Environmental Sustainability Evaluation of Iron Oxide Nanoparticles Synthesized via Green Synthesis and the Coprecipitation Method: A Comparative Life Cycle Assessment Study.

Green synthesis, based on green chemistry, is replacing the traditional methods, aiming to contribute with an enhanced environmental sustainability, which can be achieved using nontoxic compounds from biological resources, such as natural extracts from plants. In this study, the life cycle assessment (LCA) of iron oxide nanoparticles prepared through the green synthesis and the coprecipitation method is reported by following a cradle-to-gate approach. The LCA allowed quantifying and normalized the environmental impacts produced by the green synthesis (1.0 × 10-9), which used a Cymbopogon citratus (C. citratus) extract and sodium carbonate (Na2CO3). The impacts were also determined for the coprecipitation method (1.4 × 10-8) using the iron(II) salt precursor and sodium hydroxide (NaOH). The contribution of C. citratus extract and Na2CO3 as the precursor and pH-stabilizing agents, respectively, was compared regarding the iron(II) and NaOH compounds. Environmental sustainability was evaluated in human toxicity, ecosystem quality, and resource depletion. The major environmental contribution was found in the marine aquatic ecotoxicity (7.6 × 10-10 and 1.22 × 10-8 for green synthesis and the coprecipitation method) due to the highest values for ethanol (3.5 × 10-10) and electricity (1.4 × 10-8) usage since fossil fuels and wastewater are involved in their production. The C. citratus extract (2.5 × 10-12) presented a better environmental performance, whereas Na2CO3 (4.3 × 10-11) showed a slight increase contribution compared to NaOH (4.1 × 10-11). This is related to their fabrication, involving toxic compounds, land occupation, and excessive water usage. In general, the total environmental impacts are lower for the green synthesis, suggesting the implementation of environmentally friendlier compounds based on natural sources for the production of nanomaterials.

Inherent Safety Assessment of Industrial-Scale Production of Chitosan Microbeads Modified with TiO2 Nanoparticles.

In this study, the inherent safety analysis of large-scale production of chitosan microbeads modified with TiO2 nanoparticles was developed using the Inherent Safety Index (ISI) methodology. This topology was structured based on two main stages: (i) Green-based synthesis of TiO2 nanoparticles based on lemongrass oil extraction and titanium isopropoxide (TTIP) hydrolysis, and (ii) Chitosan gelation and modification with nanoparticles. Stage (i) is divided into two subprocesses for accomplishing TiO2 synthesis, lemongrass oil extraction and TiO2 production. The plant was designed to produce 2033 t/year of chitosan microbeads, taking crude chitosan, lemongrass, and TTIP as the primary raw materials. The process was evaluated through the ISI methodology to identify improvement opportunity areas based on a diagnosis of process risks. This work used industrial-scale process inventory data of the analyzed production process from mass and energy balances and the process operating conditions. The ISI method comprises the Chemical Inherent Safety Index (CSI) and Process Inherent Safety Index (PSI) to assess a whole chemical process from a holistic perspective, and for this process, it reflected a global score of 28. Specifically, CSI and PSI delivered scores of 16 and 12, respectively. The analysis showed that the most significant risks are related to TTIP handling and its physical-chemical properties due to its toxicity and flammability. Insights about this process's safety performance were obtained, indicating higher risks than those from recommended standards.

Technical Evaluation of a Levulinic Acid Plant Based on Biomass Transformation under Techno-Economic and Exergy Analyses.

Levulinic acid (LA) recently has attracted much attention as a promising biorefinery platform due to its potential to be economical and sustainable. This paper addresses technical, techno-economic, and exergetic analyses of an industrial LA production via acid-catalyzed dehydration. The process was simulated through Aspen Plus, considering a processing capacity of 15,175.60 kg/h of banana empty fruit bunches. The global productivity yield was 25.56%, producing 3883.13 kg/h of LA. The techno-economic analysis evidenced that this process may be an attractive alternative for biomass valorization, considering the obtained financial results. This process's total production cost was 0.178 $USD per kilogram of biomass and a total annualized cost of $USD 29,163,638.95. Exergy analysis revealed that this process had an irreversibility rate of 1.48 × 105 MJ/h. The pretreatment stage presented the lowest exergetic efficiency. Globally, the exergy efficiency was 53.76%, which is within the reported results for analogous biomass transformation processes.

Environmental and Exergetic Analysis of Large-Scale Production of Citric Acid-Coated Magnetite Nanoparticles via Computer-Aided Process Engineering Tools.

Considering that functional magnetite (Fe3O4) nanoparticles with exceptional physicochemical properties can be highly applicable in different fields, scaling-up strategies are becoming important for their large-scale production. This study reports simulations of scaled-up production of citric acid-coated magnetite nanoparticles (Fe3O4-cit), aiming to evaluate the potential environmental impacts (PEIs) and the exergetic efficiency. The simulations were performed using the waste reduction algorithm and the Aspen Plus software. PEI and energy/exergy performance are calculated and quantified. The inlet and outlet streams are estimated by expanding the mass and energy flow, setting operating parameters of processing units, and defining a thermodynamic model for properties estimation. The high environmental performance of the production process is attributed to the low outlet rate of PEI compared to the inlet rate. The product streams generate low PEI contribution (-3.2 × 103 PEI/y) because of the generation of environmentally friendlier substances. The highest results in human toxicity potential (3.2 × 103 PEI/y), terrestrial toxicity potential (3.2 × 103 PEI/y), and photochemical oxidation potential (2.6 × 104 PEI/y) are attributed to the ethanol within the waste streams. The energy source contribution is considerably low with 27 PEI/y in the acidification potential ascribed to the elevated levels of hydrogen ions into the atmosphere. The global exergy of 1.38% is attributed to the high irreversibilities (1.7 × 105 MJ/h) in the separation stage, especially, to the centrifuge CF-2 (5.07%). The sensitivity analysis establishes that the global exergy efficiency increases when the performance of the centrifuge CF-2 is improved, suggesting to address enhancements toward low disposal of ethanol in the wastewater.

Correction to "Synthesis and Sustainability Evaluation of a Lignocellulosic Multifeedstock Biorefinery Considering Technical Performance Indicators".

[This corrects the article DOI: 10.1021/acsomega.0c00114.].

Process Analysis of Hydrogen Production via Biomass Gasification under Computer-Aided Safety and Environmental Assessments.

The growing awareness to advance new ways to transform renewable materials for producing clean fuels, under technical and sustainable viability, is evident. In this regard, hydrogen arises as one of the cleanest and energetic biofuels in the market. This work addresses the modeling and evaluation of a biomass gasification topology employing process simulation along with an environmental and inherent safety analysis. The presented pathway considered two renewable raw materials (cassava and rice waste) based on their vast availability in north Colombia regions. We employed Aspen Plus process simulation software to model the process, setting biomasses (and ash content) as nonconventional solids in the software and inclusion of FORTRAN subroutines for handling solid properties. Otherwise, the environmental evaluation was performed applying the waste reduction algorithm (WAR). At the same time, safety assessment involves a comprehensive approach based on the inherent safety index (ISI) and the process route index (PRI) methods. Data generated from the implementation of rigorous process simulation of biomass gasification allowed us to determine the needed aspect for performing process analysis methodologies. Results revealed that this topology generates a total flow of 3944.51 kg/h with more than 97% vol of H2, from the sustainable use of 19,243 kg/h of cassava waste and 15,000 kg/h of rice straw. From the environmental viewpoint, the process showed moderately to a high overall rate of potential environmental impacts (PEIs), with a higher contribution from process sources than energy sources. It indicates that most of the generated impacts would come from self-operation than from the energy supply generation. In the case of process safety, the topology obtained an ISI score of 35, which represents that modeled gasification would operate below 50% of the expected neutral standard for a physical-chemical process. Complementing the safety evaluation, the obtained PRI suggests that compared to other processes, the analyzed topology shows relatively adequate performance considering the nature of this type of process.

Comparison of Biobutanol Production Pathways via Acetone-Butanol-Ethanol Fermentation Using a Sustainability Exergy-Based Metric.

The incorporation of sustainability aspects into the design of chemical processes has been increasing since the last century. Hence, there are several proposed methodologies and indicators to assess chemical facilities through process analysis techniques. A comprehensive assessment involving economic, environmental, safety, and exergy parameters of two alternatives for butanol production from Manihot esculenta Crantz (cassava waste) is presented in this study. The modeling of process topologies involved using Aspen Plus software. Topology 1 generated a product flow rate of 316,477 t/y of butanol, while this value was 367,037 t/y for topology 2. Both processes used a feed flow of 3,131,439 t/y of biomass. This study used seven technical indicators to evaluate both alternatives, which include the return of investment, discounted payback period, global warming potential, renewability material index, inherent safety index, exergy efficiency, and exergy of waste ratio. Otherwise, this study implemented an aggregate index to assess overall sustainability performance. The results revealed that topology 2 presented higher economic normalized scores for evaluated indicators, but the most crucial difference between these designs came from the safety and exergetic indexes. Topology 1 and topology 2 obtained weighted scores equaling to 0.48 and 0.53; therefore, this study found that the second alternative gives a more sustainable design for butanol production under evaluated conditions.

Application of Techno-economic and Sensitivity Analyses as Decision-Making Tools for Assessing Emerging Large-Scale Technologies for Production of Chitosan-Based Adsorbents.

New ways and technologies for synthesizing adsorbent materials have been emerging based on the green chemistry concept for the sustainable use of available resources. In this sense, the chitosan-based products arise as a promising technology alternative for application of several fields that include mitigation, prevention, and control of environmental issues. Nevertheless, there is a lack of information about the development and behavior of these topologies at the industrial scale. This study addressed the techno-economic and sensitivity analyses as decision-making tools to assess promising topologies for production of chitosan-based bio-adsorbents. From the data provided by process inventory, economic analysis of these routes was implemented. The evaluation allowed obtaining a start point market price for chitosan microbeads (64.40 $/t) and chitosan microbeads modified with TiO2 nanoparticles (37 $/t). The economic analysis also showed that there is a vast potential to explore the chitosan market that enables generation of very profitable businesses from the implementation of those processes, considering the obtained economic performance indicators for both topologies. It is crucial to highlight that these indicators were slightly higher for chitosan microbead production. In addition, the sensitivity analysis indicated that the chitosan-TiO2 process could resist higher fluctuations in the operating costs, which might indicate that this topology might be a reliable alternative between evaluated cases.

Design, Simulation, and Environmental Assessment of an Adsorption-Based Treatment Process for the Removal of Polycyclic Aromatic Hydrocarbons (PAHs) from Seawater and Sediments in North Colombia.

The presence of marine pollution in Cartagena Bay (Colombia) is an alarming environmental issue because of the ecotoxicological properties of contaminants such as polycyclic aromatic hydrocarbons (PAHs) that may affect the biodiversity of coastal ecosystems. In this sense, there is a need to propose alternatives to remediate the environmental pollution of such bodies of water. The aim of this work was to design an adsorption-based treatment process for the removal of PAHs from seawater and sediments. Two design cases were considered: (i) a base process without a PAH desorption unit and (ii) an alternative process including a PAH desorption unit. Both designs were simulated using Aspen Plus to obtain mass and energy balances. A parametric sensitivity analysis was carried out to determine optimum operating conditions for solvent recovery and treatment efficiency. The pressure and temperature of evaporators were selected as key parameters, as well as PAH loads in the influent. The environmental performance of base and alternative designs was also evaluated via waste reduction algorithm (WAR) methodology. A maximum recovered solvent flow rate was found when the evaporator operates at 56 °C and 0.81-0.83 atm. In addition, the total generation rate of potential environmental impacts (PEI) reported negative values for cases 1, 3, and 4 (-9.80 × 10-1, -9.25 × 10+1, -1.19 × 10+1, and 1.04 × 10+1 PEI/h). The major concern derived from this analysis is the high environmental impacts reached by the photochemical oxidation potential (PCOP) category associated with the use of hexane and acetone as solvents during PAH removal from sediments. In general, both designs of seawater and sediment treatment seem to be an environmentally friendly alternative for marine pollution remediation.

Synthesis and Sustainability Evaluation of a Lignocellulosic Multifeedstock Biorefinery Considering Technical Performance Indicators.

Nowadays, green-chemistry principles offer an approach that fits to ensure chemical process sustainability by the use of low-cost renewable raw materials, waste prevention, inherent safer designs, among others. Based on this motivation, this study presents a novel methodology for sustainable process design that comprises the synthesis of a multifeedstock optimal biorefinery under simultaneous optimization of economic and environmental targets and further sustainability evaluation using the sustainability weighted return on investment metric (SWROIM). The first step of the proposed method is the formulation of an optimization model to generate the most suitable process alternatives. The model took into account various biomasses as available raw materials for production of ethanol, butanol, succinic acid, among others. Process technologies such as fermentation, anaerobic digestion, gasification, among others, were considered for biorefinery design. Once the model synthesizes the optimal biorefinery, we used environmental, safety, economic, and energy analyses to assess the process, which is a case study for north Colombia. Process simulation generated the data needed (extended mass and energy balances, property estimation, and modeling of downstream) to develop the process analysis stage via the Aspen Plus software. Results for the environmental and economic analyses showed that the assumption considered to solve the optimization problem was adequate, yielding promising environmental and economic outcomes. Finally, the overall sustainability evaluation showed a SWROIM of 27.29%, indicating that the case study showed higher weighted performance compared to the return on investment (ROI) metric of 14.33%.

Computer-aided simulation and exergy analysis of TiO2 nanoparticles production via green chemistry.

BACKGROUND: The production of photocatalytic nanoparticles such as TiO2 has received increasing interest for biomedical and wastewater treatment applications. However, the conventional synthesis of such materials faces several environmental concerns. METHODS: In this work, green synthesis is addressed to prepare TiO2 nanoparticles at large scale using Lemongrass (Cymbopogon citratus) and titanium isopropoxide (TTIP). This process was designed and modeled using computer-aided process engineering (CAPE) in order to obtain the extended mass/energy balances, as well as operating parameters. Process simulation was carried out using the commercial software Aspen Plus®. In addition, energy performance of large-scale nanoparticle production was analyzed to identify alternatives for process improvement from an exergetic point of view. RESULTS: The production capacity of the plant was estimated as 1,496 t/y of TiO2 nanoparticles by the conversion of 32,675 t/y lemongrass and 5,724 t/y TTIP. Hence, the overall production yield is 0.26 kg TiO2/kg TTIP. Exergy analysis reported an overall exergy efficiency of 0.27% and an exergy loss of 159,824.80 MJ/h. These results suggest that such a process requires the implementation of process improvement strategies to reach a more sustainable design from energy and thermodynamic viewpoints.

Environmental and Safety Assessments of Industrial Production of Levulinic Acid via Acid-Catalyzed Dehydration.

These days, there is a need to develop novel and emerging processing pathways that permit production of value-added substances and fuels considering sustainability aspects. In this sense, levulinic acid (LA) is one of the most promising biorefinery products. This paper presents environmental and safety assessments of LA production via acid-catalyzed dehydration (ACD) of biomass. The process was modeled by using Aspen Plus process simulation software based on a capacity of 132 000 tons per annum of banana rachis (main raw material). Likewise, environmental and safety assessments were developed. Parameters such as heats of reaction, explosivity, toxicity of substances, and operational conditions along with extended mass and energy balances were used to perform safety and environmental analyses. In this regard, the modeled topology showed an inherent safety index (ISI) score of 24 with an equal contribution of 12 points for both chemical inherent safety index (CIS) and process inherent safety index (PIS). ACD showed a good safety performance, with moderate concerns related to the handling of formic acid. Moreover, the waste reduction algorithm (WAR) was used to assess environmental performance and estimate potential environmental impacts (PEIs) of the simulated topology. It was performed considering four case studies to determine the influence of mass streams (case 1), product streams (case 2), energy streams (case 3), and simultaneous products and energy contribution (case 4). This analysis showed that for this process, the total inletting flow of impacts that enter was less than the amount of these that leave the system according to a generation rate of the PEI for case 1 (-1.89 × 102 PEI/h) and case 3 (-1.83 × 102 PEI/h). From the environmental viewpoint, the major concern is associated with the photochemical oxidation potential category because of the handling of volatile organic compounds through the process.