be of interest to the biodiesel industry and other industrial sectors that generate crude glycerol as a by-product.

Environmental assessment of a novel ionic-liquid based method for recycling of PVC in composite materials.

Waste PVC is scarcely recycled due to its high chlorine content and its use in composite materials, which reduces the applicability of conventional waste treatment methods, including thermal, mechanical and chemical recycling. For this reason, alternative treatment options are being developed to increase the recyclability of waste PVC. This paper focuses on one such option which utilises ionic liquids (ILs) for material separation and dehydrochlorination of PVC contained in composite materials. Taking blisterpacks used as a packaging for medicines as an example of a composite material, the paper presents for the first time the life cycle environmental impacts of this novel PVC recycling method, in comparison with thermal treatment (low-temperature pyrolytic degradation of PVC). Three ILs were considered for the PVC recycling process: trihexyl(tetradecyl)phosphonium chloride, bromide and hexanoate. The results suggested that the impacts of the process using the first two ILs were comparable, while the system with hexanoate-based IL had 7-229 % higher impacts. Compared to the thermal treatment of waste blisterpacks, the IL assisted process had significantly higher impacts (22-819 %) in all 18 categories considered due to the greater heat requirements and the IL losses. Reducing the latter would lower most impacts by 8-41 %, while optimising the energy requirements would reduce the impacts by 10-58 %. Moreover, recovering HCl would increase significantly the environmental sustainability of the process, resulting in net-negative impacts (savings) in most categories. Overall, these improvements would lead to lower or comparable impacts to those of the thermal treatment. The findings of this study will be of interest to the polymer, recycling and related industries, as well as to process developers.

Fracking wastewater treatment: Catalytic performance and life cycle environmental impacts of cerium-based mixed oxide catalysts for catalytic wet oxidation of organic compounds.

Water scarcity and the consequent increase of freshwater prices are a cause for concern in regions where shale gas is being extracted via hydraulic fracturing. Wastewater treatment methods aimed at reuse/recycle of fracking wastewater can help reduce water stress of the fracking process. Accordingly, this study assessed the catalytic performance and life cycle environmental impacts of cerium-based mixed oxide catalysts for catalytic wet oxidation (CWO) of organic contaminants, in order to investigate their potential as catalysts for fracking wastewater treatment. For these purposes, MnCeOx and CuCeOx were tested for phenol removal in the presence of concentrated NaCl (200 g L-1), which represented a synthetic fracking wastewater. Removal of phenol in pure ("phenolic") water without NaCl was also considered for comparison. Complete (100 %) phenol and a 94 % total organic carbon (TOC) removal were achieved in both the phenolic and fracking wastewaters by utilising MnCeOx (5 g L-1) and insignificant metal leaching was observed. However, a much lower activity was observed when the same amount of CuCeOx was utilised: 23.3 % and 20.5 % for phenol and TOC removals, respectively, in the phenolic, and 69.1 % and 63 % in the fracking wastewater. Furthermore, severe copper leaching from CuCeOx was observed during stability tests conducted in the fracking wastewater. A life cycle assessment (LCA) study carried out as part of this work showed that the production of MnCeOx had 12-98 % lower impacts than CuCeOx due to the higher impacts of copper than manganese precursors. Furthermore, the environmental impacts of CWO were found to be 94-99 % lower than those of ozonation due to lower energy and material requirements. Overall, the results of this study suggest that the adoption of catalytic treatment would improve both the efficiency and the environmental sustainability of both the fracking wastewater treatment and the fracking process as a whole.

Assessing the environmental sustainability of an emerging energy technology: Solar thermal calcination for cement production.

Cement production is a highly energy-intensive process, contributing 7% to global CO2 emissions. Over 80% of the energy used in cement production is consumed by the calcination process. This paper considers a novel solar thermal technology for calcination, to investigate if it could help mitigate the climate change and other environmental impacts from cement production on a life cycle basis. The following three solar options are compared to conventional fossil-fuel calcination via life cycle assessment: a full solar system, which provides all the required thermal energy, and two hybrid systems, where the solar system provides 14% and 33% of the thermal energy, respectively. The results show that all three solar options have lower impacts than conventional calcination in 14 out of 17 categories. The full solar system is the best alternative, with major reductions in climate change (48%), fossil depletion (75%), photochemical ozone formation (92%) and terrestrial ecotoxicity (79%). Based on insolation levels in different parts of the world, the solar systems could be applied to 26% of current global cement production. This would reduce the climate change impact by 15-40%, as well as most other impacts by 14-87%, depending on the fuel mix. However, a limiting factor might be two times greater land occupation than by the conventional process. Furthermore, the solar system has higher human toxicity-cancer (102%) and metals and minerals depletion (6%) due to the construction of solar facilities. Coupling conventional calcination with carbon capture and storage (CCS) is more efficient in reducing the climate change impact (63%) than the solar system (48%) relative to conventional calcination without CCS. However, adding CCS to the solar calciner would still be a better option, decreasing the impact by 81% relative to conventional calcination without CCS. These findings will be of interest to the solar and cement industries as well as other industrial sectors using high-temperature processes.

Ultrasonic and hydrothermal mediated synthesis routes for functionalized Mg-Al LDH: Comparison study on surface morphology, basic site strength, cyclic sorption efficiency and effectiveness.

Amine functionalized layered double hydroxide (LDHs) adsorbents prepared using three different routes: co-precipitation, sono-chemical and ultrasonic-assisted high pressure hydrothermal. The prepared adsorbent samples were characterized using X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning electron microscope-Energy dispersive X-ray spectroscopy (SEM-EDX), Temperature Programmed Desorption (TPD), Brunauer-Emmett-Teller (BET), and Thermogravimetric analysis (TGA), respectively. The performance of the prepared adsorbents was tested in a controlled thermal-swing adsorption process to measure its adsorption capacity, regeneration and cyclic efficiencies subsequently. The characterisation results were compared with those obtained using the conventional preparation routes but taking into account of the impact of sonochemical and hydrothermal pre-treatment on textural properties, adsorption capacity, regeneration and cyclic efficiencies. Textural results depicts a surge in surface area of the adsorbent synthesised by hydrothermal route (311m2/g) from 25 to 171m2/g for conventional and ultrasonic routes respectively. Additionally, it has been revealed from the present study that adsorbents prepared using ultrasonic-assisted hydrothermal route exhibit a better CO2 uptake capacity than that prepared using sonochemical and conventional routes. Thus, the ultrasonic-assisted hydrothermal treatment can effectively promote the adsorption capacity of the adsorbent. This is probably due to the decrease of moderate (M-O) and weak (OH- groups) basic sites with subsequent surge in the number of strong basic sites (O2-) resulting from the hydrothermal process. Moreover, the cyclic adsorption efficiency of the ultrasonic mediated process was found to be 76% compared with 60% for conventional and 53% for hydrothermal routes, respectively. According to the kinetic model analysis, adsorption mechanism is mostly dominated by physisorption before amine modification and by chemisorption after the modification process.