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Editorial
Effective Assessment Practices for Using Sustainability Metrics: Biomass ProcessingClick to copy article linkArticle link copied!
- Francisco Vilaplana
- Sónia P. M. Ventura
- Putla Sudarsanam
- Nourredine Abdoulmoumine
- D. Julie Carrier
This publication is licensed for personal use by The American Chemical Society.
Copyright © Published 2021 by American Chemical Society
Energy and chemicals are still mostly produced from building blocks obtained from petroleum, coal, and natural gas industries. However, there is incessant demand for these commodities to be produced from sustainable production schemes, and usually, these start with building blocks derived from renewable biobased resources. Biomass is one of these streams that could supply building blocks. Biomass encompasses all feedstock produced by biological organisms and can include, but is not limited to, crop residues, herbaceous energy crops, woody crops, algae and other marine streams, or construction waste. Although present in the pulp and paper industry, biomass processing involves a complex network of operations and processes that are not present in petrochemical production operations. Thus, a clear delineation of the production operations becomes imperative so that all steps involved in biomass transformation are evaluated in terms of their environmental sustainability metrics. These metrics provide an unbiased path to evaluate biomass processing systems. In addition to social and economic considerations, a process is environmentally sustainable relative to an alternative if for similar product yields less chemical and energy inputs are required, while minimizing noxious byproducts. Environmental sustainability analysis is critical to identify hotspots, which will in turn highlight additional research needs. This editorial suggests guidelines for quantitative sustainability assessments in manuscripts focused on biomass processing to produce energy and chemicals. The guidelines are based on the types of manuscripts we receive in this area and are focused on the chemical- and biological-engineered processes carried out in biomass processing. Please note that the present guidelines do not cover catalysis as it pertains to biomass processing. Instead, we refer you to a separate ACS Sustainable Chemistry & Engineering editorial on sustainability metrics for catalysis and catalytic processes. (1)
General Concepts
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Biomass is processed in a biorefinery, which is a dedicated facility for its conversion to energy, chemicals, and other beneficial products; smooth functioning of a biomass supply chain is needed for its sustainable operation. Before arriving at the biorefinery, biomass must be produced, harvested, collected, processed, and transported. These steps are collectively referred to as the feedstock supply chain and logistics and are like biomass preparation steps carried out in agriculture and pulp and paper sectors. The operations in the feedstock supply chain and logistics could vary widely depending on the biomass type. For example, forest biomass requires planting and thinning as common operations in feedstock production, while fertilizer application and irrigation are common for crop residues production. Regardless of their production operations, biomass must be processed from a “standing in the field or forest” state to a material that is suitable for transportation to the biorefinery through a series of operations, for example, felling, delimbing, bucking, chipping, chopping, and baling. At the biorefinery, processing starts with biomass preparation, typically involving some or all of the following operations: size reduction, drying, sieving, blending, and densification. The specific preparation steps depend on the nature of the biomass as well as the extent of processing required for presentation at the throat of the reactors. Biomass conversion in the biorefinery is achieved through biochemical and thermochemical pathways. A pathway includes specific processes that transform biomass into intermediates and may consist of more general downstream processes required to separate, purify, condition, and upgrade intermediates to their final targeted products. The biochemical pathway includes relatively mature unit operations that encompass chemical or enzymatic deconstruction of starch-based, lignocellulosic, or marine feedstocks into sugars, which can then be fermented into fuels or chemicals at mild temperatures. (2) An example of this pathway includes biomass enzymatic breakdown into monomeric sugars followed by fermentation to ethanol, butanol, and other chemicals. In contrast, the thermochemical pathway employs intermediate to high temperatures, with or without catalysts and other chemicals, to deconstruct biomass into intermediate species, which could be transformed into fuels and chemicals. (3) Examples of this pathway include biomass processing by fast pyrolysis, gasification, and hydrothermal liquefaction to produce intermediate products that are further upgraded to fuel and chemicals. Additional routes, made possible by novel thermo-, electro-, and biocatalytic developments, are emerging. Sustainability assessments of the biomass processing system are more effective when they evaluate all the subsystems holistically.
Sustainability Metrics Used in Biomass Processing
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Sustainability metrics are useful to compare the intrinsic performance of biomass processes against incumbent alternatives. Thus, in addition to the conversion, yield, and selectivity, we encourage authors to use metrics such as the E-factor and global warming potential (GWP) to quantify the sustainability of their biomass processes. The diversity of the types of processes and operations necessary to transform biomass makes it challenging to prescriptively select a finite set of metrics in this area. (4,5) We encourage the authors to review ACS Sustainable Chemistry & Engineering articles as well as other sources to identify suitable metrics for their specific research areas. (4,6) For example, in the biomass supply and logistics area, chemical and energy inputs vary widely based on the feedstock types, production, and logistic operations. Typical energy inputs include the energy required to operate equipment and machineries for growing, harvesting, and in-field processing as well as for transportation. Common chemical inputs include fertilizers, herbicides, and water. While we do not focus on manuscripts that address the sustainability analysis of biomass supply chain and logistics, their energy and chemical use associated with production must be accounted. Chemical and energy inputs in biorefinery operations are generally an important share of overall inputs in biomass processing. Biomass preparation and storage generally require modest chemical inputs. However, size reduction and drying are especially energy voracious steps for biomass preparation and transportation and should be quantified. In the drying step, heat integration is a common strategy implemented to minimize the energy demand by recovering and recycling heat from other parts of the biorefinery. Because biomass is perishable and flammable, moisture, temperature, and fire risks must be monitored and managed during storage; energy inputs should be quantified.
The energy and chemical inputs during the conversion step of biomass processing are significant. In the biochemical platform, biomass pretreatment is needed to improve enzymatic activity. Except for organosolv pretreatments, this step is usually water based. However, after all pretreatment steps, some form of washing is needed, as this improves enzymatic activity. Water usage during pretreatment, washing, and enzymatic hydrolysis should be quantified with appropriate mass-based and other relevant metrics, for example, E-factor. (6) Authors are encouraged to use and report on solvent selection tools to guide their selection. The CHEM21 toolkit is an example of an appropriate solvent selection tool. (7) Disposal of byproducts that are formed during unit operations should be quantified and accounted for. Ideally, biomass disposal would be replaced through byproduct valorization; however, energy, water, and solvent usage should be tallied. The valorization of these byproducts will depend on the energy and costs required for, but not limited to, catalyst synthesis, upgrading process, and product separation and purification steps.
Water will be omnipresent during biochemical fermentation steps, and its use should be quantified through tools such as E-factor. Fermentation processes are very sensitive to temperature ranges, requiring voracious volumes of cooling water, which should be quantified. Fermentation processes usually result in targeted products in diluted form, requiring further downstream processing steps (e.g., fractionation, separation, and recovery). Approaches using CHEM21toolkit (7) are encouraged as they can nudge toward selecting fewer toxic solvents and nonsolvent operations (e.g., membrane filtration and chromatographic separations). Fermentation usually implies carbon dioxide production, which needs to be quantified and, if possible, not released to the atmosphere, implying the design of capture or valorization steps.
In the thermochemical platform, the requirements for energy and chemicals vary greatly. For example, in gas–solid thermochemical processes like fast pyrolysis and gasification, energy inputs are important, with a significant portion heating the conversion reactors to their high temperatures. In these processes, it is common to see process configurations that attempt to generate and recycle heat to offset the energy demand by promoting carbon oxidation reactions. For example, in fast pyrolysis conceptual biorefineries, biochar, the main byproduct, as well as coke formed on a catalyst’s surface are combusted to generate heat. It should be noted, however, that this approach affects the overall carbon efficiency into the products since parts of the carbon is diverted to heat generation. In such cases, strategies that valorize the flue gas generated during biochar combustion should be integrated to minimize biogenic carbon waste. Chemical inputs in the gas–solid thermochemical processes are diverse. For example, hydrogen is used to deoxygenate bio-oil, the primary product of fast pyrolysis, either in the conversion reactor or downstream processes. The use of solvents, water, and other chemicals is modest in gas–solid thermochemical processes and is largely concentrated in downstream processes. In contrast, liquid–solid thermochemical processes are typically less energy intensive because they require lower conversion temperatures and less chemical intensive because they are carried out in water or solvents. For example, in hydrothermal liquefaction, important quantities of water and solvents are used during biomass liquefaction into crude oil and separation of crude oil fractions.
Energy and chemical inputs and outputs should be quantified as their quantities are required to compute various sustainable metrics. Additionally, the conversion of biogenic carbon to desired products should be quantified since the biomass carbon can be distributed in numerous products, some of which can exert deleterious environmental impacts. For example, gaseous molecules, such as CO and CO2, are produced in most thermochemical processes and should be quantified, tracked, and, if possible, recycled to maximize biogenic carbon efficiency and minimize their deleterious environmental impacts. To the extent possible, the elemental balance of C, O, and H should be carried out and optimized toward higher carbon conversion to products. Additionally, heterogeneous catalysis can play a vital role in upgrading biomass-derived molecules to fuels and chemicals but can be deactivated. (8) The sustainability of the heterogeneous catalysts should be reported following guidelines reported in the ACS Sustainable Chemistry & Engineering editorial on sustainability metrics for catalysis and catalytic processes. (1)
Overall Process Analysis
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Techno-economic (TEA) and life cycle (LCA) analyses are two important tools for evaluating the sustainability of both biomass processes and products; however, generic TEA or LCA that do not rigorously evaluate specific process and regional realities are not encouraged. In our context, TEA evaluates the costs, benefits, risks, and uncertainties associated with transforming specific biomass from its “standing in the field” state to targeted products and coproducts through explicit processes. Similarly, LCA seeks to quantify environmental impacts over a defined domain, for example, cradle-to-gate, cradle-to-grave, gate-to-gate, and cradle-to-cradle. Both TEA and LCA rely on process or system analyses which provide material and energy inventories necessary to quantify sustainability metrics. TEA and LCA measure sustainability using economic and environmental impact indicators, including, but not limited to, levelized cost of products, cost of waste disposal, greenhouse gas emissions, ozone depletion, acidification, eutrophication, smog formation, energy usage, and ecotoxicity. TEA and LCA assumptions should be carefully evaluated. For example, but not limited to, energy that is needed for a given system can vary in terms of its environmental footprint depending on the regions and sources; similar caveats can also affect water usage. TEA and LCA studies that include uncertainty analysis are also especially encouraged. (9) The use of TEA and LCA is encouraged when evaluating multiple processes integrated into a system.
Conclusion
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Broadly, metrics associated with novel or traditional feedstocks being transformed into energy and chemicals are needed such that the sustainability of these biomass-based processes can be compared to their conventional counterparts. Future production schemes need to be economically viable as well as sustainable. For this, identification of processing hotspots is needed such that they can be addressed and amended through research. We look forward to your feedback and your manuscript submissions to ACS Sustainable Chemistry & Engineering in these areas.
Author Information
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References
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This article references 9 other publications.
- 1Debecker, D. P.; Kuok (Mimi) Hii, K.; Moores, A.; Rossi, L. M.; Sels, B.; Allen, D. T.; Subramaniam, B. Shaping effective practices for incorporating sustainability assessment in manuscripts submitted to ACS Sustainable Chemistry & Engineering: Catalysis and catalytic processes. ACS Sustainable Chem. Eng. 2021, 9, 4936– 4940, DOI: 10.1021/acssuschemeng.1c02070Google Scholar1Shaping Effective Practices for Incorporating Sustainability Assessment in Manuscripts Submitted to ACS Sustainable Chemistry & Engineering: Catalysis and Catalytic ProcessesDebecker, Damien P.; Kuok Hii, King; Moores, Audrey; Rossi, Liane M.; Sels, Bert; Allen, David T.; Subramaniam, BalaACS Sustainable Chemistry & Engineering (2021), 9 (14), 4936-4940CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)There is no expanded citation for this reference.
- 2Raud, M.; Kikas, T.; Sippula, O.; Shurpali, N. J. Potentials and challenges in lignocellulosic biofuel production technology. Renewable Sustainable Energy Rev. 2019, 111, 44– 56, DOI: 10.1016/j.rser.2019.05.020Google Scholar2Potentials and challenges in lignocellulosic biofuel production technologyRaud, M.; Kikas, T.; Sippula, O.; Shurpali, N. J.Renewable & Sustainable Energy Reviews (2019), 111 (), 44-56CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)A review. Since the Kyoto protocol, the EU renewable energy policy has been the driving force in research and development of the prodn. and use of biofuels. Therefore, the utilization of biofuels and the scientific research to widen the scope of their commercialization are being increasingly promoted. In this context, we present here an overview of the technol. developments that have occurred in the prodn. of different biofuels and their resources with a focus on the lignocellulosic biomass and biofuels derived from it. In the recent years, many technologies have evolved enabling the prodn. of different liq. biofuels from lignocellulosic biomass. Bioethanol prodn. using microbial fermn., and prodn. of bio-oil using fast pyrolysis process of biomass are some of the most widely researched and promising technologies. The first prodn. plants based on these techniques are already operational. Bioethanol prodn. from lignocellulosic biomass promises a good fuel yield under lab. scale. However, there are several challenges that need to be tackled before the prodn. process can be commercialized. We provide here an overview of the various possibilities that can be exploited for biofuel prodn. and make recommendations for increasing the prodn. efficiency with a view to improving the overall yield and lowering the prodn. costs.
- 3Ong, H.; Chen, W.-H.; Farooq, A.; Gan, Y.; Lee, K.; Ashokkumar, V. Catalytic thermochemical conversion of biomass for biofuel production: A comprehensive review. Renewable Sustainable Energy Rev. 2019, 113, 109266, DOI: 10.1016/j.rser.2019.109266Google Scholar3Catalytic thermochemical conversion of biomass for biofuel production: A comprehensive reviewOng, Hwai Chyuan; Chen, Wei-Hsin; Farooq, Abid; Gan, Yong Yang; Lee, Keat Teong; Ashokkumar, VeeramuthuRenewable & Sustainable Energy Reviews (2019), 113 (), 109266CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)A review. The increasing demand for energy and diminishing sources of fossil fuels have called for the discovery of new energy sources. The effective energy conversion process of biomass is able to fulfill energy needs. Among the advanced biomass conversion technologies, thermochem. processes hold considerable potential approaches and needed for optimization. Thus, this study presents a comprehensive review of the research and development on the effects of catalysts on the thermochem. conversion of biomass to det. the progress of catalytic thermochem. conversion processes. The effects of catalysts on torrefaction, pyrolysis, hydrothermal liquefaction, and gasification are highlighted. Aspects related to reaction conditions, reactor types, and products are discussed comprehensively with the reaction mechanisms involved in the catalytic effects. Hydrogenation and hydrodeoxygenation can occur in the presence of zeolite catalysts during fast pyrolysis while producing highly arom. bio-oil. A heterogeneous catalyst in liquefaction increases the hydrocarbon content and decreases viscosity, acid value, and oxygenated compds. in the bio-oil. Thus, expanding and enhancing knowledge about catalyst utilization in the thermochem. conversion technologies of biomass will play an important role in the generation of renewable and carbon-neutral fuels.
- 4Bartling, A.; Stone, M.; Hanes, R.; Bhatt, A.; Zhang, Y.; Biddy, M.; Davis, R.; Kruger, J.; Thornburg, N.; Luterbacher, J.; Rinaldi, R.; Samec, J.; Sels, B.; Roman-Leshkov, Y.; Beckham, G. Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation. Energy Environ. Sci. 2021, 14, 4147– 4168, DOI: 10.1039/D1EE01642CGoogle Scholar4Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionationBartling, Andrew W.; Stone, Michael L.; Hanes, Rebecca J.; Bhatt, Arpit; Zhang, Yimin; Biddy, Mary J.; Davis, Ryan; Kruger, Jacob S.; Thornburg, Nicholas E.; Luterbacher, Jeremy S.; Rinaldi, Roberto; Samec, Joseph S. M.; Sels, Bert F.; Roman-Leshkov, Yuriy; Beckham, Gregg T.Energy & Environmental Science (2021), 14 (8), 4147-4168CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Reductive catalytic fractionation (RCF) is a promising approach to fractionate lignocellulose and convert lignin to a narrow product slate. To guide research towards commercialization, cost and sustainability must be considered. Here we report a techno-economic anal. (TEA), life cycle assessment (LCA), and air emission anal. of the RCF process, wherein biomass carbohydrates are converted to ethanol and the RCF oil is the lignin-derived product. The base-case process, using a feedstock supply of 2000 dry metric tons per day, methanol as a solvent, and H2 gas as a hydrogen source, predicts a min. selling price (MSP) of crude RCF oil of $1.13 per kg when ethanol is sold at $2.50 per gal of gasoline-equiv. ($0.66 per L of gasoline-equiv.). We est. that the RCF process accounts for 57% of biorefinery installed capital costs, 77% of pos. life cycle global warming potential (GWP) (excluding carbon uptake), and 43% of pos. cumulative energy demand (CED). Of $563.7 MM total installed capital costs, the RCF area accounts for $323.5 MM, driven by high-pressure reactors. Solvent recycle and water removal via distn. incur a process heat demand equiv. to 73% of the biomass energy content, and accounts for 35% of total operating costs. In contrast, H2 cost and catalyst recycle are relatively minor contributors to operating costs and environmental impacts. In the carbohydrate-rich pulps, polysaccharide retention is predicted not to substantially affect the RCF oil MSP. Anal. of cases using different solvents and hemicellulose as an in situ hydrogen donor reveals that reducing reactor pressure and the use of low vapor pressure solvents could reduce both capital costs and environmental impacts. Processes that reduce the energy demand for solvent sepn. also improve GWP, CED, and air emissions. Addnl., despite requiring natural gas imports, converting lignin as a biorefinery co-product could significantly reduce non-greenhouse gas air emissions compared to burning lignin. Overall, this study suggests that research should prioritize ways to lower RCF operating pressure to reduce capital expenses assocd. with high-pressure reactors, minimize solvent loading to reduce reactor size and energy required for solvent recovery, implement condensed-phase sepns. for solvent recovery, and utilize the entirety of RCF oil to maximize value-added product revenues.
- 5Biddy, M.; Davis, R.; Humbird, D.; Tao, L.; Dowe, N.; Guarnieri, M.; Linger, J.; Karp, E.; Salvachua, D.; Vardon, D.; Beckham, G. The techno-economic basis for coproduct manufacturing to enable hydrocarbon fuel production from lignoceullulosic biomass. ACS Sustainable Chem. Eng. 2016, 4, 3196– 3211, DOI: 10.1021/acssuschemeng.6b00243Google Scholar5The Techno-Economic Basis for Coproduct Manufacturing To Enable Hydrocarbon Fuel Production from Lignocellulosic BiomassBiddy, Mary J.; Davis, Ryan; Humbird, David; Tao, Ling; Dowe, Nancy; Guarnieri, Michael T.; Linger, Jeffrey G.; Karp, Eric M.; Salvachua, Davinia; Vardon, Derek R.; Beckham, Gregg T.ACS Sustainable Chemistry & Engineering (2016), 4 (6), 3196-3211CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)Biorefinery process development relies on techno-economic anal. (TEA) to identify primary cost drivers, prioritize research directions, and mitigate tech. risk for scale-up through development of detailed process designs. Here, the authors conduct TEA of a model 2000 dry metric ton-per-day lignocellulosic biorefinery that employs a 2-step pretreatment and enzymic hydrolysis to produce biomass-derived sugars, followed by biol. lipid prodn., lipid recovery, and catalytic hydrotreating to produce renewable diesel blendstock (RDB). From projected near-term tech. feasibility of these steps, the authors predict that RDB could be produced at a min. fuel selling price (MFSP) of USD $9.55/gasoline-gal-equiv. (GGE), predicated on the need for improvements in the lipid productivity and yield beyond current benchmark performance. This cost is significant given the limitations in scale and high costs for aerobic cultivation of oleaginous microbes and subsequent lipid extn./recovery. In light of this predicted cost, the authors developed an alternative pathway which demonstrates that RDB costs could be substantially reduced in the near term if upgradeable fractions of biomass, in this case hemicellulose-derived sugars, are diverted to coproducts of sufficient value and market size; here, the authors use succinic acid as an example coproduct. The coprodn. model predicts an MFSP of USD $5.28/GGE when leaving conversion and yield parameters unchanged for the fuel prodn. pathway, leading to a change in biorefinery RDB capacity from 24 to 15 MM GGE/yr and 0.13 MM tons of succinic acid per yr. Addnl. anal. demonstrates that beyond the near-term projections assumed in the models here, further redns. in the MFSP toward $2-3/GGE (which would be competitive with fossil-based hydrocarbon fuels) are possible with addnl. transformational improvements in the fuel and coproduct trains, esp. in terms of C efficiency to both fuels and coproducts, recovery and purifn. of fuels and coproducts, and coproduct selection and price. Overall, this anal. documents potential economics for both a hydrocarbon fuel and bioproduct process pathway and highlights prioritized research directions beyond the current benchmark to enable hydrocarbon fuel prodn. via an oleaginous microbial platform with simultaneous coproduct manufg. from lignocellulosic biomass.
- 6Sheldon, R. A. Metrics of green chemistry and sustainability: Past, present, and future. ACS Sustainable Chem. Eng. 2018, 6, 32– 48, DOI: 10.1021/acssuschemeng.7b03505Google Scholar6Metrics of Green Chemistry and Sustainability: Past, Present, and FutureSheldon, Roger A.ACS Sustainable Chemistry & Engineering (2018), 6 (1), 32-48CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)A review concerning historic, current, and future green chem. and sustainability metrics for fine org. chem. and pharmaceutical prodn. is given. Topics discussed include: green chem. origins; catalysis soln. to pollution; mass-based green metrics (atom economy and the E [environmental] factor, other mass-based metrics, system boundaries and intrinsic E factors); sustainability metrics and the environmental impact of wastes (energy efficiency metrics, environmental impact of wastes, life cycle assessment); from environmental impact to sustainability (circular economy); the bio-based economy; and summary and future outlook.
- 7Prat, D.; Wells, A.; Hayler, J.; Sneddon, H.; McElroy, C. R.; Abou-Shehada, S.; Dunn, P. J. CHEM21 Selection guide of classical- and less classical-solvents. Green Chem. 2016, 18, 288– 296, DOI: 10.1039/C5GC01008JGoogle Scholar7CHEM21 selection guide of classical- and less classical-solventsPrat, Denis; Wells, Andy; Hayler, John; Sneddon, Helen; McElroy, C. Robert; Abou-Shehada, Sarah; Dunn, Peter J.Green Chemistry (2016), 18 (1), 288-296CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)A selection guide of common solvents has been elaborated, based on a survey of publically available solvent selection guides. In order to rank less classical solvents, a set of Safety, Health and Environment criteria is proposed, aligned with the Global Harmonized System (GHS) and European regulations. A methodol. based on a simple combination of these criteria gives an overall preliminary ranking of any solvent. This enables in particular a simplified greenness evaluation of bio-derived solvents.
- 8Foley, B.; Johnson, B.; Bhan, A. A Method for assessing catalyst deactivation: A case study on methanol-to-hydrocarbons conversion. ACS Catal. 2019, 9, 7065– 7072, DOI: 10.1021/acscatal.9b01106Google Scholar8A Method for Assessing Catalyst Deactivation: A Case Study on Methanol-to-Hydrocarbons ConversionFoley, Brandon L.; Johnson, Blake A.; Bhan, AdityaACS Catalysis (2019), 9 (8), 7065-7072CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)When deactivation is caused by the loss of active sites, conversion vs. time-onstream measurements are insufficient assessors of deactivation because these data conflate the reaction kinetics and the rate-of-change of contact time. Instead, we consider active sites as consumable akin to reacting species and on this basis propose that definitions of rate, yield, and selectivity, commonly used for describing transformations of reactants, can be transposed to describe catalyst deactivation, which we refer to as the site-loss rate, site-loss yield, and site-loss selectivity. For reaction systems where deactivation is nonselective, i.e., systems where product yields at a given contact time do not dier between fresh and partially deactivated catalysts, instantaneous site-loss rate, yield, and selectivity are assessors of deactivation. For systems where deactivation is selective, it is instead necessary to use cumulative site-loss selectivity, the ratio of total sites lost to total moles reactant consumed or converted to effluent products, to assess deactivation, a metric inversely related to the total conversion capacity and total turnovers of a catalyst. We demonstrate the utility of quantifying deactivation using the newly dened deactivation assessors by obtaining mechanistic insights into catalyst deactivation during methanol-to-hydrocarbons conversion with formaldehyde cofeeds. Site-loss selectivity of HCHO increases with increasing HCHO cofeed pressure, suggesting the existence of competing HCHO consumption pathways and suggesting that the pathways toward active site consumption are enhanced with increasing HCHO cofeed pressure.
- 9Shi, R.; Guest, J. BioSTEAM-LCA: An integrated modeling framework for gaile life cycle assessment of biorefineries under uncertainty. ACS Sustainable Chem. Eng. 2020, 8, 18903– 18914, DOI: 10.1021/acssuschemeng.0c05998Google Scholar9BioSTEAM-LCA: An integrated modeling framework for agile life cycle assessment of biorefineries under uncertaintyShi, Rui; Guest, Jeremy S.ACS Sustainable Chemistry & Engineering (2020), 8 (51), 18903-18914CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)Biorefineries will play a crit. role in sustainable bioeconomies, but projections of their environmental impacts vary widely. A core challenge with life cycle assessments (LCAs) of biorefineries is that they are often disconnected from biorefinery design, simulation, and techno-economic anal. (TEA). This lack of integration is a barrier to early stage technol. and process evaluations, reducing consistency and transparency across sustainability indicators while limiting our understanding of the relative importance of individual factors (e.g., design decisions, greenhouse gas emission accounting procedures), how these factors interact, and trade-offs or synergies with process economics. In this study, we propose a new agile LCA framework, BioSTEAM-LCA, which layers onto BioSTEAM (Biorefinery Simulation and Techno-Economic Anal. Modules, which automates biorefinery design, simulation, and TEA) to characterize the environmental impacts of biorefineries across a landscape of designs, technol. performance assumptions, and contexts. Inventory databases and impact assessment methods are integrated to enable flexible user defined LCA system models, and the implications of uncertainties throughout the prodn. system are characterized via Monte Carlo simulation. To demonstrate the capabilities of BioSTEAM-LCA, we present a case study for sugarcane ethanol prodn. Overall, BioSTEAM-LCA enables computationally efficient, agile gate-to-gate LCA to evaluate biorefinery processes, the prodn. of candidate biofuels and bioproducts, and trade-offs among productivity, economics, and environmental impacts under uncertainty. BioSTEAM-LCA is an open-source simulation platform for agile LCA-TEA of biorefineries to quantify and navigate trade-offs across dimensions (functional performance, economic, environmental) of sustainability.
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- Audrey Moores, (Executive Editor, ACS Sustainable Chemistry & Engineering)Jingwen Chen, (Executive Editor, ACS Sustainable Chemistry & Engineering)Bala Subramaniam, (Executive Editor, ACS Sustainable Chemistry & Engineering)Michael KC Tam, (Deputy Editor, ACS Sustainable Resource Management)Elizabeth J. Biddinger, (Associate Editor, ACS Sustainable Chemistry & Engineering)Dean Brady, (Associate Editor, ACS Sustainable Chemistry & Engineering)Danielle Julie Carrier, (Associate Editor, ACS Sustainable Chemistry & Engineering)Ivet Ferrer, (Associate Editor, ACS Sustainable Resource Management)Nicholas Gathergood, (Associate Editor, ACS Sustainable Chemistry & Engineering)Hongxian Han, (Associate Editor, ACS Sustainable Chemistry & Engineering)Ive Hermans, (Associate Editor, ACS Sustainable Chemistry & Engineering)King Kuok Mimi Hii, (Associate Editor, ACS Sustainable Chemistry & Engineering)Bing Joe Hwang, (Associate Editor, ACS Sustainable Chemistry & Engineering)Milad Kamkar, (Topic Editor, ACS Sustainable Resource Management)Kevin Leonard, (Associate Editor, ACS Sustainable Chemistry & Engineering)Watson Loh, (Associate Editor, ACS Sustainable Chemistry & Engineering)Say Chye Joachim Loo, (Associate Editor, ACS Sustainable Resource Management)Andrew C. Marr, (Associate Editor, ACS Sustainable Chemistry & Engineering)Michael A.R. Meier, (Associate Editor, ACS Sustainable Chemistry & Engineering)Ryuhei Nakamura, (Associate Editor, ACS Sustainable Chemistry & Engineering)Graham N. Newton, (Associate Editor, ACS Sustainable Chemistry & Engineering)Thalappil Pradeep, (Associate Editor, ACS Sustainable Resource Management)Kotaro Satoh, (Associate Editor, ACS Sustainable Chemistry & Engineering)Wil V. Srubar, III, (Associate Editor, ACS Sustainable Chemistry & Engineering)Ning Yan, (Associate Editor, ACS Sustainable Chemistry & Engineering)Asha James, (Development Editor)Mihir Jha, (Development Editor)Atal Shivhare, (Development Editor)Julio F. Serrano, (Managing Editor)Peter Licence (Editor-in-Chief). Reintroducing the INTRODUCTION: How to Write a Compelling Introduction for the ACS Sustainable Family of Journals. ACS Sustainable Resource Management 2024, 1
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- 1Debecker, D. P.; Kuok (Mimi) Hii, K.; Moores, A.; Rossi, L. M.; Sels, B.; Allen, D. T.; Subramaniam, B. Shaping effective practices for incorporating sustainability assessment in manuscripts submitted to ACS Sustainable Chemistry & Engineering: Catalysis and catalytic processes. ACS Sustainable Chem. Eng. 2021, 9, 4936– 4940, DOI: 10.1021/acssuschemeng.1c020701Shaping Effective Practices for Incorporating Sustainability Assessment in Manuscripts Submitted to ACS Sustainable Chemistry & Engineering: Catalysis and Catalytic ProcessesDebecker, Damien P.; Kuok Hii, King; Moores, Audrey; Rossi, Liane M.; Sels, Bert; Allen, David T.; Subramaniam, BalaACS Sustainable Chemistry & Engineering (2021), 9 (14), 4936-4940CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)There is no expanded citation for this reference.
- 2Raud, M.; Kikas, T.; Sippula, O.; Shurpali, N. J. Potentials and challenges in lignocellulosic biofuel production technology. Renewable Sustainable Energy Rev. 2019, 111, 44– 56, DOI: 10.1016/j.rser.2019.05.0202Potentials and challenges in lignocellulosic biofuel production technologyRaud, M.; Kikas, T.; Sippula, O.; Shurpali, N. J.Renewable & Sustainable Energy Reviews (2019), 111 (), 44-56CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)A review. Since the Kyoto protocol, the EU renewable energy policy has been the driving force in research and development of the prodn. and use of biofuels. Therefore, the utilization of biofuels and the scientific research to widen the scope of their commercialization are being increasingly promoted. In this context, we present here an overview of the technol. developments that have occurred in the prodn. of different biofuels and their resources with a focus on the lignocellulosic biomass and biofuels derived from it. In the recent years, many technologies have evolved enabling the prodn. of different liq. biofuels from lignocellulosic biomass. Bioethanol prodn. using microbial fermn., and prodn. of bio-oil using fast pyrolysis process of biomass are some of the most widely researched and promising technologies. The first prodn. plants based on these techniques are already operational. Bioethanol prodn. from lignocellulosic biomass promises a good fuel yield under lab. scale. However, there are several challenges that need to be tackled before the prodn. process can be commercialized. We provide here an overview of the various possibilities that can be exploited for biofuel prodn. and make recommendations for increasing the prodn. efficiency with a view to improving the overall yield and lowering the prodn. costs.
- 3Ong, H.; Chen, W.-H.; Farooq, A.; Gan, Y.; Lee, K.; Ashokkumar, V. Catalytic thermochemical conversion of biomass for biofuel production: A comprehensive review. Renewable Sustainable Energy Rev. 2019, 113, 109266, DOI: 10.1016/j.rser.2019.1092663Catalytic thermochemical conversion of biomass for biofuel production: A comprehensive reviewOng, Hwai Chyuan; Chen, Wei-Hsin; Farooq, Abid; Gan, Yong Yang; Lee, Keat Teong; Ashokkumar, VeeramuthuRenewable & Sustainable Energy Reviews (2019), 113 (), 109266CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)A review. The increasing demand for energy and diminishing sources of fossil fuels have called for the discovery of new energy sources. The effective energy conversion process of biomass is able to fulfill energy needs. Among the advanced biomass conversion technologies, thermochem. processes hold considerable potential approaches and needed for optimization. Thus, this study presents a comprehensive review of the research and development on the effects of catalysts on the thermochem. conversion of biomass to det. the progress of catalytic thermochem. conversion processes. The effects of catalysts on torrefaction, pyrolysis, hydrothermal liquefaction, and gasification are highlighted. Aspects related to reaction conditions, reactor types, and products are discussed comprehensively with the reaction mechanisms involved in the catalytic effects. Hydrogenation and hydrodeoxygenation can occur in the presence of zeolite catalysts during fast pyrolysis while producing highly arom. bio-oil. A heterogeneous catalyst in liquefaction increases the hydrocarbon content and decreases viscosity, acid value, and oxygenated compds. in the bio-oil. Thus, expanding and enhancing knowledge about catalyst utilization in the thermochem. conversion technologies of biomass will play an important role in the generation of renewable and carbon-neutral fuels.
- 4Bartling, A.; Stone, M.; Hanes, R.; Bhatt, A.; Zhang, Y.; Biddy, M.; Davis, R.; Kruger, J.; Thornburg, N.; Luterbacher, J.; Rinaldi, R.; Samec, J.; Sels, B.; Roman-Leshkov, Y.; Beckham, G. Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation. Energy Environ. Sci. 2021, 14, 4147– 4168, DOI: 10.1039/D1EE01642C4Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionationBartling, Andrew W.; Stone, Michael L.; Hanes, Rebecca J.; Bhatt, Arpit; Zhang, Yimin; Biddy, Mary J.; Davis, Ryan; Kruger, Jacob S.; Thornburg, Nicholas E.; Luterbacher, Jeremy S.; Rinaldi, Roberto; Samec, Joseph S. M.; Sels, Bert F.; Roman-Leshkov, Yuriy; Beckham, Gregg T.Energy & Environmental Science (2021), 14 (8), 4147-4168CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Reductive catalytic fractionation (RCF) is a promising approach to fractionate lignocellulose and convert lignin to a narrow product slate. To guide research towards commercialization, cost and sustainability must be considered. Here we report a techno-economic anal. (TEA), life cycle assessment (LCA), and air emission anal. of the RCF process, wherein biomass carbohydrates are converted to ethanol and the RCF oil is the lignin-derived product. The base-case process, using a feedstock supply of 2000 dry metric tons per day, methanol as a solvent, and H2 gas as a hydrogen source, predicts a min. selling price (MSP) of crude RCF oil of $1.13 per kg when ethanol is sold at $2.50 per gal of gasoline-equiv. ($0.66 per L of gasoline-equiv.). We est. that the RCF process accounts for 57% of biorefinery installed capital costs, 77% of pos. life cycle global warming potential (GWP) (excluding carbon uptake), and 43% of pos. cumulative energy demand (CED). Of $563.7 MM total installed capital costs, the RCF area accounts for $323.5 MM, driven by high-pressure reactors. Solvent recycle and water removal via distn. incur a process heat demand equiv. to 73% of the biomass energy content, and accounts for 35% of total operating costs. In contrast, H2 cost and catalyst recycle are relatively minor contributors to operating costs and environmental impacts. In the carbohydrate-rich pulps, polysaccharide retention is predicted not to substantially affect the RCF oil MSP. Anal. of cases using different solvents and hemicellulose as an in situ hydrogen donor reveals that reducing reactor pressure and the use of low vapor pressure solvents could reduce both capital costs and environmental impacts. Processes that reduce the energy demand for solvent sepn. also improve GWP, CED, and air emissions. Addnl., despite requiring natural gas imports, converting lignin as a biorefinery co-product could significantly reduce non-greenhouse gas air emissions compared to burning lignin. Overall, this study suggests that research should prioritize ways to lower RCF operating pressure to reduce capital expenses assocd. with high-pressure reactors, minimize solvent loading to reduce reactor size and energy required for solvent recovery, implement condensed-phase sepns. for solvent recovery, and utilize the entirety of RCF oil to maximize value-added product revenues.
- 5Biddy, M.; Davis, R.; Humbird, D.; Tao, L.; Dowe, N.; Guarnieri, M.; Linger, J.; Karp, E.; Salvachua, D.; Vardon, D.; Beckham, G. The techno-economic basis for coproduct manufacturing to enable hydrocarbon fuel production from lignoceullulosic biomass. ACS Sustainable Chem. Eng. 2016, 4, 3196– 3211, DOI: 10.1021/acssuschemeng.6b002435The Techno-Economic Basis for Coproduct Manufacturing To Enable Hydrocarbon Fuel Production from Lignocellulosic BiomassBiddy, Mary J.; Davis, Ryan; Humbird, David; Tao, Ling; Dowe, Nancy; Guarnieri, Michael T.; Linger, Jeffrey G.; Karp, Eric M.; Salvachua, Davinia; Vardon, Derek R.; Beckham, Gregg T.ACS Sustainable Chemistry & Engineering (2016), 4 (6), 3196-3211CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)Biorefinery process development relies on techno-economic anal. (TEA) to identify primary cost drivers, prioritize research directions, and mitigate tech. risk for scale-up through development of detailed process designs. Here, the authors conduct TEA of a model 2000 dry metric ton-per-day lignocellulosic biorefinery that employs a 2-step pretreatment and enzymic hydrolysis to produce biomass-derived sugars, followed by biol. lipid prodn., lipid recovery, and catalytic hydrotreating to produce renewable diesel blendstock (RDB). From projected near-term tech. feasibility of these steps, the authors predict that RDB could be produced at a min. fuel selling price (MFSP) of USD $9.55/gasoline-gal-equiv. (GGE), predicated on the need for improvements in the lipid productivity and yield beyond current benchmark performance. This cost is significant given the limitations in scale and high costs for aerobic cultivation of oleaginous microbes and subsequent lipid extn./recovery. In light of this predicted cost, the authors developed an alternative pathway which demonstrates that RDB costs could be substantially reduced in the near term if upgradeable fractions of biomass, in this case hemicellulose-derived sugars, are diverted to coproducts of sufficient value and market size; here, the authors use succinic acid as an example coproduct. The coprodn. model predicts an MFSP of USD $5.28/GGE when leaving conversion and yield parameters unchanged for the fuel prodn. pathway, leading to a change in biorefinery RDB capacity from 24 to 15 MM GGE/yr and 0.13 MM tons of succinic acid per yr. Addnl. anal. demonstrates that beyond the near-term projections assumed in the models here, further redns. in the MFSP toward $2-3/GGE (which would be competitive with fossil-based hydrocarbon fuels) are possible with addnl. transformational improvements in the fuel and coproduct trains, esp. in terms of C efficiency to both fuels and coproducts, recovery and purifn. of fuels and coproducts, and coproduct selection and price. Overall, this anal. documents potential economics for both a hydrocarbon fuel and bioproduct process pathway and highlights prioritized research directions beyond the current benchmark to enable hydrocarbon fuel prodn. via an oleaginous microbial platform with simultaneous coproduct manufg. from lignocellulosic biomass.
- 6Sheldon, R. A. Metrics of green chemistry and sustainability: Past, present, and future. ACS Sustainable Chem. Eng. 2018, 6, 32– 48, DOI: 10.1021/acssuschemeng.7b035056Metrics of Green Chemistry and Sustainability: Past, Present, and FutureSheldon, Roger A.ACS Sustainable Chemistry & Engineering (2018), 6 (1), 32-48CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)A review concerning historic, current, and future green chem. and sustainability metrics for fine org. chem. and pharmaceutical prodn. is given. Topics discussed include: green chem. origins; catalysis soln. to pollution; mass-based green metrics (atom economy and the E [environmental] factor, other mass-based metrics, system boundaries and intrinsic E factors); sustainability metrics and the environmental impact of wastes (energy efficiency metrics, environmental impact of wastes, life cycle assessment); from environmental impact to sustainability (circular economy); the bio-based economy; and summary and future outlook.
- 7Prat, D.; Wells, A.; Hayler, J.; Sneddon, H.; McElroy, C. R.; Abou-Shehada, S.; Dunn, P. J. CHEM21 Selection guide of classical- and less classical-solvents. Green Chem. 2016, 18, 288– 296, DOI: 10.1039/C5GC01008J7CHEM21 selection guide of classical- and less classical-solventsPrat, Denis; Wells, Andy; Hayler, John; Sneddon, Helen; McElroy, C. Robert; Abou-Shehada, Sarah; Dunn, Peter J.Green Chemistry (2016), 18 (1), 288-296CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)A selection guide of common solvents has been elaborated, based on a survey of publically available solvent selection guides. In order to rank less classical solvents, a set of Safety, Health and Environment criteria is proposed, aligned with the Global Harmonized System (GHS) and European regulations. A methodol. based on a simple combination of these criteria gives an overall preliminary ranking of any solvent. This enables in particular a simplified greenness evaluation of bio-derived solvents.
- 8Foley, B.; Johnson, B.; Bhan, A. A Method for assessing catalyst deactivation: A case study on methanol-to-hydrocarbons conversion. ACS Catal. 2019, 9, 7065– 7072, DOI: 10.1021/acscatal.9b011068A Method for Assessing Catalyst Deactivation: A Case Study on Methanol-to-Hydrocarbons ConversionFoley, Brandon L.; Johnson, Blake A.; Bhan, AdityaACS Catalysis (2019), 9 (8), 7065-7072CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)When deactivation is caused by the loss of active sites, conversion vs. time-onstream measurements are insufficient assessors of deactivation because these data conflate the reaction kinetics and the rate-of-change of contact time. Instead, we consider active sites as consumable akin to reacting species and on this basis propose that definitions of rate, yield, and selectivity, commonly used for describing transformations of reactants, can be transposed to describe catalyst deactivation, which we refer to as the site-loss rate, site-loss yield, and site-loss selectivity. For reaction systems where deactivation is nonselective, i.e., systems where product yields at a given contact time do not dier between fresh and partially deactivated catalysts, instantaneous site-loss rate, yield, and selectivity are assessors of deactivation. For systems where deactivation is selective, it is instead necessary to use cumulative site-loss selectivity, the ratio of total sites lost to total moles reactant consumed or converted to effluent products, to assess deactivation, a metric inversely related to the total conversion capacity and total turnovers of a catalyst. We demonstrate the utility of quantifying deactivation using the newly dened deactivation assessors by obtaining mechanistic insights into catalyst deactivation during methanol-to-hydrocarbons conversion with formaldehyde cofeeds. Site-loss selectivity of HCHO increases with increasing HCHO cofeed pressure, suggesting the existence of competing HCHO consumption pathways and suggesting that the pathways toward active site consumption are enhanced with increasing HCHO cofeed pressure.
- 9Shi, R.; Guest, J. BioSTEAM-LCA: An integrated modeling framework for gaile life cycle assessment of biorefineries under uncertainty. ACS Sustainable Chem. Eng. 2020, 8, 18903– 18914, DOI: 10.1021/acssuschemeng.0c059989BioSTEAM-LCA: An integrated modeling framework for agile life cycle assessment of biorefineries under uncertaintyShi, Rui; Guest, Jeremy S.ACS Sustainable Chemistry & Engineering (2020), 8 (51), 18903-18914CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)Biorefineries will play a crit. role in sustainable bioeconomies, but projections of their environmental impacts vary widely. A core challenge with life cycle assessments (LCAs) of biorefineries is that they are often disconnected from biorefinery design, simulation, and techno-economic anal. (TEA). This lack of integration is a barrier to early stage technol. and process evaluations, reducing consistency and transparency across sustainability indicators while limiting our understanding of the relative importance of individual factors (e.g., design decisions, greenhouse gas emission accounting procedures), how these factors interact, and trade-offs or synergies with process economics. In this study, we propose a new agile LCA framework, BioSTEAM-LCA, which layers onto BioSTEAM (Biorefinery Simulation and Techno-Economic Anal. Modules, which automates biorefinery design, simulation, and TEA) to characterize the environmental impacts of biorefineries across a landscape of designs, technol. performance assumptions, and contexts. Inventory databases and impact assessment methods are integrated to enable flexible user defined LCA system models, and the implications of uncertainties throughout the prodn. system are characterized via Monte Carlo simulation. To demonstrate the capabilities of BioSTEAM-LCA, we present a case study for sugarcane ethanol prodn. Overall, BioSTEAM-LCA enables computationally efficient, agile gate-to-gate LCA to evaluate biorefinery processes, the prodn. of candidate biofuels and bioproducts, and trade-offs among productivity, economics, and environmental impacts under uncertainty. BioSTEAM-LCA is an open-source simulation platform for agile LCA-TEA of biorefineries to quantify and navigate trade-offs across dimensions (functional performance, economic, environmental) of sustainability.