Processes 03 00634
Processes 03 00634
Processes 03 00634
3390/pr3030634
OPEN ACCESS
processes
ISSN 2227-9717
www.mdpi.com/journal/processes
Review
1
Swanson School of Engineering, Department of Civil and Environmental Engineering,
University of Pittsburgh, Pittsburgh, PA 15621, USA; E-Mails: ggz2@pitt.edu (G.G.Z.);
nev11@pitt.edu (N.V.); shc82@pitt.edu (S.S.C.)
2
Glenn Department of Civil Engineering, Clemson University, Clemson, SC 29631, USA;
E-Mail: amy.landis@asu.edu
Abstract: The current methodological approach for developing sustainable biofuel processes
and supply chains is flawed. Life cycle principles are often retrospectively incorporated in
the design phase resulting in incremental environmental improvement rather than selection
of fuel pathways that minimize environmental impacts across the life cycle. Further,
designing sustainable biofuel supply chains requires joint consideration of economic,
environmental, and social factors that span multiple spatial and temporal scales. However,
traditional life cycle assessment (LCA) ignores economic aspects and the role of ecological
goods and services in supply chains, and hence is limited in its ability for guiding decision-
making among alternatives—often resulting in sub-optimal solutions. Simultaneously
incorporating economic and environment objectives in the design and optimization of
emerging biofuel supply chains requires a radical new paradigm. This work discusses key
research opportunities and challenges in the design of emerging biofuel supply chains
and provides a high-level overview of the current “state of the art” in environmental
sustainability assessment of biofuel production. Additionally, a bibliometric analysis of over
20,000 biofuel research articles from 2000-to-present is performed to identify active topical
areas of research in the biofuel literature, quantify the relative strength of connections
between various biofuels research domains, and determine any potential research gaps.
Processes 2015, 3 635
Keywords: biofuels; sustainability; sustainable biofuel supply chain; next generation biofuels;
bibliometric analysis; multiobjective optimization; multiscale modeling; life cycle assessment
1. Introduction
Chemical technologies and the chemical process industry provide a range of useful and valuable
products derived from biobased resources for use in personal care products, health products,
agrochemicals, and transportation fuels. However, the production of these products is accompanied by
generation of vast quantities of wastes and a range of harmful emissions to air, water, and soil. There is
increasing realization that resource consumption and anthropogenic-derived impacts can have
long-standing consequences on global ecological systems, and place strain on the natural
biogeochemical cycles that support human life. Published findings from the millennium ecosystem
assessment (MEA)—an international collaboration designed to assess the impact and widespread
consequences of environmental change for human and ecological well-being, indicate that in the second
half of the 20th century anthropogenic-derived resource degradation and overconsumption of natural
capital have changed ecosystems more rapidly and extensively than in any comparable period in human
history [1]. Rockstrom and colleagues assessed that the Earth has transgressed planetary boundaries for
climate change, biodiversity, nitrogen cycle balance and is fast approaching the limit of safe operating
space for global freshwater use, land use change, ocean acidification and global phosphorous cycle
balance [2–5].
Traditional methods of chemical process design have primarily relied on finding the economic
optimum subject to physical constraints, namely satisfying the heat and material balances and
thermodynamic limitations. However, concerns over the depleting fossil energy sources, mounting
regulatory compliance and the resulting push towards environmentally conscious process design are
forcing designers to consider reduced environmental impact as one of the product design objectives.
Business leaders have begun to realize that such a shift towards more sustainable design practices can
not only minimize the environmental impact of industrial activity but is also crucial for long term success
and sustainability of their enterprises.
The emerging field of sustainability science and engineering is developing tools to recognize,
quantify, and reconcile resource limitations; human needs, and optimize global and human benefit. The
concept of sustainability is multifaceted; encompassing the entirety of the human enterprise, interfacing
with environmental, social, political, and economic issues, and as such is highly interdisciplinary. The
outstanding challenge facing the chemical industry is the incorporation of environmental and
sustainability objectives along with traditional design objectives in the development of emerging
chemical processes. The rapid development of biofuels as a potentially sustainable and cleaner
replacement for conventional fuels represents a unique challenge for the chemical industry that requires
simultaneous consideration of economic, social, and ecological aspects and thus exemplifies an excellent
content in which to understand the challenges and opportunities for designing sustainable supply chains.
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Global climate change, volatile petroleum prices, energy security issues, and resource depletion have
driven nations to consider adding renewable and alternative energy options to their energy portfolios.
Transportation as well as the power and electricity generation sector constitute the two largest
greenhouse gas (GHG) emitting sectors in the United States, accounting for 27% and 31% of total GHG
emitted in 2013 respectively [6]. Accordingly, this has prompted the development of United States (U.S.)
regulatory programs as well as European directives designed to mitigate GHG emissions from the
transportation and power generation sector while concurrently increasing domestic energy independence
and security. In 2007 the U.S. congress passed the Energy Independence and Security Act (EISA) [7],
which mandates the production of 36 billion gallons of biofuels by the year 2022, and stipulates that a
percentage must be derived from conventional, cellulosic biofuel, biomass-based diesel, and advanced
biofuels. Additionally, EISA sets yearly volumetric biofuel production targets and requires renewable
fuels achieve minimum reductions in overall life cycle GHG emissions relative to baseline petroleum
fuels. Similarly, in 2009 the European Union (EU) passed the renewable energy directive (RED) [8].
This legislation requires that the EU obtain 20% of its total energy consumption from renewable sources,
and derive 10% of energy consumption within the transportation sector from renewable resources by
2020. Furthermore, the EU imposed a 5% cap on the amount of food crop-derived biofuels used to meet
the EU’s 2020 goal, in an effort to mitigate the potential social and economic impacts of competition
between crops for food vs. fuel. The RED sets minimum life cycle GHG emission reductions targets of
35% relative to baseline petroleum fuels for the year 2010, increasing to 50% in 2017 and 60% in 2018.
Currently ethanol from corn is the most widely produced and utilized biofuel in the United States.
However, critical concerns have been raised about the potential of corn ethanol and other first generation
biofuels in mitigating climate change and reducing dependence on fossil fuels. It has been contended
that the direct and indirect land use change effects may possibly negate the GHG reduction potential of
first generation biofuels possibly resulting in overall higher life cycle GHG emissions relative to baseline
petroleum fuels [9–11]. In addition, first generation biofuels require changes in the existing
transportation infrastructure such as modifications to vehicle engines and fuel pipelines. Further, the
production and use of first generation biofuels have resulted in deleterious impacts on ecosystem goods
and services such as soil erosion, water and air pollution, and loss of biodiversity, and thus have
prompted the development of next generation biofuels [12].
A myriad of feedstocks and conversion platforms pathways are currently under development for next
generation biofuel production, shown in Figure 1. Common biofeedstocks include sugarcane and corn,
lignocellulosic biomass, algae, and oil-seeds. Lignocellulosic feedstocks include agricultural residues
such as corn stover and forest residues; energy crops such as switchgrass, Miscanthus, and poplar; and
industrial/municipal solid wastes. Additionally, several non-food lipid sources including algae and
Jatropha are being considered for biofuel production. The “Billion Ton Study” jointly conducted by the
US Department of Energy (DOE) and the US Department of Agriculture (USDA) provides a detailed
quantification of available biomass in the US for producing fuels and biobased products, and estimates
that up to 1.6 billion tons of dry biomass can be produced annually in the contiguous U.S. for meeting
growing energy demands without displacing critical food, fiber, or feed crops [13]. These findings are
Processes 2015, 3 637
compelling as they suggest that the U.S. has the capacity to support a large-scale domestic biofuels and
bioproducts market.
Sugarcane/Corn Hydrolysis
Fermentation
Grain Catalysis Ethanol
Sugars Coproduct
Biochemical Fermentation
Lignocellulosic Water-Gas-Shift
Hydrogen
Feedstock Gasification MeOH Synthesis
Syngas F-T Synthesis
• Agricultural residue
• Forest resources Coproduct Methanol
• Energy Crops Pyrolysis/Liquefaction
MTG
• Industrial & Municipal
solid waste
Hydrocarbon Biofuels
• Green Gasoline
• Renewable Diesel
Hydro-processing • Aviation Fuel
Algae and Oil- Lipid Extraction
Figure 1. Feedstocks and conversion pathways for biofuel production. MTG: Methanol to
Gasoline. F-T Synthesis: Fischer-Tropsch Synthesis.
decentralized, small-scale combustion and anaerobic digestion conversion systems [53–55]. The biofuel
research landscape is rapidly evolving in regards to process multiplicity, complexity, and scope. A
comprehensive review of historical trends in biofuel production and policy are beyond the scope of the
current work but can be found in several notable studies [56–58]. Sustainable commercialization of
biofuel production will require simultaneously addressing multiple technical, economic, social, and
environmental challenges that occur throughout the supply chain, and thus inherently necessitates a
collaborative approach.
Understanding the full range of potential environmental, social, and economic impacts of biofuel
production prior to its widespread commercialization and use is pivotal for avoiding unintended
consequences and for guiding the sustainable development of the biofuels industry [59]. Moreover,
holistic assessment of the widespread direct and indirect impacts of biofuel production requires
integrating data and information across multiple research domains and rigorous analysis of
peer-reviewed literature. As such, collaboration and synthesis across multiple disciplines is necessary
for environmentally conscious decision-making. However the degree to which interdisciplinary research
is occurring between biofuel research domains is often not well-understood or studied, such information
is critical for determining research gaps, fragmentation between research domains, and for guiding the
future trajectory of research in biofuels.
We performed a bibliometric analysis to: (1) identify active topical areas of research in the biofuel
literature; and (2) quantify the relative strength of connection between various biofuels research domains
via analyzing the occurrence and co-occurrence frequency of author supplied and indexed keywords
from over 20,000 biofuels articles published from 2000 to present. The resulting analysis provides useful
insights regarding the strength of connection and coupling between various research domains in the
biofuel literature, as well as potential research gaps, i.e., research areas that may require further synthesis
and integration. Keywords for over 20,700 articles were obtained using the search-term “Biofuels” from
the SCOPUS database [60]. In absence of author-supplied keywords, indexed keywords were used. This
approach was leveraged over using both author-supplied keywords and indexed keywords, so as to avoid
potential double counting. Keywords were aggregated into 36 topic areas related to 7 broad themes;
shown in Table 1. The analysis expands on the method of identifying and aggregating keywords provided
in Ridley et al. [61], please see supporting information for a complete list of keywords and method of
data aggregation. The analytic framework and bibliometric algorithm established in Van Eck and
Waltman was used to detect the number of co-occurrences of select keywords [62]. The co-occurrence
data was mapped via network software (ORA) [63] to visualize the dynamic interactions between select
biofuel research domains. The strength of the linkage between research topics (nodes) indicates its
relative co-occurrence and is proportional to the line width, while the size of the node indicates its
relative occurrence.
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Table 1. Themes and topics for author supplied and indexed keywords. A detailed list of all
keywords is in Table S1.
Theme Topic Example Keywords
Food Security Food Supply, Food Crop
Human Health Mortality, Asthma
GHGs Greenhouse Gases, Carbon Dioxide
Particulate Matter,
Air Quality (Non-GHGs)
Volatile Organic Compounds
Soil Resources Soil Organic Carbon, Soil Fertility
Environmental & Human
Indirect Land Use Change,
Wellbeing Land Use Change
Direct Land Use Change
Water Resources Groundwater, Water Footprint
Biodiversity Wildlife, Biodiversity
Life Cycle Analysis,
Life Cycle Assessment
Life Cycle Assessment
Ecosystem Services Ecosystem Services, Ecosystems
Technoeconomic analysis,
Cost of Production
Infrastructure
Supply and Demand,
Economy Market Forces
Cost Competitiveness
Policy RFS2, EISA, LCFS
Trade Import, Export, Tariff
Feedstock Production and Agronomics Biomass Production, Agronomics
Production Distribution,
Feedstock Logistics Pretreatment, Biomass transportation
Technology & Infrastructure
Fuel Distribution and Infrastructure Pipeline, Fuel Storage
Aviation Fuel Aviation Fuel, Jet Fuel
Biodiesel Biodiesel, Biodiesel Blend
Ethanol Ethanol, Lignocellulosic Ethanol
Biofuels Drop in replacement
Hydrocarbon Biofuel
biofuel, Renewable Diesel
Butanol Butanol, Biobutanol
Biogas Biogas, Biomethane
Pyrolysis Fast Pyrolysis, Pyrolysis oil
Gasification Gasification, BTL
Conversion Platforms Transesterification Esterification, FAME
Hydrolysis Hydrolysis, Fermentation
Anaerobic Digestion Anaerobic Digestion
Woody Biomass Willow, Poplar
Perennial Grasses Switchgrass, Miscanthus
Feedstocks
Oil Seeds Jatropha, Soybean, Rapeseed
Algae Microaglae, Macroalgae
Sugarcane Bagasse, Corn Stover, Forest
Agricultural Residue
Residue
Feedstocks
Industrial & Municipal Waste Waste Cooking Oil, Vegetable Oil
Grains & Sugar Crops Corn, Wheat, Rye
Thermodynamics N/A Exergy, Emergy
Adapted from Ridley et al. [61].
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Biodiesel
Aviation Fuel Biogas
Fuel Distribution & Infrastructure Butanol
Feedstock Production & Agronomics Ethanol
Feedstock Logistics
Hydrocarbon Biofuel
Trade
Anaerobic Digestion
Policy
Gasification
Market Forces
Hydrolysis
Costs of Production
Pyrolysis
Water Resources
Transesterification
Soil Resources
Agricultural Residue
Figure 2 presents a co-occurrence network graph, illustrating the connectivity between various
research topics in the biofuels literature. Figure 2 reveals that greenhouse gases, biodiesel, ethanol,
transesterification, and hydrolysis had the highest frequency of co-occurrence in the literature, while
market forces, trade, biodiversity, ecosystems goods and services (EGS), thermodynamics, aviation fuel,
and hydrocarbon biofuels were not well represented. Nodes with no connections represent research fields
that lack significant collaborations with other research areas in the biofuel literature, and may be
emerging or nascent topics. Figure 2 reveals that substantial research has been invested in evaluating
GHG emissions related to biofuel production, while little effort has been made to evaluate impacts on
soil resources, human health, food security, biodiversity, and ecological goods and services. While GHG
emissions represent an important sustainability aspect for biofuel production, other categories must also
be considered so that biofuels do not inadvertently shift their impacts to other domains.
Furthermore, the lack of research (represented by lack of connecting links) on ecological goods and
services, biodiversity, soil resources, and water resources is alarming, as prior research has suggested
that the adoption of first generation biofuels have resulted in higher rates of deforestation and soil
Processes 2015, 3 642
erosion, loss of biodiversity, and increased stress on water resources [64,65]. Hydrocarbon biofuels as
well as aviation fuels were found to have marginal to no connectivity with other research domains, as
these biofuels represent emerging topics and have only recently received widespread scientific inquiry.
As such, further collaborative research is needed in all aspects of these emerging fuel platforms. The
network diagram shows sparse scientific coverage on the market forces and/or trade aspects of biofuel
production, despite consistent growth in the international trade of biomass/biofuels over the past decade.
Failure to consider the broader trade and market implications of biofuel production could have
significant global economic and social repercussions. This is particularly important for developing
countries that are increasing biofuel exports to meet international policy mandated volumetric biofuel
production and renewable energy targets, as developing nations are often highly sensitive to the potential
adverse impacts of biofuel production including accelerated destruction of natural ecosystems,
agricultural runoff and soil erosion, increased food insecurity and malnutrition, and global climate
change. The results of the bibliographic analysis highlight the need for further interdisciplinary research
so to assess any potential dynamic interactions, feedbacks, trade-offs, and mitigate any unintended
consequences of biofuel production.
The process of introducing and implementing environmentally benign strategies in chemical process
design started with the introduction of heat integration strategies. These schemes were primarily
introduced in response to the energy crisis at that time and not only led to reduction in the overall energy
consumption in production plants but also increased revenues by minimizing the plant operating costs.
Although these strategies introduced the concept of environmentally conscious design, they generally
had a narrow scope and boundary. Traditionally, the chemical process industry has responded to the
environmental challenge by resorting to end-of-pipe solutions or pollution remediation such as recycling,
waste treatment, and disposal. Although these practices are valuable, they may require vast capital and
operating expenditures and can often shift the domain of pollution by moving it outside the analysis
boundary. It is for this reason that in the last decade strategies and concepts such as green chemistry, life
cycle assessment, environmentally conscious process design, and design for environment have come
into prominence [66,67]. These concepts are attractive with their primary focus on avoiding waste
generation rather than waste minimization. The unifying theme behind these approaches is to look at
systems holistically by expanding the system boundary in traditional process design. Although, expanding
the system boundary for a more holistic analysis is appealing, it presents a new challenge associated with
the need for increased amount of data and computational time. With appreciation of such challenges and
to address the shortcomings of some of these earlier approaches, process systems engineering has
gradually expanded its analysis boundary from the narrowly focused process scale to the life cycle or
supply chain scale and more recently to the ecosystem scale [68–72]. These approaches take a more
holistic view by focusing on the entire life cycle or supply and demand webs of the selected products or
processes. Zhuang et al. reviewed several existing modeling approaches for sustainable chemical production
and their applications at multiple scales ranging from metabolism, to the life cycle, to ecosystems, and
proposed a multi-scale approach integrating these models into a single cohesive framework [73].
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Recent interest in biofuels has led to the development and use of models and computational tools at
multiple scales including large-scale crop models, detailed chemical process design simulations, life
cycle assessment models, and mathematical optimization tools. While these computational methods each
Processes 2015, 3 644
provide unique and novel insights into the sustainability of emerging biofuels, these tools are often used
in isolation and thus are limited in their ability for guiding decision-making. Synthesis of these models
and tools into a unified framework, via collaboration between researchers across disciplines and modeling
scales is required to provide a broader understanding of the sustainability of emerging biomass-to-fuel
supply chains. Accordingly, this work discusses a modular multi-scale and multi-objective framework
spanning from the field/lab scale, to the detailed process scale, the life cycle scale, and finally the
ecosystems scale for holistic sustainability assessment of biofuel production; see Figure 3. The
envisioned multi-scale approach evaluates the process in a hierarchical fashion, starting from the
field/lab scale and expanding the system boundaries as successive scales are added. Information from
lab/field trials such as reactor kinetic studies, pilot-scale biomass growth trials, and experimental trials
on biofuel yields are used to parameterize design blocks and crop models used at the process level.
Information such as liquid product distribution and operating plant utility requirements obtained via the
process level is subsequently utilized to model unit processes in the supply chain. Information at the
supply chain is coupled with the larger economy and ecosystems via the use of environmentally extended
economic models. The proposed framework synthesizes results obtained from models/methods across
disciplines and scales (i.e., the lab/field scale, process scale, supply chain, and ecosystem scale) to inform
process design and decision-making. Insights obtained from models/methods at differing scales (as well
as their limitations) are disseminated between researchers working at different modeling tiers. This
multi-scale interdisciplinary approach provides stakeholders different tiers of decision-making criteria
(i.e., capital and operating costs, environmental damages, or ecological impacts), and thus a holistic
understanding of the broader consequences of emerging fuel pathways. Further, such an approach is
conceptually attractive since it facilitates the evaluation procedure starting with simple systems and
increasing complexity gradually as successive information layers are added. This approach can allow for
screening out bad alternatives, for example, those with a negative economic potential early in the design
stage thus saving computational time and providing a range of alternatives to the decision maker while
avoiding arbitrary combinations. Further, the proposed framework considers multi-objective optimization
over the broader superstructure to identify supply chain configurations that optimize ecological and
economic performance while simultaneous achieving minimum threshold sustainability criteria. Design
opportunities and challenges for each scale of analysis are discussed in the following sections.
The first level of analysis involves field trials and laboratory scale experiments such as model
compound studies [74,75], effects of catalysts and reactor conditions on product streams [76], estimation
of fuel properties [77], reactor kinetic studies [78,79], pilot-scale biomass growth trials [80], and the
effect of varying fertilizer and management practice on biomass yield [81,82]. This research is often
focused on understanding the mechanism or principles underlying experimental observation, or determining
the technically feasibility of an emerging technology. Factorial designs are often implemented to study
the effect of each effect factor on the response variable (i.e., biofuel yield), as well as the effect of
interactions between factors on the response variable [83]. Further, data at the field/lab scale typically
has low uncertainty, and is often used for calibration and parameterization in process models.
4.2. Process Scale
Processes 2015, 3 645
The next tier of analysis involves the use of agricultural crop models as well as traditional process
design analysis. A variety of large-scale crop models have been developed to simulate bioenergy crop
production including herbaceous crops (e.g., EPIC, ALMANAC, MISCANMOD, MISCANFOR,
WIMOVAC, Agro-IBIS, Agro-BGC, APSIM, AUSCANE, LPJmL, CANEGRO), woody bioenergy
crops (e.g., 3PG, SECRETS), and crassulacean acid metabolism crops (e.g., EPI) [84]. These models
simulate biomass yield, nutrient cycling, water requirements, carbon flux, and other key parameters
under different crop management practices. Recent efforts have been made to integrate these models
with Geographic Information System (GIS) to create spatially explicit large-scale crop models [85].
Conversion of biomass to fuel can be modeled using conventional process simulators such as Aspen
Plus, ChemCAD, or SuperPro [86]. Inputs to the biorefinery generally include raw materials and utilities
such as biomass, steam, electricity, and cooling water. Similarly, final products typically include biofuel,
coproducts, waste, and emissions. Process simulators provide a scientifically rigorous method for
determining the utility requirements as well as material and energy flows for conversion of biomass to
renewable transportation fuel. Information at this scale of analysis is often used for developing
technoeconomic models [30,87], with the primary objective of maximizing material and energy
efficiency while concurrently minimizing operating costs. Life cycle considerations such as the
embodied impacts of material and energy inputs are not considered within the scope of analysis at this
scale, thus decision-making based solely on information at the process scale could result in unsustainable
design choices. For example, analysis based solely on the process scale could result in selection of high
quality resources (i.e., fossil fuels) for maximizing plant performance and economics; however, these
resources often have high upstream environmental or human health impacts.
The third level of analysis extends the analytic boundary to consider the material, energy, and
emissions flows throughout the entire supply chain. This holistic systems approach captures environmental
impacts that are outside the purview of the traditional process design boundary. Life Cycle Assessment
(LCA) is one of the most common approaches for evaluating the environmental impact of a product or
a process over its entire life cycle, and in recent years has emerged as the predominant method for
analyzing the environmental sustainability of emerging biofuel platforms [88–95]. LCA considers
impacts throughout all stages of the fuel life cycle—from raw material acquisition, to fuel conversion,
and final use. LCA allows for a comprehensive understanding of the environmental impacts that occur
at each stage of the supply chain, enabling the LCA practitioner to identify processes responsible for
highest environmental burden and thus target these areas for process improvement. LCA can be used to
quantify the anticipated impacts of a product or service prior to its widespread adoption, thus identifying
and avoiding potential environmental pollutants, wastes, and environmental damages before they
become embedded within the supply chain. Further, LCA can be used to compare the environmental
performance between two products with the same functionality and can inform environmentally
conscious decision-making. Garcia and You reviewed major challenges and opportunities in supply
chain design and optimization—identifying several key technical challenges including: (i) multiscale
challenges; (ii) multiobjective and sustainability challenges; and (iii) multi-player challenges [96].
Processes 2015, 3 646
LCA is a data intensive approach and has been extensively applied to study biofuel systems over the
past decade. Several different LCA modeling methods have been developed; the most widely used LCA
approach (i.e., Process-LCA) defines a finite boundary by selecting the most important processes in a
life cycle [97]. Data concerning the resource consumption and emissions for these processes are
developed and compiled to generate a life cycle inventory (LCI). The life cycle impact assessment
(LCIA) phase translates the energy, resource, and emissions flows identified in the LCI into their
potential consequences for human health and the environment, and consists of a two-step process of
impact classification and quantitative characterization. The classification step links each LCI flow with
its related impacts on resource use, human health, and the environment. The characterization step
calculates the magnitude of the associated impacts in terms of a reference unit for each category via
multiplying the related resource, material, or energy flows with their respective impact factors.
Translating the environmental impacts to a reference unit provides a common basis or measure for the
generated impact, so that different emissions and resources can be compared and aggregated
using a common unit. Data required for LCA can be obtained via commercial life cycle databases
(e.g., ecoinvent [98]), publicly available life cycle data (e.g., OpenLCA [99], USLCI [100],
GREET [101]), information from the open literature, or proprietary information.
Although widely used, process LCA suffers from many limitations including the use of an arbitrary
life cycle boundary, combining data in disparate units and at multiple spatial and temporal scales, dealing
with high dimensionality data involving varying degrees of uncertainty, and dealing with processes
having a range of emissions [11]. Furthermore, for a system that simultaneously produces multiple
products and coproducts these is no universally accepted method as to how to apportion the
environmental impacts amongst said products. This is particularly important for biofuel systems in which
non-fuel coproducts represent a significant fraction of total market value, mass, or energy flow as the
choice of allocation procedure can often yield divergent results concerning the sustainability of these
systems [102,103]. Additionally, biofuel LCAs often utilize differing functional units, system
boundaries, allocation schemes, impact assessment methods, and report different sustainability metrics.
Consequently, it is not unusual for LCA practitioners to obtain contradictory LCA results for the same
system; this discrepancy has led to several harmonization and meta-analysis studies in the biofuels
literature [104,105]. Data used in process LCA is at an intermediate scale since it is typically averaged
to represent manufacturing processes, thus making it of limited use for making environmentally
conscious engineering decisions about an individual process or equipment, which are at a finer scale, or
for evaluating the effect on the macro economy, which is at a coarser scale.
Input-output (IO) models, first developed by Nobel Prize winning economist Wassily Leontief,
provide a mathematical framework for quantifying the inter-industrial connections and economic flows
between different industrial sectors in the economy [106]. The traditional IO framework can be extended
to consider the environmental impacts, emissions, and resource use for industrial sectors in the economy;
and thus be utilized to perform LCA at the economy scale. This approach, known as Economic
Processes 2015, 3 647
Input-Output LCA (EIO-LCA) [107], does not suffer from the challenge of defining a finite life cycle
boundary as does Process LCA. Further, EIO-LCA uses a relatively complete network, but at a coarse
scale of resolution. Data at this scale often do not include the use phase of the life cycle. Recently, Bakshi
and colleagues have developed Ecologically-based Life Cycle Assessment (EcoLCA), an environmentally
extended input-output life cycle model capable of accounting for the consumption/role of ecosystem
goods and services in a life cycle framework [108,109]. The EcoLCA model extends the traditional I-O
framework to consider the direct and indirect environmental impacts that result from economic activities;
including ecological and natural resource consumption, emissions, land-use, and other environmental
impact categories [110–112]. EcoLCA quantifies ecological resource consumption using a hierarchy of
thermodynamic metrics including energy, industrial cumulative exergy consumption (ICEC), and
ecological cumulative exergy consumption (ECEC), as well as mass flow. However, while exergy-based
methods for thermodynamic aggregation of natural resource consumption may provide useful insights,
these methods have their own limitations and are debated in the literature [113–120]. Research on
combining the best advantages of Process LCA and EIO-LCA has also resulted in Hybrid LCA approaches,
which combine the details of Process LCA with the greater completeness of EIOLCA [121,122]. Hybrid
LCA attempts to balance computational tractability, completeness, and the use of detailed information.
LCA models may also differ in the approach employed to address the material and energy flows in
the system under investigation. The attributional LCA (ALCA) methodology, which has been utilized
for a vast majority of the LCA studies, attempts to quantify the flow of resources and emissions from a
product system and its subsystems. Emissions and their impact are attributed to the final product by one
of the several available methods (allocation or system expansion). However, researchers have argued
that it is not fully possible to draw conclusions on future changes by using only ALCA [123,124]. In
contrast, consequential LCA (CLCA) methodology, aims to explain how the physical flows to and from
the technosphere may change in response to a change in the life cycle of the product or service [125].
CLCAs attempt to consider a much broader system boundary. The most commonly employed form of a
CLCA considers the use of economic models that track monetary, material, and energy flows across
economic systems. This is generally accomplished using marginal data and is accounted for on the basis
of price elasticity of supply and demand [126–128].
The US Environmental Protection Agency (US EPA) has used a multi-market multi-region partial
equilibrium model to determine land use change emissions in biofuel lifecycles. Several dynamic
general/partial equilibrium models have been used to predict the implications of biofuel policy and
commercialization on land use, international/domestic trade, and GHG fluxes and commodity markets
within the agricultural sector including the Global Trade Analysis Project (GTAP), the Market
Allocation Model, the Forestry and Agricultural Sector Optimization Model (FASOM), and the Food
and Agricultural Policy Research Institute model, LEI-TAP model, and Modular Applied General
Equilibrium Tool, Center for Agricultural and Rural Development model, International Model for Policy
Analysis of Agricultural Commodities and Trade model, Common Agricultural Policy Regional Impact
Analysis model, the Worldwide Agribusiness Linkage Program and Commodity Simulation Model, and
the Modeling International Relationships in Applied General Equilibrium model [129–134]. However,
Processes 2015, 3 648
lack of model transparency and high complexity often limit the utility of these approaches. Furthermore,
these models often vary in regards to data requirements, scope, and model resolution. For example,
models such as FASOM have high resolution for the United States but lack information regarding
international trade; while models such as GTAP can provide estimates for domestic and international
land-use change but at a low level resolution. Synthesis and coupling these dynamic economic models
with biophysical land-use models such as the Integrated Model to Assess the Greenhouse Effect,
Conversion of Land Use and its Effects as well as energy models such as the PRIMES Energy System
Model can help support informed decision making [135,136]. However, it is important to note that that
economic systems exhibit structural inconstancy (i.e., change in individual behavior in response to
a policy change), and coupling economic and biophysical models will increase overall model
uncertainty [137]. Plevin et al. pair an economic-computable general equilibrium model with a CO2
emissions estimation model and conclude that due to parametric uncertainties, the results obtained
should be used for developing a range of possible results for comparison purposes rather than as
deterministic estimates of land use change emissions [138].
LCAs of emerging technologies are difficult to conduct due to lack of technology specific data,
dynamic and rapidly evolving systems, and isolation of environmental research from technical
developments [139]. Prospective LCAs involve estimating environmental impacts of possible future
scenarios and are affected by the choice of time horizon, complexity of the system, and extent of
stakeholder engagement. Studies have used approaches such as scenario analysis [140,141], participatory
methods involving expert elicitations and stakeholder opinions [139] and modeling of economic transactions
to understand market-mediated effects [142]. Many of the challenges associated with prospective LCA
can be overcome with inclusion of life cycle thinking at an early stage in research and development
(R&D) via a collaborative dialogue between industry experts, stakeholders, and LCA practitioners.
Analysis at the supply chain or life cycle scale is often focused on improving efficiency and reducing
environmental impacts across the life cycle, utilizing methods and metrics such as eco-efficiency, life
cycle GHG emissions, net energy analysis, water footprint, and others. However, these methods fail to
capture the impact of biofuel life cycles on ecological goods and services, i.e., the fundamental goods
and services provided by nature that sustain human life and are the fodder for all man-made capital and
industrial activity [143]. Consequently, decisions based on these methods could result in unsustainable
choices including heightened depletion and degradation of natural capital and ecosystems [111,144,145].
The final tier of analysis extends the analytic scope to consider the role of ecological goods and
services throughout the supply chain. As ecological goods and services play a fundamental role in
sustaining industrial activity, it is paramount to account for their role in evaluating the impact and
sustainability of emerging biofuel platforms. Examples of ecological goods and services include: timber,
food, water, energy resources, clean air, minerals and ores, purification of air and water resources, flood
and drought mitigation, pollination of crops and vegetation, maintenance of global biodiversity, as well
as climate and disease regulation [146–148]. Since it is computationally intractable to model the
complete supply chain by including each process as done at the life cycle level of analysis, the approach
leveraged at this scale of analysis is closely related to existing hybrid (i.e., tiered) LCA methods in which
Processes 2015, 3 649
a process level model is used to determine process level consumption of ecological goods and services
while economy wide-impacts are incorporated using EcoLCA [108,109,112,116,149].
Process level flows of ecological goods and services can be modeled using a host of computational
models. Detailed models such as Century, EPIC, APEX, and SWAT can be used to simulate the effects
of land management decisions on soil, water, nutrients and watersheds; however, these tools are data
intensive and suffer from high model complexity [150–152]. The Integrated Valuation of Ecosystems
Services and Tradeoffs (InVEST) modeling suite can be used to quantify and map a variety of regional
ecosystems goods services as well as biodiversity for both terrestrial and marine environments including
crop pollination, habitat quality, habitat risk assessment, managed timber production, managed fish
aquaculture, marine water quality, sediment retention, water purification, carbon sequestration, and
others [153]. Further, InVEST model(s) are open-source, generally simpler, more transparent, and user
friendly as compared to the aforementioned approaches. Synthesizing these computational models with
EcoLCA can provide a holistic understanding of the potential impacts and tradeoffs of biofuel production
on ecological resources and biodiversity. Although this tier of analysis is the most comprehensive it
often has high uncertainty due to (i) variability that is propagated and compounded at each preceding
level of analysis (i.e., from lab/field scale, to process scale, to supply chain); and (ii) high uncertainty in
the modeling approaches used to quantify ecological goods and services.
Bakshi and colleagues have developed and applied a hybrid EcoLCA framework to investigate
the sustainability of petroleum transportation fuels as well as select first and second-generation
biofuels [110,111]. More recently, this framework has been applied to study emerging microalgal biofuel
systems [145]. The results of these studies reveal that biofuels have high renewability but typically have
low thermodynamic return on investment relative to baseline petroleum fuels. The low energy return on
investment for biofuels is concerning as prior studies have suggested that a liquid technical fuel must
achieve minimum threshold energy return on investment (EROI) values to sustain society. Failure to
meet this minimum EROI criterion could result in widespread economic and social ramifications as more
useful work must be expended by society for fuel production and thus cannot sustain other economic
activities [154,155]. Recently, Bakshi and colleagues have developed a conceptual framework for
designing technological and ecological systems that encourages synergy between human activity and
nature [70,156]. The proposed techno-ecological synergy (TES) framework considers the demand of
ecological goods and services from technological systems at multiple spatial scales ranging from the
individual process scale, to supply chains and life cycles, as well as the supply of ecological good and
services from ecological systems ranging from regional, to watershed, to global. The TES framework
aims to reduce overconsumption of natural capital, and promotes technological systems to operate within
safe ecological boundaries at multiple analytic scales. Application of the TES framework can provide
unique insights into the sustainability of emerging biofuel supply chains.
4.5. Accounting for Multiple Objectives and Scales in Designing Sustainable Biofuel
Processes/Supply Chains
footprint, EROI, or economic potential) can lead to the unintended consequence of trading one environmental
problem for another. Many studies have focused on evaluating bioenergy potential encompassing several
criteria—economic performance, environmental and social impact and have developed several tools that
quantify these indicators [157]. For example, the SCORE Model developed by Krajnc and Domac uses
a mix of qualitative and quantitative indicators such as contribution to forest management, impact of
regional unemployment, CO2 emissions, and percentage of self-sufficiency in electricity production, to
analyze the sustainability of woody biomass production [158].
Studies often employ various optimization techniques to design an optimal biomass supply chain
based on multiple criteria [159,160]. Formulating the design problem as a mathematical optimization
task has been a common approach for analyzing technological systems. The design problem is generally
formulated as either a mixed integer linear or non-linear optimization problem [161,162]. Research
efforts have also resulted in coupling the design problem with LCA by quantifying the life cycle impacts
of process alternatives. This could be accomplished using either single objective or multi-objective
optimization (MOP) resulting in designs or options that represent the best compromise between the
selected design criteria [163,164] Several studies have utilized MOP for the strategic design and
implementation of biofuel systems. Zamboni et al. developed a spatially explicitly mixed integer linear
program (MILP) optimization model for bioethanol production systems that simultaneously considers
supply chain costs and life cycle GHG emissions [165,166]. De Meyer et al. developed a generalized
mathematical model, OPTIMASS, that optimizes over strategic and tactical decisions, and can be used
to investigate the potential effect of policy changes, emerging biofeedstocks, technological
adoption/evolution, and logistics on the environmental sustainability of biofuel supply chains [167].
Čuček et al. coupled MOP with a regional biomass supply chain model [168]. Mele et al. developed a
MILP optimization model to optimize economic and environmental objectives of the biofuel production
chain, and applied the model to the sugarcane industry in Argentina [169]. More recently, Yue et al.
developed a multi-objective life cycle optimization framework and applied it to study emerging
hydrocarbon biofuel production [170]. MOP can be used to identify design solutions that optimize
economic, environmental, and ecological dimensions of biofuel production; this set of optimal points
constitutes a Pareto frontier in the design-solution space. Moreover, solutions that do not lie on the Pareto
frontier are either infeasible or are sub-optimal. The Pareto frontier is particularly useful in MOP
problems since by restricting attention to the set of choices that are Pareto efficient, a designer can
evaluate tradeoffs within this set, rather than considering the full range of every parameter. Further, MOP
can be used to identify the optimal mix of useful coproducts satisfying the selected set of life cycle
environmental constraints. An alternative to mathematical programing is a heuristic approach that
employs algorithms based on artificial intelligence to obtain a satisfactory local optimal solution, when
a global optimal solution is not possible. Studies have employed various algorithms such as particle
swarm optimization, genetic algorithms or honeybee foraging algorithms to identify a range of optimal
solutions for various aspects of the biomass supply chain [171–173]. These approaches are expected to
lead to the identification of synergies between feedstock production, processing methods, and the final
mix of fuels and coproducts for the sustainable design of biorefineries [170,174,175].
Processes 2015, 3 651
Emerging hydrocarbon biofuel platforms have a high degree of uncertainty [176], due to lack of
commercialization, climatic variability, technological evolution, material and energy price volatility,
variability in supply and demand dynamics, dynamic effects in ecosystems, and changes in biofuel incentives
and legislation over time. Further, sources of modeling uncertainty generally include: (i) parameter
uncertainty; (ii) technological uncertainty; (iii) random error; (iv) systematic uncertainty; (v) methodological
uncertainty; (vi) parametric variability; (vii) structural uncertainty; (viii) algorithmic/interpolation
uncertainty; and (ix) policy uncertainty. These sources of uncertainty introduce variability at each stage
of the analysis, which are compounded and propagated with subsequent modeling scales and the use of
higher complexity models. Several commons approaches are often utilized to quantify uncertainty in
environmental sustainability analysis including stochastic modeling and one-at-a-time (OAT) sensitivity
analysis [177–179]. It is important to note that the primary utility of environmental sustainability analysis
is to identify potential environmental impacts or damages of emerging technologies at early stages of
R&D. However, recommendations at the design/conceptual phase typically have high uncertainty, which
is often only reduced after large investments and progress in R&D have been made. As such,
environmental sustainability analysis of emerging technologies inherently faces a tradeoff between
utility and uncertainty. Additionally, for biofuel production uncertainty in upstream processes can
translate into heightened risk downstream. For example, farmers are often reluctant to grow second
generation biofeedstocks due to their high fixed cost of production, long establishment period, and
uncertainty regarding the demand for these crops. However, the lack of large-scale agricultural
production of second generation biofeedstocks generates heightened risk for developing next generation
biorefineries, thus potentially limiting the demand for second-generation biofeedstocks.
The framework outlined in this study has multiple features that make it conceptually attractive;
however, the approach faces several challenges: (I) Interdisciplinary research requires effective
communication, transfer, and synthesis of domain specific knowledge and data across research fields.
This requires that collaborators become proficient in the colloquial terminology commonly used in said
research fields, so that domain specific modeling results and technical information can be exchanged
efficiently and information is not lost at the interface of research fields. (II) The long timeframe required
for laboratory/field trials as well as the development and implementation of modeling tools may limit
the effectiveness of this approach, as the “state of the art” may have changed or the technical system
evolved from its prior conception at the start of the analysis. However, this issue can be addressed via
several means. Streamlined models and methods can help reduce the computation time necessary for
model development and implementation. Further, open source databases and the use of “big data” may
help reduce the time required for data acquisition. Additionally, the modeling approach should be
iterative; models should be configured to use the most robust, accurate and up-to-date data, with
modeling tiers providing feedback-loops to inform the strategic design and development of biofuel
processes and supply chains. (III) Differing models/tools may have contrasting assumptions, conflicting
theoretical premises, and may report the results using disparate metrics. Additionally, the results may be
Processes 2015, 3 652
subjective and have high degree of uncertainty. For these reasons, results should not be considered
deterministic outcomes, but probabilistic measures to be used for comparative purposes [180].
In its inception, first generation biofuels were touted as a revolutionary new renewable and sustainable
fuel source. Technological exuberance and naivety lead to their large-scale commercialization without
proper consideration of the potential consequences for industry and the environment. Since then, a
multitude of studies have shown that the production and use first generation biofuels has resulted in
detrimental impacts on the ecosphere, environment, economy, and social welfare [64,181]. As biofuel
production is inherently interconnected with various critical sectors of the economy (i.e., agriculture,
transportation, etc.), it is crucial to understand the potential widespread impact of biofuels on economics,
environment, and human welfare before their widespread adoption and commercialization. Accordingly,
a new paradigm is needed for the design of sustainable biofuel processes supply chains, and is contingent
on collaboration across research domains and evaluation of potential impacts over multiple spatial and
temporal scales. This work discussed a novel modular multiscale and multiobjective framework for
analyzing emerging biofuel supply chains. While process-scale analysis is the most reductionist and is
commonly employed in engineering analysis and traditional process design, this narrowly focused
approach fails to capture broader environmental externalities; such shortsightedness could jeopardize
the sustainability of emerging biofuel systems. The conceptual multiscale and multiobjective framework
presented in this work addresses these limitations by optimizing economic and environmental objectives
over the field/lab scale, process scale, supply chain, and ecosystems scale. This broad-based
interdisciplinary approach is critical for guiding the sustainable development of the biofuels industry and
for mitigating and avoiding any unintended consequences. Further, the results of the bibliographic
analysis support the need for such a collaborative framework. Next generation biofuels represent a
promising opportunity for the chemical industry and sustainability engineers to work hand in hand, and
transform the traditional paradigm from “end of pipe” solutions to innovative, state of the art, and
sustainable design solutions.
Acknowledgments
This material is based upon work supported by the National Science Foundation Graduate
Research Fellowship under Grant No. (DGE-1247842). Any opinion, findings, and conclusions or
recommendations expressed in this material are those of the authors(s) and do not necessarily reflect the
views of the National Science Foundation. This work is supported by the National Institute of Food
and Agriculture, United States Department of Agriculture (USDA) (Agriculture and Food Research
Initiative Competitive Grant No. 2012-67009-19717). Any opinions, findings and conclusions or
recommendations expressed in this material are those of the authors and do not necessarily reflect the
views of USDA.
Author Contributions
GGZ and NV wrote the manuscript and conducted the bibliometric analysis. SSC performed the
network analysis and constructed the bibliometric network figure. VK coordinated the study, and
assisted/guided in the development and analysis of the network figure. VK and AEL reviewed the
manuscript. All authors read and approved the final manuscript.
Processes 2015, 3 653
Conflicts of Interest
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